Process and system for producing upgraded products from residues - Patents.com

Abstract

Embodiments of the present disclosure are directed to a process for producing an upgraded product from a residue, including upgrading of an atmospheric or vacuum residue, comprising separating the residue by passing it through a solvent deasphalting (SDA) unit, which includes an asphaltene separation unit that separates the residue into an asphaltene pitch and a stream comprising deasphalted oil (DAO) and resin, followed by a resin separation unit that separates the stream comprising DAO and resin into separate DAO and resin streams, treating the resin stream with supercritical water (SCW) to produce an upgraded resin stream, and hydrotreating a portion of the upgraded resin stream and the DAO stream to produce an upgraded product.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. patent application Ser. No. 17 / 160,699, filed Jan. 28, 2021, entitled “PROCESSES AND SYSTEMS FOR PRODUCING UPGRADED PRODUCT FROM RESIDUE,” the entire contents of which are incorporated herein by reference. [Technical field]

[0002] SUMMARY OF THE DISCLOSURE Embodiments of the present disclosure relate generally to processes and systems for producing upgraded products from residues. [Background technology]

[0003] Generally, solvent deasphalting (SDA) process is employed in oil refineries to extract valuable components from residual oil. In the conventional SDA process, residual oil is separated into deasphalted oil (DAO) and asphaltene pitch by using a hydrocarbon solvent. The typical solvent is a light paraffinic solvent (with carbon numbers ranging from 3 to 5). Asphaltenes have high polarity and large molecular weights, resulting in poor solubility in paraffinic solvents. Therefore, the solvent used in the SDA process can precipitate the asphaltene pitch, and the SDA process separates the DAO from the residual oil. The residual oil cannot be processed by catalytic hydrotreating due to the high metal content and inertness of large molecules, but the DAO separated from the residual oil has acceptable qualities for catalytic hydrotreating, such as low metal content. Therefore, the SDA process has been used in the industry for many years as one of the major upgrading processes for residual oil.

[0004] However, in the SDA process, a significant portion of the residual oil is rejected to become asphaltene pitch. To maintain a certain quality of DAO for subsequent hydroprocessing, the liquid yield of the DAO must traditionally be 80 mass% or less. Conversely, hydroprocessing of DAO with liquid yields greater than 80% must be carried out under harsh conditions, such as temperatures greater than 400°C and hydrogen pressures greater than 20 MPa, to obtain marketable fuel and chemical feedstocks. In most cases, refineries optimize the liquid yield of DAO to maximize the production of end products while minimizing the operating costs of hydroprocessing. Thus, in most conventional SDA processes, the DAO yield is limited by the following hydroprocessing unit.

[0005] However, in an alternative SDA process, the residual oil is separated into a stream of DAO, a resin considered to be the final fraction of the DAO, and an asphaltene pitch. The resin has a higher impurity content and a higher boiling range than the DAO, but can be hydrotreated. However, the resin alone cannot be hydrotreated without using harsh conditions. Summary of the Invention [Problem to be solved by the invention]

[0006] Thus, there is a continuing need for improved systems and processes for upgrading residues using mild hydrotreating conditions while minimizing the production of low-value asphaltene pitch. [Means for solving the problem]

[0007] Embodiments of the present disclosure fill this need by separating the resin stream from the residual oil and treating the resin stream with supercritical water (SCW) prior to hydrotreating. The SCW-treated resin can then be hydrotreated under mild hydrotreating conditions to increase the yield of marketable upgraded products while minimizing the formation of asphaltene pitch.

[0008] According to one or more embodiments of the present disclosure, a process for producing an upgraded product from a residue, including upgrading an atmospheric residue or a vacuum residue, may include separating the residue through an SDA unit, the SDA unit including an asphaltene separation unit that separates the residue into an asphaltene pitch and a stream comprising DAO and resin, and then a resin separation unit that separates the stream comprising DAO and resin into separate DAO and resin streams, treating the resin stream with SCW to produce an upgraded resin stream, and hydrotreating a portion of the upgraded resin stream and the DAO stream to produce the upgraded product.

[0009] According to one or more other aspects of the present disclosure, a system for producing an upgraded product from a residue, including upgrading of an atmospheric residue or a vacuum residue, may include an SDA unit operable to separate the residue, the SDA unit including an asphaltene separation unit that separates the residue into an asphaltene pitch and a stream comprising DAO and resin, and a resin separation unit that subsequently separates the stream comprising DAO and resin into separate DAO and resin streams; an SCW unit downstream of the SDA unit, the SCW unit operable to treat the resin stream with supercritical water to produce an upgraded resin stream; and a hydrotreating unit downstream of the SCW unit, the hydrotreating unit operable to hydrotreat a portion of the upgraded resin stream and the DAO stream to produce the upgraded product.

[0010] Additional features and advantages of the described embodiments will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description, or may be learned by practice of the described embodiments, including the following detailed description, as well as the drawings and claims.

[0011] The following detailed description of specific embodiments of the present disclosure can be best understood when read in conjunction with the following drawings, where like structure is indicated with like reference numerals and in which: [Brief description of the drawings]

[0012] [Figure 1] FIG. 1 is a schematic diagram of a system and process for producing an upgraded product from residue upgrading, according to one or more embodiments of the present disclosure. [Diagram 2] FIG. 1 is a schematic diagram of another system and process for producing an upgraded product from retentate upgrading, in accordance with one or more embodiments of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] For purposes of illustrating the simplified schematic diagrams and descriptions of Figures 1-2, numerous well-known valves, temperature sensors, pressure sensors, electronic controllers, pumps, etc. that may be employed by one skilled in the art of a particular chemical processing operation are not included. Furthermore, ancillary components often included in a chemical processing operation, such as, for example, air supplies, heat exchangers, surge tanks, compressors, or other related systems, are not shown. It will be understood that these components are within the spirit and scope of the presently disclosed embodiments. However, operative components such as those described in this disclosure may be added to the embodiments described in this disclosure.

[0014] Additionally, it should be noted that the arrows in the drawings refer to process flows. However, the arrows may equally refer to transfer lines that may serve to transfer process flows between two or more system components. Additionally, the arrows connecting the system components define the inlet or outlet of each given system component. The direction of the arrows generally corresponds to the main direction of material movement of the flows contained within the physical transfer lines indicated by the arrows. Additionally, the arrows not connecting two or more system components refer to product streams exiting the illustrated system or system inlet streams entering the illustrated system. The product streams may be further processed in an associated chemical processing system or commercialized as an end product. The system inlet streams may be streams transferred from an associated chemical processing system or may be raw raw material streams. Some arrows may represent recycle streams, which are output streams of the system components that are recycled back into the system. However, it should be understood that in some embodiments, any representative recycle stream may be replaced with a system inlet stream of the same material, and a portion of the recycle stream may exit the system as a system product.

[0015] Additionally, arrows in the drawings may generally indicate process steps that transfer streams from one system component to another. For example, an arrow pointing from one system component to another may represent the "passing" of a system component effluent to another, which may include the contents of a process stream "exiting" or "removing" from one system component and the "introduction" of its product stream contents to another system component.

[0016] Where two or more lines intersect in the schematic flow diagrams of Figures 1-2, it should be understood that two or more process streams are "mixed" or "combined." Mixing or combining may also include mixing by direct introduction of both streams into the same reactor, separation device, or other system component. For example, where two streams are depicted as being combined just prior to entering a separation unit or reactor, it should be understood that in some embodiments, the streams may be equivalently introduced separately into the separation unit or reactor and combined within the reactor.

[0017] Reference will now be made in more detail to various embodiments, some of which are illustrated in the accompanying drawings. Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts.

[0018] definition As used in this disclosure, a "reactor" refers to a vessel in which one or more chemical reactions can occur between one or more reactants, optionally in the presence of one or more catalysts. For example, a reactor can include a tank or tubular reactor configured to operate as a batch reactor, a continuous stirred tank reactor (CSTR), or a plug flow reactor. Examples of reactors include packed bed reactors, such as fixed bed reactors, and fluidized bed reactors. One or more "reaction zones" may be disposed within the reactor. As used in this disclosure, a "reaction zone" refers to the region within the reactor where a particular reaction occurs. For example, a packed bed reactor with multiple catalyst beds can have multiple reaction zones, with each reaction zone defined by the volume of each catalyst bed.

[0019] As used in this disclosure, a "separator" refers to any separation device or system of separation devices that at least partially separates one or more chemicals mixed in a process stream from one another. For example, a separator can selectively separate materials of different chemical species, phases, or sizes from one another to form one or more chemical fractions. Examples of separators include, but are not limited to, distillation columns, flash drums, knock-out drums, knock-out pots, centrifuges, cyclones, filters, traps, scrubbers, expansion devices, membranes, solvent extraction devices, and the like. It should be understood that the separation processes described in this disclosure may not be able to completely separate all of one chemical component from all of another chemical component. It should be understood that the separation processes described in this disclosure "at least partially" separate different chemical components from one another, and that even if not explicitly stated, separation may include only partial separation. As used in this disclosure, one or more chemical components can be "separated" from a process stream to form a new process stream. Generally, a process stream can enter a separator and be split or separated into two or more process streams of desired composition.

[0020] As used in this disclosure, "asphaltene" refers to a hydrocarbon composition that consists primarily of carbon, hydrocarbons, nitrogen, oxygen, and sulfur, with trace amounts of vanadium, nickel, iron, and other metals. Without wishing to be bound by theory, asphaltene refers to the portion of petroleum that is insoluble in paraffinic solvents (the soluble portion is called maltenes).

[0021] As used in this disclosure, "supercritical water" or "SCW" refers to water at pressures and temperatures above its critical pressure and temperature such that there are no distinct phases and materials can dissolve like a liquid while still exhibiting the diffusivity of a gas. At temperatures and pressures above the critical temperature and pressure of water, the boundary between the liquid and gas phases disappears and the fluid has the properties of both liquid and gaseous materials. SCWs can dissolve organic compounds like organic solvents and have excellent diffusivity like a gas. By adjusting the temperature and pressure, the properties of the SCW can be continually "tuned" to be more liquid or more gaseous. SCWs have a lower density and lower polarity compared to liquid subcritical water, greatly expanding the range of possible chemistry that can be performed in water.

[0022] As used in this disclosure, "catalyst" refers to any substance that increases the rate of a particular chemical reaction. The catalysts described in this disclosure can be utilized to promote a variety of reactions, including, but not limited to, cracking (including aromatic cracking), demetallization, desulfurization, and denitrogenation.

[0023] Further, it should be understood that a stream may be named based on the components of that stream, and that a component named for a stream may be the majority component of that stream (e.g., including 50%, 70%, 90%, 95%, 99%, 99.5%, or even 99.9% by weight of the stream's contents up to 100% by weight of the stream's contents). A component of a stream should also be understood to be disclosed as passing from one system component to another if a stream containing that component is disclosed as passing from one system component to another. For example, a disclosed "DAO stream" passing from a first system component to a second system component should be understood to equally disclose a "DAO" passing from the first system component to the second system component, and so forth.

[0024] System for upgrading residues to produce upgraded products SUMMARY OF THE DISCLOSURE Embodiments of the present disclosure are directed to a system for upgrading a residue, such as an atmospheric residue, a vacuum residue, or both, to produce an upgraded product, such as naphtha, gas oil, vacuum gas oil, or a combination thereof. Referring to Figures 1 and 2, a system 10 for upgrading a residue 101 is shown generally. The system 10 may be utilized in a process to produce an upgraded product 301 from the upgrading of the residue 101.

[0025] A residue 101 may be introduced into the system 10. Various compositions are contemplated for the residue 101. In one or more embodiments, the residue 101 may include an atmospheric residue, a vacuum residue, or both.

[0026] In some embodiments, the residue 101 may have an American Petroleum Institute (API) gravity value of 25 or less, or 22 or less. The residue 101 may have an API gravity of 1-25, 1-22, 10-25, 5-25, 8-22, or 16.

[0027] In some embodiments, the residue 101 may have a true boiling point (TBP) at which 10% of the fraction vaporizes at a temperature of 600 degrees Fahrenheit (°F) or greater, 650°F (343.3°C) or greater, or 900°F (482.2°C) or greater. TBP may be measured by ASTM D2892 or ASTM D5236.

[0028] The residue 101 may have an asphaltene content of 1% or more, or 2% or more by weight. In some embodiments, the residue 101 may have an asphaltene content of 2% to 50%, 2% to 30%, 2% to 20%, 2% to 10%, 5% to 50%, 5% to 30%, 5% to 20%, or 5% to 10% by weight. Asphaltene content can be measured by n-heptane insoluble fraction (ASTM D6560 or IP143).

[0029] The residue 101 may include heavy metals such as vanadium, nickel, iron, or combinations thereof. In some embodiments, the residue 101 may have a total metal content of 20 ppm by weight (ppmw) or more, or 30 ppmw or more. In some embodiments, the residue 101 may have a total metal content of 20 ppmw to 500 ppmw, 20 ppmw to 400 ppmw, 20 ppmw to 300 ppmw, 20 ppmw to 200 ppmw, 30 ppmw to 500 ppmw, 30 ppmw to 400 ppmw, 30 ppmw to 300 ppmw, or 30 ppmw to 200 ppmw.

[0030] SDA Unit - Asphaltene Separation Unit and Resin Separation Unit Continuing with reference to FIGS. 1-2, the residue 101 may be introduced into an SDA unit 100 and separated into an asphaltene pitch 112, a DAO stream 121, and a resin stream 122, as previously described.

[0031] The SDA unit 100 may include an asphaltene separation unit 110 capable of separating the residue 101 into an asphaltene pitch 112 and a stream 111 comprising DAO and resin (remaining residue). The asphaltene separation unit 110 may reduce the asphaltene content of the residue 101 from 30% by weight to 0.1% by weight or less, or even 0.01% by weight or less. The remaining residue 111 (stream comprising DAO and resin) may have less than 0.1% by weight or even less than 0.01% by weight of asphaltene compounds. The asphaltene pitch 112 may comprise at least 70%, at least 80%, at least 90%, or at least 95% of the asphaltene compounds from the residue 101.

[0032] Without being bound to any particular theory, asphaltenes can precipitate in crude oil production pipelines and cause processing problems because they can impede pipeline flow. Furthermore, asphaltenes can easily turn into coke when exposed to high temperatures, which can be undesirable and problematic. Asphaltenes are often used synonymously with pitch and bitumen; however, pitch and bitumen contain asphaltenes, but may also contain other fraction contaminants, such as maltenes, which are non-asphaltenic fractions.

[0033] Asphaltenes typically contain an aromatic core attached to aliphatic carbon side chains. Without being bound to a particular theory, the increased aromaticity of asphaltenes may lead to interactions with other aromatic compounds, including polycyclic compounds. Aromatic bonds exhibit greater bond energy than aliphatic carbon-carbon bonds and are therefore less susceptible to cracking. The use of supercritical water helps to suppress intermolecular reactions through a caging effect, but the aromatic moieties may be unreactive at reaction temperatures. Thus, the side chains present in asphaltenes may break away from the aromatic core, but the aromatic moieties remain intact. The aromatic moieties begin to stack together, forming multiple layers of aromatic sheets, which may convert to coke. As previously mentioned, coke is undesirable and may impede pipeline flow or create other processing problems.

[0034] With further reference to Figures 1-2, the asphaltene separation unit 110 may operate at temperatures from 10°C to 315°C, 10°C to 300°C, 10°C to 250°C, 10°C to 200°C, 30°C to 315°C, 30°C to 300°C, 30°C to 250°C, or 30°C to 200°C.

[0035] In some embodiments, the asphaltene separation unit 110 can operate at a pressure of 0.05 MPa to 10 MPa, 0.05 MPa to 8 MPa, 0.05 MPa to 5 MPa, 0.1 MPa to 10 MPa, 0.1 MPa to 8 MPa, 0.1 MPa to 5 MPa, 0.5 MPa to 10 MPa, 0.5 MPa to 8 MPa, 0.5 MPa to 5 MPa, 1 MPa to 10 MPa, 1 MPa to 8 MPa, or 1 MPa to 5 MPa.

[0036] The asphaltene separation unit 110 may include a solvent. The asphaltene pitch 112 may be separated from the residue 101 by contacting the solvent. A variety of solvents are contemplated for the asphaltene separation unit 110. In one or more embodiments, the solvent may be selected from propane, butanes, pentanes, or combinations thereof. In some embodiments, the volume ratio of the solvent to the residue 101 may be 2:1 to 20:1, 2:1 to 10:1, 3:1 to 20:1, or 3:1 to 10:1. The residence time of the residue 101 in the asphaltene separation unit 110 may be 10 minutes (min) to 60 minutes, 10 to 50 minutes, 20 to 60 minutes, or 20 to 50 minutes.

[0037] In some embodiments, the asphaltene pitch 112 may have a mass yield of 10% to 90%, 10% to 80%, 10% to 60%, 10% to 40%, 20% to 90%, 20% to 80%, 20% to 60%, 20% to 40%, 30% to 90%, 30% to 80%, 30% to 60%, or 30% to 40% of the residue 101.

[0038] In some embodiments, the asphaltene pitch 112 can have an API gravity of -30 to -5, -30 to -10, -30 to -5, -20 to -5, -20 to -10, or -20 to -5.

[0039] In some embodiments, the asphaltene pitch 112 may have a total metals content of 50 ppmw to 1,000 ppmw, 50 ppmw to 500 ppmw, 50 ppmw to 400 ppmw, 50 ppmw to 300 ppmw, 100 ppmw to 1,000 ppmw, 100 ppmw to 500 ppmw, 100 ppmw to 400 ppmw, 100 ppmw to 300 ppmw, 200 ppmw to 1,000 ppmw, 200 ppmw to 500 ppmw, 200 ppmw to 400 ppmw, or 200 ppmw to 300 ppmw.

[0040] As previously discussed, the DAO and resin containing stream 111 can be separated from the residue 101 in the asphaltene separation unit 11. In some embodiments, the DAO and resin containing stream 111 can have an API gravity of 2-23, 2-20, 2-15, 2-13, 5-23, 5-20, 5-15, 5-13, 8-23, 8-20, 8-15, 8-13, 10-23, 10-20, 10-15, or 10-13.

[0041] In some embodiments, the DAO and resin containing stream 111 may have an asphaltene content of 1% to 30%, 1% to 20%, 1% to 10%, 1% to 5%, 0.5% to 30%, 0.5% to 20%, 0.5% to 10%, 0.5% to 5%, 0.1% to 30%, 0.1% to 20%, 0.1% to 10%, 0.1% to 5%, or 0.1% to 1% of the asphaltene content of the feed 101.

[0042] In some embodiments, the stream 111 comprising the DAO and resin may have a total metal content of 1 ppm to 50 ppm by weight, 1 ppm to 30 ppm by weight, 1 ppm to 20 ppm by weight, 1 ppm to 10 ppm by weight, 1 ppm to 2 ppm by weight, 0.1 ppm to 50 ppm by weight, 0.1 ppm to 30 ppm by weight, 0.1 ppm to 20 ppm by weight, 0.1 ppm to 10 ppm by weight, or 0.1 ppm to 2 ppm by weight.

[0043] In some embodiments, the DAO and resin stream 111 may have a Conradson Carbon Residue (CCR) content of 1-20%, 1-10%, 1-5%, 0.1-20%, 0.1-10%, or 0.1-5% by weight. CCR may refer to a laboratory test value measured by ASTM D189 that indicates the tendency to form coke.

[0044] As previously mentioned, the SDA unit 100 may further include a resin separator 120 capable of separating the DAO and resin containing stream 111 into a DAO stream 121 and a resin stream 122. The resin separator 120 may be located downstream of the asphaltene separator 110. The resin separator 120 may be in fluid communication with the asphaltene separator 110 for passing the DAO and resin containing stream 111. The DAO and resin containing stream 111 may be passed directly from the asphaltene separator 110 to the resin separator 120.

[0045] In some embodiments, the resin separation apparatus 120 can operate at a temperature of 10°C to 315°C, 10°C to 300°C, 10°C to 250°C, 10°C to 200°C, 30°C to 315°C, 30°C to 300°C, 30°C to 250°C, or 30°C to 200°C.

[0046] In some embodiments, the resin separation apparatus 120 can operate at a pressure of 0.05 MPa to 10 MPa, 0.05 MPa to 8 MPa, 0.05 MPa to 5 MPa, 0.1 MPa to 10 MPa, 0.1 MPa to 8 MPa, 0.1 MPa to 5 MPa, 0.5 MPa to 10 MPa, 0.5 MPa to 8 MPa, 0.5 MPa to 5 MPa, 1 MPa to 10 MPa, 1 MPa to 8 MPa, or 1 MPa to 5 MPa.

[0047] The resin separation unit 120 may include a solvent. A variety of solvents are contemplated for the resin separation unit 120. In one or more embodiments, the solvent may be selected from solvents used in the asphaltene separation unit. In one or more embodiments, the solvent may be selected from propane, butanes, pentanes, or combinations thereof. In some embodiments, the volume ratio of solvent to DAO and resin containing stream 111 may be 2:1 to 20:1, 2:1 to 10:1, 3:1 to 20:1, or 3:1 to 10:1. The residence time of the DAO and resin containing stream 111 in the resin separation unit 120 may be 10 to 60 minutes, 10 to 50 minutes, 20 to 60 minutes, or 20 to 50 minutes.

[0048] As discussed above, resin separator 120 may be operable to separate DAO stream 121 and resin stream 122 from DAO and resin containing stream 111. In some embodiments, DAO stream 121 may have a mass yield of 10% to 50%, 10% to 45%, 10% to 40%, 20% to 50%, 20% to 45%, 20% to 40%, 30% to 50%, 30% to 45%, or 30% to 40% of the residue 101.

[0049] In some embodiments, the DAO stream 121 can have an API gravity of 10-30, 10-25, 15-30, or 15-25.

[0050] In some embodiments, the DAO stream 121 can have an asphaltene content of 7% or less, 6% or less, or 5% or less by weight. The DAO stream 121 can have an asphaltene content of 0.01% to 7%, 0.01% to 6%, 0.01% to 5%, 0.1% to 7%, 0.1% to 6%, or 0.1% to 5% by weight.

[0051] In some embodiments, the DAO stream 121 can have a total metals content of 25 ppmw or less, 20 ppmw or less, or 15 ppmw or less. The DAO stream 121 can have a total metals content of 0.1 ppmw to 25 ppmw, 0.1 ppmw to 20 ppmw, 0.1 ppmw to 15 ppmw, 0.1 ppmw to 10 ppmw, 1 ppmw to 25 ppmw, 1 ppmw to 20 ppmw, 1 ppmw to 15 ppmw, or 1 ppmw to 10 ppmw.

[0052] In some embodiments, the DAO stream 121 can have a CCR content of 15% by weight or less, 10% by weight or less, or 7% by weight or less. The DAO stream 121 can have a CCR content of 0.1% to 15% by weight, 0.1% to 10% by weight, 0.1% to 7% by weight, 1% to 15% by weight, 1% to 10% by weight, or 1% to 7% by weight.

[0053] In some embodiments, the DAO stream 121 may have a TBP where 30% of the fraction vaporizes at a temperature of 1200° F. or less, 1100° F. or less, or 1050° F. or less. TBP may be measured by ASTM D2892 or ASTM D5236.

[0054] 1 and 2, a resin stream 122 may be obtained separated from the resin separator 120. The resin stream 122 may be denser or heavier than the DAO stream 121, but lighter than the asphaltene pitch 112. The resin stream 122 may contain more aromatic hydrocarbons with highly aliphatically substituted side chains, and may also contain metals such as nickel and vanadium. The resin stream 112 may include materials from which the asphaltene pitch 112 and the DAO stream 121 were removed.

[0055] In some embodiments, the resin stream 122 may have a mass yield of 10% to 40%, 10% to 35%, 10% to 30%, 20% to 40%, 20% to 35%, or 20% to 30% of the residue 101.

[0056] In some embodiments, the resin stream 122 can have an API gravity of 1-20, 1-15, 1-10, 5-20, 5-15, or 5-10.

[0057] In some embodiments, the resin stream 122 may have an asphaltene content of 1% to 10%, 1.5% to 10%, 2% to 10%, 1% to 8%, 1.5% to 8%, or 2% to 8% of the asphaltene content of the residue 101. In an embodiment, the asphaltene content of the resin stream 122 may be higher than the asphaltene content of the DAO stream 121. In an embodiment, the asphaltene content of the resin stream 122 may be lower than the asphaltene content of the asphaltene pitch 112. In some embodiments, the resin stream 122 may have an asphaltene content of 0.1% to 5%, 0.1% to 3%, 0.1% to 2%, 0.3% to 5%, 0.3% to 3%, or 0.3% to 2% by weight.

[0058] In some embodiments, the resin stream 122 may have a total metals content of 10% to 70%, 10% to 60%, 20% to 70%, 20% to 60%, 30% to 70%, or 30% to 60% of the total metals content of the residue 101. In one embodiment, the total metals content of the resin stream 122 may be higher than the total metals content of the DAO stream 121. In one embodiment, the total metals content of the resin stream 122 may be lower than the total metals content of the asphaltene pitch 112. In some embodiments, the resin stream 122 may have a total metals content of 0.1 ppmw to 25 ppmw, 0.1 ppmw to 20 ppmw, 1 ppmw to 25 ppmw, or 1 ppmw to 20 ppmw.

[0059] In some embodiments, the resin stream 122 may have a CCR content of 10% to 120%, 10% to 100%, 30% to 120%, 30% to 100%, 50% to 120%, 50% to 100%, 60% to 120%, or 60% to 100% of the CCR content of the residue 101. In an embodiment, the CCR content of the resin stream 122 may be higher than the CCR content of the DAO stream 121. In an embodiment, the CCR content of the resin stream 122 may be lower than the CCR content of the asphaltene pitch 112. In some embodiments, the resin stream 122 may have a CCR content of 0.1% to 20%, 0.1% to 10%, 0.1% to 8%, 0.1% to 5%, 1% to 7%, or 1% to 5% by weight.

[0060] SCW Unit 1 and 2, the system 10 may further include an SCW unit 200. The SCW unit 200 may be located downstream of the SDA unit 100. The SCW unit 200 may treat the resin stream 122 with SCW to generate an upgraded resin stream 201. The SCW unit 200 may be in fluid communication with the resin separator 120 to pass the resin stream 122. The resin stream 122 may be passed directly from the resin separator 120 to the SCW unit 200.

[0061] The SCW may be introduced into the SCW unit 200. Prior to introducing the SCW, a water stream may be pressurized and heated to produce the SCW. In some embodiments, the water stream may include demineralized water, distilled water, boiler feed water (BFW), and deionized water.

[0062] The SCW may have a pressure of 22.1 MPa or greater, which is about the critical pressure of water. In some embodiments, the SCW may have a pressure of 22.1 megapascals (MPa) to 32 MPa, 22.9 MPa to 31.1 MPa, 23 MPa to 30 MPa, 24 MPa to 28 MPa, 25 MPa to 29 MPa, 26 MPa to 28 MPa, 25 MPa to 30 MPa, 26 MPa to 29 MPa, or 23 MPa to 28 MPa.

[0063] The SCW may have a temperature of about the critical temperature of water, or greater, 374° C. In some embodiments, the SCW may have a temperature of 374° C. to 600° C., 400° C. to 550° C., 400° C. to 500° C., 400° C. to 450° C., or 450° C. to 500° C.

[0064] As discussed above, the resin stream 122 may be introduced into the SCW unit 200. In some embodiments, the resin stream 122 may be combined with the SCW prior to introducing the resin stream 122 into the SCW unit 200. In one or more embodiments, the weight ratio of the SCW to the resin stream 122 may be between 20:1 and 0.1:1, between 20:1 and 1:1, between 20:1 and 5:1, between 10:1 and 0.1:1, between 10:1 and 1:1, or between 10:1 and 5:1.

[0065] In some embodiments, the resin stream 122 may be preheated to a temperature of 500° C. or less, 400° C. or less, or 300° C. or less prior to introduction of the resin stream 122 into the SCW unit 200. The resin stream 122 may be preheated to a temperature of 200° C. to 500° C., 80° C. to 500° C., 100° C. to 500° C., 120° C. to 500° C., 50° C. to 400° C., 80° C. to 400° C., 100° C. to 400° C., 120° C. to 400° C., 50° C. to 300° C., 80° C. to 300° C., 100° C. to 300° C., or 120° C. to 300° C.

[0066] The SCW unit 200 may include a reactor. The resin stream 122 may be treated with the SCW in the reactor to produce a reactor effluent. In some embodiments, the reactor may include an isothermal reactor or a non-isothermal reactor. In embodiments, the reactor may include a tubular vertical reactor, a tubular horizontal reactor, a vessel reactor, a tank reactor having an internal mixing device such as an agitator, or any combination of these reactors.

[0067] In one embodiment, the SCW unit 200 can be operated in the presence of a catalyst. In another embodiment, the SCW unit 200 can be operated in the absence of a catalyst and an externally supplied hydrogen gas (H2). H2 gas can be produced by the steam reforming reaction and the water gas shift reaction, and can then be utilized in the upgrading reaction. Without being bound to a particular theory, H2 gas can be stable and may require the use of a catalyst to "activate" H2 for utilization in the hydrogenation reaction. However, the hydrogen gas produced from the steam reforming reaction and the water gas shift reaction of this embodiment can produce "active" H2 gas as an intermediate, which can be utilized in the upgrading reaction without the need for the use of an external catalyst.

[0068] In some embodiments, the reactor can be operated at a temperature above the critical temperature of water and a pressure above the critical pressure of water. In some embodiments, the reactor can be operated at a temperature of 380°C to 550°C, 400°C to 550°C, 420°C to 550°C, 380°C to 500°C, 400°C to 500°C, 420°C to 500°C, 380°C to 460°C, 400°C to 460°C, or 420°C to 460°C.

[0069] In some embodiments, the reactor can operate at a pressure of 23 MPa to 40 MPa, 25 MPa to 40 MPa, 23 MPa to 35 MPa, 25 MPa to 35 MPa, 23 MPa to 30 MPa, 25 MPa to 30 MPa, 23 MPa to 28 MPa, or 25 MPa to 28 MPa.

[0070] In some embodiments, the internal fluids, including the SCW and resin flow 122 in the reactor, may have a Reynolds number of 3000 or greater, a Reynolds number of 4000 or greater, or a Reynolds number of 5000 or greater to maintain turbulence and avoid hydrocarbon precipitation in the reactor.

[0071] In some embodiments, the residence time of the internal fluid within the reactor can be between 0.1 minutes to 60 minutes, 0.5 minutes to 60 minutes, 1 minute to 60 minutes, 0.1 minutes to 30 minutes, 0.5 minutes to 30 minutes, 1 minute to 30 minutes, 0.1 minutes to 10 minutes, 0.5 minutes to 10 minutes, or 1 minute to 10 minutes.

[0072] In some embodiments, the temperature of the fluid at the end of the reactor may be higher than the temperature of the fluid at the inlet of the reactor. The "end" and "inlet" positions of the reactor may refer to 90 to 100% of the total length of the reactor and 0 to 5% of the total length of the reactor, respectively.

[0073] The SCW unit 200 may further include a heat exchanger downstream of the reactor. The reactor effluent may be introduced into the heat exchanger to produce a heat exchanged stream. The reactor effluent may be cooled in the heat exchanger. In one embodiment, the heat exchanger may include a double pipe heat exchanger.

[0074] The SCW unit 200 may further include a pressure drop device downstream of the heat exchanger. The heat exchanged stream may be introduced into the pressure drop device to produce a reduced pressure stream. The pressure drop device may include a back pressure regulator, a pressure control valve, or both.

[0075] The SCW unit 200 may further include a separation unit downstream of the pressure drop device. The reduced pressure stream may be introduced into the separation unit to be separated into an upgraded resin stream 201 and a residue product 202. In an embodiment, the separation unit may be selected from a vacuum distillation unit, a flash column, a solvent separator, or a combination thereof. When the separation unit includes a flash column and a vacuum distillation unit, the flash column may separate the reduced pressure stream into a distillate and an atmospheric residue fraction. The residue fraction from the flash column may be introduced into the vacuum distillation unit to be separated into an upgraded resin stream 201 and a residue product 202.

[0076] In some embodiments, the upgraded resin stream 201 may have a mass yield of 30% to 80%, 30% to 70%, 40% to 80%, 40% to 70%, 50% to 80%, 50% to 70%, 60% to 80%, or 60% to 70% of the resin stream 122.

[0077] In some embodiments, the upgraded resin stream 201 may have an API gravity of 10-30, 10-25, 10-20, 15-30, 15-25, or 15-20.

[0078] The upgraded resin stream 201 may have qualities, such as asphaltene content, total metals content, and CCR content, comparable to the qualities of the DAO stream 121. In some embodiments, the upgraded resin stream 201 may have an asphaltene content of 10% by weight or less, 8% by weight or less, or 7% by weight or less. The upgraded resin stream 201 may have an asphaltene content of 0.01% to 10% by weight, 0.01% to 8% by weight, 0.01% to 7% by weight, 0.1% to 10% by weight, 0.1% to 8% by weight, or 0.1% to 7% by weight.

[0079] In some embodiments, the upgraded resin stream 201 may have a total metals content of 30 ppmw or less, 25 ppmw or less, 15 ppmw or less, 12 ppmw or less, or 6 ppmw or less. The upgraded resin stream 201 may have a total metals content of 0.01 ppmw to 30 ppmw, 0.01 ppmw to 25 ppmw, 0.01 ppmw to 15 ppmw, 0.01 ppmw to 12 ppmw, 0.01 ppmw to 6 ppmw, 0.1 ppmw to 30 ppmw, 0.1 ppmw to 25 ppmw, 0.1 ppmw to 15 ppmw, 0.1 ppmw to 12 ppmw, or 0.1 ppmw to 6 ppmw.

[0080] In some embodiments, the upgraded resin stream 201 may have a CCR content of 25% by weight or less, 20% by weight or less, or 15% by weight or less. The upgraded resin stream 201 may have a CCR content of 0.01% to 25% by weight, 0.01% to 20% by weight, 0.01% to 15% by weight, 0.1% to 25% by weight, 0.1% to 20% by weight, or 0.1% to 15% by weight.

[0081] In some embodiments, the upgraded resin stream 201 may have a TBP where 30% of the fraction vaporizes at a temperature below 1200° F., below 1100° F., or below 1050° F. TBP may be measured by ASTM D2892 or ASTM D5236.

[0082] 1 and 2, the upgraded resin stream 201 may be discharged from the SCW unit 200. The upgraded resin stream 201 may be mixed with the DAO stream 121. Referring to FIG. 2, a portion of the upgraded resin streams 203, 204 may be recycled. In some embodiments, a portion of the upgraded resin stream 203 may be recycled to the asphaltene separation unit 110. A portion of the upgraded resin stream 203 may be combined with the retentate 101 upstream of the asphaltene separation unit 110. In some embodiments, if the quality of the upgraded resin is worse than the quality of the DAO stream 121, such as the total metal content or CCR content, the upgraded resin stream 203 may be recycled to the asphaltene separation unit 110. In some embodiments, a portion of the upgraded resin stream 204 may be recycled by combining the upgraded resin stream 204 with the remaining retentate 111 upstream of the resin separation unit 120. In some embodiments, if the quality of the upgraded resin stream 203 exceeds the quality of the DAO stream 121 , the upgraded resin stream 203 may be recycled to the resin separator 120 .

[0083] 1 and 2, the residual product 202 may be separated from the resin separator 200. The residual product 202 may be discharged from the system 10.

[0084] In some embodiments, the residual product 202 may have a mass yield of 10% to 60%, 10% to 50%, 10% to 40%, 20% to 60%, 20% to 50%, 20% to 40%, 30% to 60%, 30% to 50%, or 30% to 40% of the resin stream 122.

[0085] In some embodiments, the bottoms product 202 can have an API gravity of 1-15, 1-10, 5-15, or 5-10.

[0086] In some embodiments, the residual product 202 may have an asphaltene content of 5% by weight or less, 4% by weight or less, or 3% by weight or less. The residual product 202 may have an asphaltene content of 0.1% to 5% by weight, 0.1% to 4% by weight, 0.1% to 3% by weight, 1% to 5% by weight, 1% to 4% by weight, or 1% to 3% by weight.

[0087] In some embodiments, the residue product 202 may have a total metals content of 35 ppmw or less, 30 ppmw or less, or 25 ppmw or less. The residue product 202 may have a total metals content of 10 ppmw to 35 ppmw, 10 ppmw to 30 ppmw, 10 ppmw to 25 ppmw, 20 ppmw to 35 ppmw, 20 ppmw to 30 ppmw, or 20 ppmw to 25 ppmw.

[0088] In some embodiments, the residual product 202 may have a CCR content of 35% by weight or less, 30% by weight or less, or 25% by weight or less. The residual product 302 may have a CCR content of 0.1% to 35% by weight, 0.1% to 30% by weight, 0.1% to 25% by weight, 1% to 35% by weight, 1% to 30% by weight, or 1% to 25% by weight.

[0089] Hydrotreating Unit As mentioned above, the system 10 may further include a hydrotreating unit 300 downstream of the SCW unit 200. The hydrotreating unit 300 may be operable to hydrotreat a portion of the upgraded resin stream 201 and the DAO stream 121 to produce an upgraded product 301 including naphtha, gas oil, vacuum gas oil, or combinations thereof.

[0090] The hydrotreating unit 300 may be in fluid communication with the SCW unit 200 to pass the upgraded resin stream 201. The upgraded resin stream 201 may be passed directly from the SCW unit 200 to the hydrotreating unit 300. In some embodiments, the upgraded resin stream 201 may be combined with the DAO stream 121 to produce a mixture prior to introducing the upgraded resin stream 201 into the hydrotreating unit 300.

[0091] In some embodiments, the mixture of the upgraded resin stream 201 and the DAO stream 121 can have a moisture content of less than 0.3%, less than 0.2%, or about 0.1% by weight. In some embodiments, each of the upgraded resin stream 201 and the DAO stream 121 can have a moisture content of less than 0.3%, less than 0.2%, or 0.1% by weight.

[0092] In some embodiments, the mixture of upgraded resin stream 201 and DAO stream 121 may have an API gravity of 10-30, 10-25, 15-30, or 15-25.

[0093] In some embodiments, the mixture of upgraded resin stream 201 and DAO stream 121 may have an asphaltene content of 0.1% to 10% by weight, 0.01% to 8% by weight, 0.01% to 5% by weight, 0.1% to 10% by weight, 0.1% to 8% by weight, or 0.1% to 5% by weight.

[0094] In some embodiments, the mixture of upgraded resin stream 201 and DAO stream 121 may have a total metals content of 0.01 ppmw to 30 ppmw, 0.01 ppmw to 25 ppmw, 0.01 ppmw to 15 ppmw, 0.01 ppmw to 12 ppmw, 0.01 ppmw to 6 ppmw, 0.1 ppmw to 30 ppmw, 0.1 ppmw to 25 ppmw, 0.1 ppmw to 15 ppmw, 0.1 ppmw to 12 ppmw, or 0.1 ppmw to 6 ppmw.

[0095] In some embodiments, the mixture of upgraded resin stream 201 and DAO stream 121 may have a CCR content of 0.01% to 25% by weight, 0.01% to 20% by weight, 0.01% to 15% by weight, 0.1% to 25% by weight, 0.1% to 20% by weight, or 0.1% to 15% by weight.

[0096] Hydroprocessing unit 300 may include a single reactor or multiple reactors, hi some embodiments, hydroprocessing unit 300 may include two to three reactors in series.

[0097] The hydrotreating unit 300 can be operated under mild hydrotreating conditions. Under mild hydrotreating conditions, the hydrotreating unit 300 can help remove impurities and increase the hydrogen content of the feed hydrocarbon. The hydrotreating unit 300 can remove 90% or more, or 95% or more, by weight, of the total sulfur, nitrogen, and metal content based on the mixture of the DAO stream 121 and the upgraded resin stream 201. The hydrotreating unit 300 can improve the crackability of the upgraded resin stream 201 and the DAO stream 121. Thus, it is an excellent feedstock for the fluid catalytic cracker and the steam cracker. Various reactions can be carried out in the hydrotreating unit 300, such as hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrocracking, hydroisomerization, or a combination thereof.

[0098] In some embodiments, the mild hydrotreating conditions are 0.1 hours -15 hours from -1 , or 0.1 hours -1 3 hours from -1 The reactor may include a liquid hourly space velocity (LHSV) throughout the reactor. The reactor may include a catalyst bed including a catalyst. The catalyst may include a heterogeneous catalyst, a homogeneous catalyst, or both. In an embodiment, the catalyst may include NiMo, CoMo, NiCoMo, or combinations thereof supported on alumina, zeolite, amorphous silica-alumina, or combinations thereof.

[0099] In some embodiments, mild hydrotreating conditions may include a catalyst bed temperature of 300°C to 450°C, 320°C to 450°C, 340°C to 450°C, 300°C to 430°C, 320°C to 430°C, 340°C to 430°C.

[0100] In some embodiments, hydroprocessing unit 300 may require an external supply of molecular hydrogen. In one or more embodiments, mild hydroprocessing conditions may include a hydrogen partial pressure of 1 MPa to 15 MPa, 2 MPa to 15 MPa, 3 MPa to 15 MPa, or 3.5 MPa to 15 MPa.

[0101] In one or more embodiments, the weight ratio of hydrogen to the mixture of upgraded resin stream 201 and DAO stream 121 is 200 Nm 3 / kl (kiloliter) to 1500Nm 3 / kl, or 200Nm 3 / kl to 1200Nm 3 / kl.

[0102] As previously mentioned, the hydrotreating unit 300 can produce an upgraded product 301. Under mild conditions, the hydrotreating unit 300 can convert 25% or more by weight of the mixture of the DAO stream 121 and the upgraded resin stream 201 to the upgraded product 301. The upgraded product 301 can include naphtha, gas oil, vacuum gas oil, or a combination thereof. The upgraded product 301 can have less than 1% metals in the mixture of the DAO stream 121 and the upgraded resin stream 201. The upgraded product 301 can have less than 5% CCR in the mixture of the DAO stream 121 and the upgraded resin stream 201. The demetallization and de-CCR performance of the hydrotreating unit 300 can be in the range of 95% to 99%. The desulfurization and denitrogenation performance of the hydrotreating unit 300 can be in the range of 95% to 99%.

[0103] Process for upgrading residue to produce upgraded product Further embodiments of the present disclosure are directed to a process utilizing the above-referenced system 10. As previously mentioned, the residue 101 can be upgraded by the SDA unit 100, including the asphaltene separation unit 110 and the resin separation unit 120, the SCW unit 200, and the hydrotreating unit 300. The following description will focus on the differences between the residue upgrading system 10 and the residue upgrading process, and therefore the undescribed parts will be taken from the residue upgrading system 10 described above.

[0104] 1 and 2, the process may include separating a residue 101 through an SDA unit 100 including an asphaltene separation unit 110 and a resin separation unit 120. The residue 101 may be introduced into the asphaltene separation unit 110 and separated into an asphaltene pitch 112 and a stream 111 containing DAO and resin. The stream 111 containing DAO and resin may be introduced into the resin separation unit 120 and separated into a DAO stream 121 and a resin stream 122. The resin stream 122 may be introduced into the SCW unit 200 and treated with SCW to produce an upgraded resin stream 201. A residue product 202 may be separated from the resin stream 122. The upgraded resin stream 201 may be introduced into a hydrotreating unit 300. In some embodiments, the upgraded resin stream 201 may be mixed with the DAO stream 121 before introducing the upgraded resin stream 201 into the hydrotreating unit 300. A portion of the upgraded resin stream 201 and the DAO stream 121 may be hydrotreated to produce an upgraded product 301.

[0105] 2, the process may further include recycling a portion of the upgraded resin stream 203 to the asphaltene separation unit 110. In some embodiments, the upgraded resin stream 203 may be combined with the retentate 101 prior to introducing the upgraded resin stream 203 into the asphaltene separation unit 110.

[0106] 2, the process may further include recycling a portion of the upgraded resin stream 204 to the resin separator 120. In some embodiments, the upgraded resin stream 204 may be combined with the remaining retentate 111 prior to introducing the upgraded resin stream 204 into the resin separator 120. EXAMPLES

[0107] The following examples illustrate one or more additional features of the present disclosure, and it should be understood that these examples are not intended to limit in any way the scope of the disclosure or the appended claims.

[0108] Example 1 An experimental simulation of an embodiment having the system configuration and characteristics shown in Figure 1 was carried out using the process simulator ASPEN-HYSYS. Table 2 contains data on the vacuum residue fed to the asphaltene separation unit.

[0109] [Table 2]

[0110] The vacuum residue was fed to an asphaltene separator. n-butane was used as a solvent in the asphaltene separator. The asphaltene separator was operated at a solvent / oil ratio of 8 / 1 vol / vol, 50° C., and 2.9 MPa to produce a stream containing DAO and resin with a mass yield of about 60%, reduce the sulfur and metal content, and separate an asphaltene pitch with a mass yield of 40% based on the vacuum residue. Table 3 includes the stream characteristics and composition of the asphaltene pitch. The stream containing DAO and resin was then fed to a resin separator. The resin separator uses n-butane as a solvent. Most of the solvent in the asphaltene separator moved with stream 111 and was used for the resin separator. The solvent contained in the asphaltene pitch was removed by steam. The resin separator was operated at 40° C. and 2.0 MPa to produce a DAO stream with a mass yield of 35% and a resin stream with a mass yield of 25% based on the vacuum residue. Tables 4 and 5 below contain the flow properties and compositions for the DAO and resin streams, respectively.

[0111] [Table 3]

[0112] [Table 4]

[0113] [Table 5]

[0114] The resin and water streams were fed through separate plunger type pumps to an SCW unit equipped with a gas-fired heater, a mixing device, a mixture heater, a reactor, a heat exchanger, a pressure drop device, a flash column, and a vacuum distillation unit. The water stream was pumped at a flow rate of 1027.5 metric tons per day (MTD) to 27 MPa and then preheated to 520°C in the gas-fired heater. The resin stream was pumped at a flow rate of 822 MTD to 27 MPa and then preheated to 230°C in the gas-fired heater. The water to resin feed weight ratio was 1.25:1. The preheated water stream and the preheated resin stream were mixed in the mixing device and then injected into the mixture preheater, which consisted of a 3.35 inch inside diameter (ID) and 25 meter long austenitic stainless steel helical tube. The temperature of the mixed stream at the outlet of the mixture preheater was 452°C. The preheated mixed stream was then fed into a reactor to produce a reactor effluent. The reactor consisted of seven austenitic stainless steel pipes in series, each with an ID of 20.7 inches and a length of 10 meters. The reactor was surrounded by brick-type insulation to keep the temperature drop within 5°C. The residence time of the preheated mixed stream in the reactor was approximately 150 seconds.

[0115] The reactor effluent was then fed to a heat exchanger (double-tube heat exchanger) and cooled to produce a heat-exchanged stream having a temperature of about 250° C. The heat-exchanged stream was then fed to a pressure reduction device (two-stage pressure control valve) to produce a reduced pressure stream having a pressure of 0.9 MPa. The reduced pressure stream was fed to a flash column and separated into a distillate and an atmospheric residue fraction. The atmospheric residue fraction was fed to a vacuum distillation unit after removing water in an oil-water separator and separated into a residue product and an upgraded resin stream. Tables 6 and 7 below contain the stream properties and compositions for the residue product and upgraded resin stream, respectively.

[0116] [Table 6]

[0117] [Table 7]

[0118] The liquid yield of the upgraded resin stream in the SCW unit was about 97.1 wt% based on the resin stream. 2.9 wt% of the resin stream was lost to gas and water (dissolved in water). The upgraded resin stream was mixed with the DAO stream and then introduced into the hydrotreating unit. Table 8 below includes the stream characteristics and composition for the mixture of the upgraded resin stream and the DAO stream.

[0119] [Table 8]

[0120] The mixture of upgraded resin stream and DAO stream was introduced into the hydrotreater unit and fractionated into four fractions: naphtha, gas oil, vacuum gas oil (VGO), and vacuum residue (VR). The hydrotreater unit was operated under mild conditions (380°C, 11 MPa, LHSV 0.75 / hr, H2 / oil=800 nm3 / m3). Table 9 contains the stream characteristics and compositions for the four fractions.

[0121] [Table 9]

[0122] Comparative Example 2 Experimental simulations of the configuration and characteristics of an embodiment of a system without a resin separator and with an asphaltene separator were performed using the process simulator ASPEN-HYSYS. The vacuum residue listed in Table 2 was fed to the asphaltene separator. The asphaltene separator was operated under the same conditions as in Example 1, and based on the vacuum residue, the vacuum residue was separated into an asphaltene pitch with a mass yield of 65% and a DAO stream with a mass yield of 35%. Tables 10 and 11 below contain the stream characteristics and compositions for the asphaltene pitch and DAO streams, respectively.

[0123] [Table 10]

[0124] [Table 11]

[0125] Comparison between Example 1 and Comparative Example 2 Comparing the system and process of Example 1 with the system and process of Comparative Example 2, the system and process of Example 1 utilizing an SDA unit including an asphaltene separator and a resin separator together with an SCW unit allows for more efficient residue upgrading. The feed to the hydrotreating unit (DAO stream in Table 11) has similar characteristics to the mixture stream in Table 8. However, in Example 1, 42% more mass flow feed (upgraded resin stream and DAO stream in Example 1 vs. DAO stream in Comparative Example 2) was available to the hydrotreating unit under mild conditions. Example 1 shows the advantage of SCW processing of resins, with higher production of feed to the hydrotreating unit and less waste to asphaltene pitch. Example 1 can feed 55.3% (11,061.5 BPD / 20,000 BPD) of vacuum residue to the hydrotreating unit. In contrast, in Comparative Example 2, 39.1% (7,812.6 BPD / 20,000 BPD) can be fed to the hydrotreating unit. To achieve the same throughput without SCW treatment of the resin fraction, SDA would need to produce more DAO; however, this DAO would contain more impurities. These impurities could significantly reduce the life of the hydrotreating catalyst, for example, by at least half.

[0126] A first aspect of the disclosure is directed to a process for producing an upgraded product from a residue, including upgrading of an atmospheric or vacuum residue, the process including separating the residue through an SDA unit, the SDA unit including an asphaltene separation unit that separates the residue into an asphaltene pitch and a stream comprising DAO and resin, followed by a resin separation unit that separates the stream comprising DAO and resin into separate DAO and resin streams, treating the resin stream with SCW to produce an upgraded resin stream, and hydrotreating a portion of the upgraded resin stream and the DAO stream to produce the upgraded product.

[0127] A second embodiment of the present disclosure may include the first embodiment, further including the step of mixing the upgraded resin stream with DAO prior to the hydrotreating step.

[0128] A third embodiment of the present disclosure further includes recycling a portion of the upgraded resin stream to the asphaltene separation unit, and may include the first embodiment or the second embodiment, where the upgraded resin stream is combined with the residue prior to the separation step.

[0129] A fourth aspect of the present disclosure may include any of the first to third aspects, further comprising the step of recirculating a portion of the upgraded resin stream by combining the upgraded resin stream with the remaining residue prior to the step of separating the remaining residue.

[0130] A fifth embodiment of the present disclosure may include any of the first to fourth embodiments, wherein the residue has an API gravity of 22 or less.

[0131] A sixth aspect of the present disclosure may include any of the first through fifth aspects, wherein the residue has an asphaltene content of 2 wt.% or greater.

[0132] A seventh aspect of the present disclosure may include any of the first to sixth aspects, wherein the residue has a total metals content of 20 ppmw or greater.

[0133] An eighth embodiment of the present disclosure may include any of the first through seventh embodiments, wherein the DAO has an asphaltene content of 7 wt.% or less.

[0134] A ninth aspect of the present disclosure may include any of the first to eighth aspects, wherein the DAO has a total metal content of 25 ppmw or less.

[0135] A tenth aspect of the present disclosure may include any of the first to ninth aspects, wherein the DAO has a CCR content of 15% by weight or less.

[0136] An eleventh aspect of the present disclosure may include any of the first to tenth aspects, wherein the resin stream has an asphaltene content of 1% to 10% of the asphaltene content of the retentate.

[0137] A twelfth aspect of the present disclosure may include any of the first to eleventh aspects, wherein the resin stream has a total metal content of 10% to 70% of the total metal content of the residue.

[0138] A thirteenth aspect of the present disclosure may include any of the first to twelfth aspects, wherein the resin stream has a CCR content of 10% to 120% of the CCR content of the retentate.

[0139] A fourteenth aspect of the present disclosure may include any of the first to thirteenth aspects, wherein the weight ratio of SCW to resin flow is from 10:1 to 0.1:1.

[0140] A fifteenth aspect of the present disclosure may include any of the first to fourteenth aspects, wherein the treating step is carried out at a temperature of 380°C to 500°C.

[0141] A sixteenth aspect of the present disclosure may include any of the first to fifteenth aspects, wherein hydrotreating the upgraded resin stream removes at least a portion of one or more of metals, nitrogen, or sulfur content from the upgraded resin stream.

[0142] A seventeenth aspect of the present disclosure may include any of the first to sixteenth aspects, wherein the upgraded products include naphtha, gas oil, vacuum gas oil, or a combination thereof.

[0143] An eighteenth aspect of the present disclosure is directed to a system for producing an upgraded product from a residue, including upgrading of an atmospheric or vacuum residue, the system including an SDA unit operable to separate the residue, the SDA unit including an asphaltene separation unit that separates the residue into an asphaltene pitch and a stream comprising DAO and resin, and a resin separation unit that subsequently separates the stream comprising DAO and resin into separate DAO and resin streams; an SCW unit downstream of the SDA unit operable to treat the resin stream with supercritical water to produce an upgraded resin stream; and a hydrotreating unit downstream of the SCW unit operable to hydrotreat a portion of the upgraded resin stream and the DAO stream to produce an upgraded product.

[0144] A nineteenth embodiment of the present disclosure may include the eighteenth embodiment, wherein a portion of the upgraded resin stream is recycled to the asphaltene separation unit, and the upgraded resin stream is combined with the retentate upstream of the asphaltene separation unit.

[0145] A twentieth aspect of the present disclosure may include the eighteenth or nineteenth aspect, wherein a portion of the upgraded resin stream is recirculated by combining the upgraded resin stream with the remaining residue upstream of the resin separation device.

[0146] It is noted that in one or more of the following claims, the term "wherein, where, in which" is utilized as a transitional phrase. For purposes of defining the present technology, this term is introduced in the claims as an open-ended transitional phrase used to introduce a description of a set of properties of a structure, and should be interpreted in the same manner as the more commonly used open-ended preamble term "comprising." For purposes of defining the present technology, the transitional phrase "consisting of" may be introduced in the claims as a closed preamble term limiting the scope of the claim to the recited components or steps and naturally occurring impurities. For purposes of defining the present technology, the transitional phrase "consisting essentially of" may be introduced in the claims to limit the scope of one or more claims to the recited elements, components, materials, or method steps, as well as any unrecited elements, components, materials, or method steps that do not materially affect the novel properties of the claimed subject matter. The transitional phrases "consisting of" and "consisting essentially of" may be interpreted as a subset of open-ended transitional phrases such as "comprising," "containing," and so the use of an open-ended phrase introducing a description of a series of elements, components, materials, or steps should be interpreted as also disclosing the description of the series of elements, components, materials, or steps using the closed terms "consisting of" and "consisting essentially of." For example, a description of a composition "comprising" components A, B, and C should also be interpreted as disclosing compositions "consisting of" components A, B, and C, as well as compositions "consisting essentially of" components A, B, and C. Quantitative values ​​expressed in this application may be deemed to include open-ended embodiments consistent with the transitional phrases "comprising" and "containing," as well as closed or partially closed embodiments consistent with the transitional phrases "consisting of" and "consisting essentially of."

[0147] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. The verb "comprise" and its conjugations should be construed as referring to elements, components, or steps in a non-exclusive manner. A referenced element, component, or step can be present in, utilized, or used in conjunction with other elements, components, or steps not expressly referenced.

[0148] Furthermore, when an amount, concentration, or other value or parameter is given as a range, a preferred range, or a list of a preferred upper value and a preferred lower value, this should be understood as specifically disclosing all ranges formed from any pairing of the upper limit or preferred value of the range with the lower limit or preferred value of the range, regardless of whether the range is disclosed individually. When a numerical range is described herein, unless otherwise stated, the range is intended to include its endpoints, as well as all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values ​​described when defining the range. When a component is indicated as being present in a range starting from 0, such a component is an optional component (i.e., it may or may not be present). When present, the optional component may be at least 0.1% by weight of the composition or copolymer.

[0149] Where materials, methods, or machines are described herein using the terms "known to those skilled in the art," "conventional," or words or phrases of similar meaning, this term is intended to mean that the description covers materials, methods, and machines that are conventional at the time of the filing of this application.

[0150] It should be understood that any two quantitative values ​​assigned to a property can constitute a range for that property, and all combinations of ranges formed from all listed quantitative values ​​for a given property are contemplated in the present disclosure. The subject matter of the present disclosure has been described in detail with reference to specific embodiments. It should be understood that a detailed description of an element or feature of one or more embodiments does not necessarily imply that element or feature is essential to that particular embodiment or any other embodiment. Moreover, it should be apparent to those skilled in the art that various modifications and changes can be made to the described embodiments without departing from the spirit and scope of the claimed subject matter. Preferred embodiments of the present invention will be described below in detail. EMBODIMENT 1 1. A process for producing an upgraded product from a residue comprising upgrading an atmospheric or vacuum residue, comprising: separating said residue by passing it through a solvent deasphalting (SDA) unit, said SDA unit including an asphaltene separation unit which separates said residue into an asphaltene pitch and a stream comprising deasphalted oil (DAO) and resin, and a resin separation unit which subsequently separates said DAO and resin stream into separate DAO and resin streams; treating the resin stream with supercritical water (SCW) to produce an upgraded resin stream; and hydrotreating a portion of said upgraded resin stream and said DAO stream to produce said upgraded product. A method comprising: EMBODIMENT 2 2. The method of embodiment 1, further comprising the step of mixing the upgraded resin stream with the DAO prior to the hydrotreating step. EMBODIMENT 3 3. The method of claim 1 or 2, further comprising recycling a portion of the upgraded resin stream to the asphaltene separation unit, wherein the upgraded resin stream is combined with a residue prior to the separation step. EMBODIMENT 4 4. The method of any one of claims 1 to 3, further comprising the step of recirculating a portion of the upgraded resin stream by combining the upgraded resin stream with a stream comprising the DAO and resin prior to the step of separating the remaining residue. EMBODIMENT 5 5. The method of any one of the preceding claims, wherein the retentate has an API gravity of 22 or less. EMBODIMENT 6 6. The method of any one of the preceding claims, wherein the residue has an asphaltene content of 2 mass percent (wt%) or greater, a total metals content of 20 parts per million by mass (ppmw) or greater, or both. EMBODIMENT 7 7. The method of any one of the preceding claims, wherein the DAO has an asphaltene content of 7 wt% or less, a total metals content of 25 ppmw or less, a CCR content of 15 wt% or less, or a combination thereof. EMBODIMENT 8 8. The method of any one of the preceding claims, wherein the resin stream has an asphaltene content of 1% to 10% of the asphaltene content of the retentate, a total metal content of 10% to 70% of the total metal content of the retentate, a CCR content of 10% to 120% of the CCR content of the retentate, or a combination thereof. EMBODIMENT 9 9. The method of any one of the preceding claims, wherein the weight ratio of the SCW to the resin stream is from 10:1 to 0.1:1. EMBODIMENT 10 10. The method of any one of the preceding claims, wherein the treating step is carried out at a temperature of 380 degrees Celsius (°C) to 500°C. EMBODIMENT 11 11. The method of any one of the preceding claims, wherein the hydrotreating of the upgraded resin stream removes at least a portion of one or more of metal, nitrogen, or sulfur content from the upgraded resin stream. EMBODIMENT 12 12. The method of any one of the preceding claims, wherein the upgraded products comprise naphtha, gas oil, vacuum gas oil, or a combination thereof. EMBODIMENT 13 1. A system for producing an upgraded product from a residue, including upgrading of atmospheric or vacuum residue, comprising: a solvent deasphalting (SDA) unit operable to separate the residue, the SDA unit comprising an asphaltene separation unit that separates the residue into an asphaltene pitch and a stream comprising deasphalted oil (DAO) and resin, and a resin separation unit that subsequently separates the stream comprising DAO and resin into separate DAO and resin streams; a supercritical water (SCW) unit downstream of the SDA unit, the SCW unit operable to treat the resin stream with supercritical water to produce an upgraded resin stream; and a hydrotreating unit downstream of the SCW unit, the hydrotreating unit operable to hydrotreat the upgraded resin stream and a portion of the DAO stream to produce the upgraded product; Including, the system. EMBODIMENT 14 14. The system of embodiment 13, wherein a portion of the upgraded resin stream is recycled to the asphaltene separation unit, and the upgraded resin stream is combined with the retentate upstream of the asphaltene separation unit. EMBODIMENT 15 15. The system of claim 13 or 14, wherein a portion of the upgraded resin stream is recirculated by combining the upgraded resin stream with a stream containing the DAO and resin upstream of the resin separator. [Explanation of symbols]

[0151] 10. System 100 Solvent Deasphalting (SDA) Unit 101 Residue 110 Asphaltene Separation Unit 111 Remaining Residue (Stream containing DAO and Resin) 112 Asphaltene Pitch 120 Resin separation equipment 121 Deasphalted Oil (DAO) Flow 122 Resin flow 200 Supercritical Water (SCW) Unit 201 Upgraded Resin Flow 202 Residual products 203 Upgraded Resin Flow 204 Upgraded Resin Flow 300 Hydrotreating Unit 301 Upgraded Creations

Claims

1. 1. A process for producing an upgraded product from a residue comprising upgrading an atmospheric or vacuum residue, comprising: separating said residue through a solvent deasphalting (SDA) unit comprising an asphaltene separation unit which separates said residue into an asphaltene pitch and a stream comprising deasphalted oil (DAO) and resin, and a resin separation unit which subsequently separates said stream comprising DAO and resin into separate DAO and resin streams; treating the resin stream with supercritical water (SCW) to produce an upgraded resin stream; and hydrotreating a portion of said upgraded resin stream and said DAO stream to produce said upgraded product. A method comprising:

2. The method of claim 1, further comprising the step of mixing a portion of the upgraded resin stream with the DAO prior to hydrotreating the portion of the upgraded resin stream with the DAO stream.

3. 2. The method of claim 1, further comprising recycling a portion of the upgraded resin stream to the asphaltene separation unit, wherein the upgraded resin stream is combined with the retentate prior to passing the retentate through the SDA unit for separation.

4. 2. The method of claim 1, further comprising the step of recirculating a portion of the upgraded resin stream by combining the upgraded resin stream with a stream comprising the DAO and the resin prior to separating the streams comprising the DAO and the resin in the resin separator.

5. 2. The method of claim 1, wherein the residue has an American Petroleum Institute (API) gravity value of 22 or less.

6. 10. The method of claim 1, wherein the residue has an asphaltene content of 2 mass percent (wt%) or greater, a total metals content of 20 parts per million by weight (ppmw) or greater, or both.

7. 2. The method of claim 1, wherein the DAO has an asphaltene content of 7 wt% or less, a total metals content of 25 ppmw or less, a CCR content of 15 wt% or less, or a combination thereof.

8. 2. The method of claim 1, wherein the resin stream has an asphaltene content of from 1% to 10% of the asphaltene content of the retentate, a total metals content of from 10% to 70% of the total metals content of the retentate, a CCR content of from 10% to 120% of the CCR content of the retentate, or a combination thereof.

9. The method of claim 1, wherein the weight ratio of the SCW to the resin stream is from 10:1 to 0.1:

1.

10. The method of claim 1, wherein the process of treating the resin stream with supercritical water (SCW) to produce an upgraded resin stream is performed at a temperature of 380 degrees Celsius (°C) to 500°C.

11. The method of claim 1, wherein at least a portion of one or more of metal, nitrogen, or sulfur content is removed from the upgraded resin stream by hydrotreating a portion of the upgraded resin stream and the DAO stream.

12. 12. The method of any one of claims 1 to 11, wherein the upgraded products comprise naphtha, gas oil, vacuum gas oil, or combinations thereof.

13. 1. A system for producing an upgraded product from a residue, including upgrading of atmospheric or vacuum residue, comprising: a solvent deasphalting (SDA) unit operable to separate the residue, the SDA unit comprising: an asphaltene separation unit that separates the residue into an asphaltene pitch and a stream comprising deasphalted oil (DAO) and resin; and a resin separation unit that subsequently separates the stream comprising DAO and resin into separate DAO and resin streams; a supercritical water (SCW) unit downstream of the SDA unit, the SCW unit operable to treat the resin stream with supercritical water to produce an upgraded resin stream; and a hydrotreating unit downstream of the SCW unit and operable to hydrotreat the upgraded resin stream and a portion of the DAO stream to produce the upgraded product. Including, the system.

14. 14. The system of claim 13, wherein a portion of the upgraded resin stream is recycled to the asphaltene separation unit, and the upgraded resin stream is combined with the retentate upstream of the asphaltene separation unit.

15. 15. The system of claim 13 or 14, wherein a portion of the upgraded resin stream is recirculated by combining the upgraded resin stream with a stream containing the DAO and the resin upstream of the resin separator.

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