WO2024012991A1 - Aquaprocessing of crude and heavy hydrocarbon feedstocks - Google Patents

Aquaprocessing of crude and heavy hydrocarbon feedstocks Download PDF

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Publication number
WO2024012991A1
WO2024012991A1 PCT/EP2023/068754 EP2023068754W WO2024012991A1 WO 2024012991 A1 WO2024012991 A1 WO 2024012991A1 EP 2023068754 W EP2023068754 W EP 2023068754W WO 2024012991 A1 WO2024012991 A1 WO 2024012991A1
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Prior art keywords
stream
aquaprocessing
unit
fed
catalyst
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PCT/EP2023/068754
Other languages
French (fr)
Inventor
Ravichander Narayanaswamy
Prashil Prakash Lakhete
Alexander Stanislaus
Mathew John
Kankan Bhaumik
Abdulrahman Shahid SARANG
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Sabic Global Technologies B.V.
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Publication of WO2024012991A1 publication Critical patent/WO2024012991A1/en

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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/34Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
    • C10G9/36Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/12Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G69/00Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/04Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G69/00Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/06Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of thermal cracking in the absence of hydrogen
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G7/00Distillation of hydrocarbon oils
    • C10G7/06Vacuum distillation
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/201Impurities
    • C10G2300/205Metal content
    • C10G2300/206Asphaltenes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04Diesel oil

Definitions

  • the invention generally concerns systems and methods for producing diesel and low sulfur fuel oil or lube oil products from a hydrocarbon feedstock while also producing high value chemical products.
  • a system can include an aquaprocessing unit coupled to a crude distillation unit (CDU) and/or a vacuum distillation unit (VDU) where vacuum residue (VR) from the VDU is fed to the aquaprocessing unit for processing under conditions to yield produce diesel, fuel oil and/or pitch.
  • CDU crude distillation unit
  • VDU vacuum distillation unit
  • VR vacuum residue
  • VR vacuum residue
  • VR vacuum residue
  • VR vacuum residue
  • Pyoil may additionally be fed to the aquaprocessing unit, where it is aquaprocessed along with the VR to yield desirable products such as diesel and fuel oil.
  • the diesel and/or fuel oil is hydrotreated to remove sulfur to a desired level to meet commercial needs, such as to meet specifications for European Diesel or very low sulfur fuel oil.
  • Diesel fuel is an important fuel for the automotive and trucking industries.
  • Fuel oil is an important heating fuel for commercial and residential use. Both diesel fuel and fuel oil are produced from crude oil, which may contain sulfur. Sulfur promotes fuel oxidation, which causes emissions that are undesirable as they are environmental pollutants. In order to meet emission standards, diesel and fuel oil should be low in sulfur content to reduce pollution and to meet current standards. Typically, sulfur is removed by hydrotreating.
  • diesel and heating oil have been prepared by subjecting various heavier crude oil cuts, such as vacuum residue, to catalytic hydrocracking processes. These hydrocracking processes are energy intensive and do not always provide sufficient yields of product. As demand for diesel and fuel oil products grows, and more efficient systems and processes for preparing diesel and fuel oil products are desired.
  • the discovery can include a system that provides an aquaprocessing unit that is fluidly connected with a VDU to receive vacuum residue and process it under conditions suitable to produce diesel and/or fuel oil.
  • the aquaprocessing unit may also have an inlet for receiving pyoil for processing along with, or instead of, the VR.
  • This set-up can reduce costs associated with the use of the currently-used crackers and can also reduce the amount of energy needed to produce diesel and fuel oil.
  • Aquaprocessing is the hydrocracking of hydrocarbons in the presence of (a) one or more catalysts and (b) a solvent to keep asphaltenes dissolved, at a temperature in the range of 280 to 550 °C and a pressure in the range of 40 to 200 barg.
  • the aquaprocessing conditions can include a hydrogen to hydrocarbon ratio from 200 to 2000 NL/L of liquid feed and the aquaprocessing can be carried out with or without added steam.
  • One process relates to producing low sulfur diesel.
  • the process comprises the steps of flowing a hydrocarbon feed into an aquaprocessing unit having an aquaprocessing catalyst disposed therein; contacting the hydrocarbon feed with the first catalyst at a temperature in the range of from 275 to 400 °C to produce an aquaprocessing effluent having a boiling point ranging from 35 to 650°C; separating the aquaprocessing effluent to form a first stream including a hydrocarbon fraction having a boiling point below 305°C and a second stream including a hydrocarbon fraction having a boiling point above 305°C, wherein the second stream includes the diesel; and hydrotreating the second stream to remove sulfur to produce a hydrotreated second stream including the low sulfur diesel having containing 0 ppm to 50 ppm sulfur.
  • An aspect of the invention is related to a process for producing very low sulfur fuel oil, the method including the steps of flowing a hydrocarbon feed into an aquaprocessing having an aquaprocessing catalyst disposed therein; contacting the hydrocarbon feed with the first catalyst at a temperature in the range of from 275 to 400 °C to produce an aquaprocessing effluent; separating the aquaprocessing effluent to form a first stream including a hydrocarbon fraction having a boiling point below 350°C and a second stream including a hydrocarbon fraction having a boiling point above 350°C, wherein the second stream includes fuel oil having a boiling point of above 350 to 600°C; hydrotreating the second stream to remove sulfur to produce a hydrotreated second stream including the very low sulfur fuel oil having containing 0 to 50 ppm sulfur.
  • An aspect of the present invention relates to a process for steam cracking a feed produced by an aquaprocessing process.
  • This process includes the steps of flowing a hydrocarbon feed into an aquaprocessing having an aquaprocessing catalyst disposed therein; contacting the hydrocarbon feed with the first catalyst at a temperature in the range of from 275 to 400 °C to produce an aquaprocessing effluent having a boiling point in the range of 35°C to 400 °C; and feeding at least a first fraction of the aquaprocessing effluent to a steam cracker and steam cracking the first fraction to produce olefins.
  • An aspect of the present invention relates to a process for processing a hydrocarbon feed, wherein the process includes the steps of flowing a hydrocarbon feed into an aquaprocessing unit having an aquaprocessing catalyst disposed therein, wherein the hydrocarbon feed is a heavy feed has a boiling point greater than 275 to 900°C, preferably 275 to 400°C, or preferably 500 to 900°C; contacting the hydrocarbon feed with the first catalyst at a temperature in the range of from 275 to 400°C to produce an aquaprocessing effluent having a boiling point ranging 35 to 400°C; separating the aquaprocessing effluent to form a first lights stream including a hydrocarbon fraction having a boiling point of from 25 to 300°C, a first heavy stream including a hydrocarbon fraction having a boiling point above 300°C, and a gaseous stream; separating the first lights stream into a second lights stream having a boiling point ranging from 70 to 140°C and a remaining lights fraction; feeding the second light stream to a cata
  • C# hydrocarbons wherein “#” is a positive integer, is meant to describe all hydrocarbons having # carbon atoms.
  • C#+ hydrocarbons is meant to describe all hydrocarbon molecules having # or more carbon atoms.
  • C9+ hydrocarbons is meant to describe a mixture of hydrocarbons having 9 or more carbon atoms.
  • Aquaprocessing is the hydrocracking of hydrocarbons in the presence of (a) one or more aquaprocessing catalysts and (b) a solvent to keep asphaltenes dissolved, at a temperature in the range of 280 to 550 °C and a pressure in the range of 40 to 200 barg.
  • the aquaprocessing conditions can include a hydrogen to hydrocarbon ratio from 200 to 2000 NL/L of liquid feed and the aquaprocessing can be carried out with or without added steam.
  • Hydrocarbons are generally defined as molecules formed primarily by carbon and hydrogen atoms. Hydrocarbons may also include other elements such as, but not limited to, halogens, metallic elements, nitrogen, oxygen, and/or sulfur. Hydrocarbon fluids may include, entrain, or be entrained in non-hydrocarbon fluids such as hydrogen, nitrogen, carbon monoxide, carbon dioxide, hydrogen sulfide, water, and/or ammonia. [0016] The terms “about” or “approximately” are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment, the terms are defined to be within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.
  • wt.% refers to a weight percentage of a component, a volume percentage of a component, or molar percentage of a component, respectively, based on the total weight, the total volume of material, or total moles, that includes the component.
  • 10 grams of component in 100 grams of the material is 10 wt.% of component.
  • the systems and processes of the present invention can “comprise,” “consist essentially of,” or “consist of’ particular ingredients, components, compositions, etc. disclosed throughout the specification.
  • a basic and novel characteristic of the systems and methods of the present invention are their abilities to produce olefin products (e.g., ethylene) in a cost and energy efficient manner by having an ethane steam cracker unit capable of receiving ethane from a mixed feed steam cracker unit and feeding the C2+ products produced by the ethane steam cracker unit to the mixed feed steam cracker unit.
  • FIG. 1 illustrates an embodiment of a system to produce diesel and/or fuel oil products from a hydrocarbon feed provided to an aquaprocessing unit.
  • FIG. 2 illustrates an embodiment of a system to produce diesel and/or fuel oil products from a hydrocarbon feed provided to an aquaprocessing unit and other processes operative with the system to yield additional hydrocarbon products.
  • the mixed hydrocarbon feed can be fed to a mixed hydrocarbon steam cracking unit to produce petroleum products and ethane.
  • the ethane can be provided to an independent ethane cracking unit to produce ethylene and/or a C2+ hydrocarbons stream, which can be recycled to the mixed hydrocarbon steam cracking unit.
  • An advantage of this set-up is that the mixed hydrocarbon steam cracking unit can be operated at optimal conditions for C2+ cracking while the ethane steam cracking unit can be operated at optimal conditions to crack ethane.
  • System 100 for producing diesel and/or fuel oil products is described.
  • System 100 can include a vacuum distillation unit 102, an aquaprocessing unit 104, and a pygas hydrotreating (DPHG) unit 106.
  • a hydrocarbon feed 108 enters vacuum distillation unit 102 and is separated into various heavy and light fractions, with the heaviest fraction being vacuum residue which is fed to aquaprocessing unit 104.
  • the hydrocarbon feed will typically be crude oil, which may first be processed in a crude oil distillation unit (CDU).
  • CDU crude oil distillation unit
  • Crude oil can be the petroleum extracted from geologic formations in its unrefined form.
  • the term crude oil can also include petroleum that has been subjected to water-oil separations and/or gas-oil separation and/or desalting and/or stabilization.
  • Non-limiting examples of crude oil include Arabian Heavy, Arabian Light, other Gulf crudes, Brent, North Sea crudes, North and West African crudes, Indonesian, Chinese crudes, West Texas crude, and mixtures thereof, but also shale oil, tar sands, gas condensates and bio-based oils.
  • the crude oil used as feed to the process of the present invention preferably is conventional petroleum having an API gravity of more than 20° API as measured by the ASTM D287 standard.
  • the crude oil used in the process of the present invention is a light crude oil having an API gravity of more than 30° API.
  • the crude oil used in the process of the present invention can include Arabian Light Crude Oil.
  • Arabian Light Crude Oil typically has an API gravity of between 32- 36° API and a sulfur content of between 1.5-4.5 wt. %.
  • the vacuum residue may be subjected to a solvent deasphalting step to remove asphaltenes prior to being fed into the aquaprocessing unit.
  • hydrocarbons may be included in the feed 108, including plastics, oligomers from plastic pyrolysis, synthetic crude oil or hydrocarbons from plastics pyrolysis or any combination of these can be co-processed with crude oil feeds in the aquaprocessing unit 104.
  • the vacuum residue and/or other hydrocarbon feed can be aquaprocessed under conditions sufficient to yield either or both diesel 112 and/or fuel oil 114.
  • the conditions are sufficient to produce diesel.
  • the conditions are suitable to produce fuel oil.
  • Vacuum residue 110 can exit vacuum distillation unit 102 and enter aquaprocessing unit 104.
  • the vacuum residue, and optionally pyoil 118 is subjected to aquaprocessing in the presence of an aquaprocessing catalyst at a temperature of 275 °C to 400 °C (e.g., 300 °C, 325 °C, 350 °C, 375 °C, 400 °C, or any value or range there between) to yield an aquaprocessing effluent.
  • an aquaprocessing catalyst at a temperature of 275 °C to 400 °C (e.g., 300 °C, 325 °C, 350 °C, 375 °C, 400 °C, or any value or range there between) to yield an aquaprocessing effluent.
  • the vacuum residue is not completely cracked so as to yield more diesel and/ or fuel oil products.
  • System 200 can include a vacuum distillation unit 202, an aquaprocessing unit 204, and an DPHG unit 206.
  • a hydrocarbon feed 208 enters vacuum distillation unit 202 and is separated into various heavy and light fractions, including a VDU lights fraction 209, a VDU naphtha stream 211, with the heaviest fraction being vacuum residue 210 which is fed to aquaprocessing unit 204.
  • the hydrocarbon feed will typically be crude oil, which may first be processed in a crude oil distillation unit (CDU).
  • CDU crude oil distillation unit
  • the vacuum residue may be subjected to a solvent deasphalting step to remove asphaltenes prior to being fed into the aquaprocessing unit, or in the aquaprocessing unit.
  • hydrocarbons may be included in the feed 208, including plastics, oligomers from plastic pyrolysis, synthetic crude oil or hydrocarbons from plastics pyrolysis or any combination of these can be co-processed with crude oil feeds in the aquaprocessing unit 204.
  • the vacuum residue and/or other hydrocarbon feed can be aquaprocessed under conditions sufficient to yield diesel 212 and, a aquaprocessed naphtha stream 203, a lights stream 205, and a very low sulfur fuel oil and/or pitch stream 207.
  • the conditions are sufficient to produce diesel.
  • the conditions are suitable to produce fuel oil.
  • Vacuum residue 210 can exit vacuum distillation unit 202 and enter aquaprocessing unit 20404.
  • the vacuum residue, and optionally pyoil 218, is subjected to aquaprocessing at a temperature of 275 °C to 400 °C (e.g., 300 °C, 325 °C, 350 °C, 375 °C, 400 °C, or any value or range there between) and/or an appropriate pressure.
  • a temperature and pressure the vacuum residue is not completely cracked so as to yield more diesel and/ or fuel oil products.
  • VDU naphtha stream 211 is fed to steam cracker 220, and aquaprocessed naphtha stream 203 is fed into steam cracker 220 or is combined with VDU naphtha stream 211 to form combined naphtha stream 221 which is fed into steam cracker 220.
  • VDU light stream 209 and aquaprocessed lights stream 205 are fed to gas plant 222 are reacted under conditions to produce a gas plant lights stream 251 and fuel gas 223.
  • Gas plant lights stream 221 is fed to steam cracker 220, wherein, along with the naphtha stream 221 (or individual VDU naphtha stream 221 and aquaprocessed naphtha stream 203) are reacted under conditions to produce a hydrogen stream 253, an ethylene stream 224, a propylene stream 225 and a raw C4 stream 226.
  • Steam cracker 220 also produces a pygas stream 227 which is fed to DPHG unit 206, which is processed in DPHG unit 206 to yield a bottom C9+ stream 228 and a C6-C8 hydrocarbon stream 229 which is directed to a BTX extraction unit 230.
  • BTX extraction unit separates the various BTX components into a xylene stream 231, a benzene stream 232 and a toluene stream 233 which are recovered as product.
  • a C5-C8 stream 252 is also produced by BTX extraction unit and is fed to steam cracker 220 for steam cracking.
  • Bottom C9+ stream 228 is mixed with a steam cracked C9+ stream 234 from steam cracker 220 to form pyoil stream 218 which is fed back into aquaprocessor 204 for further aquaprocessing.
  • Aspects of the invention provide a process for producing low sulfur diesel by flowing a hydrocarbon feed into an aquaprocessing having an aquaprocessing catalyst disposed therein; contacting the hydrocarbon feed with the aquaprocessing catalyst at a temperature in the range of from 275 to 400 °C to produce an aquaprocessing effluent; separating the aquaprocessing effluent to form a first stream including a hydrocarbon fraction having a boiling point below 305°C and a second stream including a hydrocarbon fraction having a boiling point above 305°C, wherein the second stream includes the diesel; and hydrotreating the second stream to remove sulfur to produce a hydrotreated second stream including the low sulfur diesel having containing 0 to 50 ppm sulfur.
  • the second stream may further include very low sulfur fuel oil containing 0 to 50 ppm sulfur.
  • the process further includes the step of processing crude oil in a vacuum distillation unit to produce a vacuum distillation residue; wherein the hydrocarbon feed includes the vacuum distillation residue.
  • the process may also include the step of separating the vacuum distillation product into a lights vacuum distillation fraction having a boiling point in a range of and a heavy vacuum distillation fraction having a boiling point range higher than that of the lights vacuum distillation fraction, and a naphtha range cut having a boiling point in a range of 35 to 400°C; and feeding the heavy vacuum distillation fraction from a bottom of the vacuum distillation unit to an aquaprocessing unit.
  • the process may further include the step of feeding the second stream to a steam cracking unit; and steam cracking the second stream to produce olefins.
  • the process may optionally also include the step of flowing steam into the first aquaprocessing unit.
  • the first aquaprocessing unit includes a fixed bed reactor.
  • the first catalyst is selected from
  • the invention relates to a process for producing very low sulfur fuel oil including the steps of flowing a hydrocarbon feed into an aquaprocessing having an aquaprocessing catalyst disposed therein; contacting the hydrocarbon feed with the first catalyst at a temperature in the range of from 275 to 400 °C to produce an aquaprocessing effluent; separating the aquaprocessing effluent to form a first stream including a hydrocarbon fraction having a boiling point below 350°C and a second stream including a hydrocarbon fraction having a boiling point above 350°C, wherein the second stream includes fuel oil; and hydrotreating the second stream to remove sulfur to produce a hydrotreated second stream including the very low sulfur fuel oil having containing from 0 to 50 ppm sulfur.
  • the process may further include the step of feeding the second stream to a steam cracking unit; and steam cracking the second stream to produce olefins.
  • the process may optionally also include the step of flowing steam into the first aquaprocessing unit.
  • the first aquaprocessing unit includes a fixed bed reactor.
  • the aquaprocessing catalyst may include a dissolved portion and a dispersed portion.
  • the dissolved portion of the catalyst includes an organometallic compound having one or more of Ni, Mo, Co, W, Zr.
  • the dissolved portion of the catalyst may include metal naphthenates and/or octanoates having hydrogenation activity.
  • the dispersed portion of the catalyst is a selection from the list consisting of an alkali metal hydroxide or oxide, Ni-Mo oxides or sulphides, Co-Mo oxides or sulphides, W-Mo oxides or sulphides on alumina or zeolites or any combination of these having hydro-processing and/or hydrogen transfer activity.
  • Aspects also relate to a process for steam cracking a feed produced by an aquaprocessing process including the steps of flowing a hydrocarbon feed into an aquaprocessing having an aquaprocessing catalyst disposed therein; contacting the hydrocarbon feed with the first catalyst at a temperature in the range of from 275 to 400 °C to produce an aquaprocessing effluent having a boiling point in the range of 35°C to 400 °C; and feeding at least a first fraction of the aquaprocessing effluent to a steam cracker and steam cracking the first fraction to produce olefins.
  • Any of the above processes may include pyoil in the hydrocarbon feed to the aquaprocessing unit, or may separately provide the pyoil via a suitable inlet.
  • the pyoil may be from an additional process in the system.
  • the pyoil is produced in a pygas hydrotreating unit (DPHG).
  • DPHG pygas hydrotreating unit
  • any of the processes described herein may include one or more of the following in the hydrocarbon feed: crude oil, plastics, oligomers from plastic pyrolysis, synthetic crude oil, crude oil cut, and hydrocarbons from plastics pyrolysis. These may be in addition to, or instead of, vacuum residue and/or the pyoil.
  • Aspects also relate to a process for processing a hydrocarbon feed, the process including the steps of flowing a hydrocarbon feed into an aquaprocessing having an aquaprocessing catalyst disposed therein, wherein the hydrocarbon feed is optionally vacuum residue; contacting the hydrocarbon feed with the first catalyst at a temperature in the range of from 275 to 400 °C to produce an aquaprocessing effluent having a boiling point ranging 35 to 650 °C; separating the aquaprocessing effluent to form a first lights stream including a hydrocarbon fraction having a boiling point of from 25 to 305°C, a first heavy stream including a hydrocarbon fraction having a boiling point above 305°C, and a gaseous stream; separating the first lights stream into a second lights stream having a boiling point ranging from 70 to 140°C and a remaining lights fraction; feeding the second light stream to a catalytic naphtha reformer including a second catalyst to produce aromatics by contacting the second lights stream with the second catalyst at a temperature of from under
  • Embodiment l is a process for producing low sulfur diesel, the process including the steps of flowing a hydrocarbon feed into an aquaprocessing having an aquaprocessing catalyst disposed therein; contacting the hydrocarbon feed with the first catalyst at a temperature in the range of from 275 to 400 °C to produce an aquaprocessing effluent having a boiling point ranging from 35 to 650 °C; separating the aquaprocessing effluent to form a first stream containing a hydrocarbon fraction having a boiling point below 305°C and a second stream containing a hydrocarbon fraction having a boiling point above 305°C, wherein the second stream contains the diesel; and hydrotreating the second stream to remove sulfur to produce a hydrotreated second stream containing the low sulfur diesel having containing from 0 to 50 ppm sulfur.
  • Embodiment 2 is the process of embodiment 1, wherein the second stream further contains very low sulfur fuel oil containing from 0 to 50 ppm sulfur.
  • Embodiment 3 is the process of embodiment 1, wherein the process further contains the step of processing crude oil in a vacuum distillation unit to produce a vacuum distillation residue; wherein the hydrocarbon feed contains the vacuum distillation residue.
  • Embodiment 4 is the process of embodiment 3, further including the steps of separating the vacuum distillation product into a lights vacuum distillation fraction a heavy vacuum distillation fraction having a boiling point higher than the lights vacuum distillation fraction and a naphtha range cut; and feeding the heavy vacuum distillation fraction from a bottom of the vacuum distillation unit to an aquaprocessing unit.
  • Embodiment 5 is the process of embodiment 1, further including the step of feeding the second stream to a steam cracking unit; and steam cracking the second stream to produce olefins.
  • Embodiment 6 is the process of embodiment 1, further including the step of flowing steam into the first aquaprocessing unit.
  • Embodiment 7 is the process of embodiment 1, wherein the first aquaprocessing unit contains a fixed bed reactor.
  • Embodiment 8 is the process of embodiment 1, wherein the first catalyst contains particulate and dissolved catalysts, preferably wherein the dissolved catalyst includes an organometallic compound having one or more of Ni, Mo, Co, W, Zr, preferably in the form of metal naphthenates and/or octanoates, and/or wherein the dispersed portion of the catalyst is a selection from the list consisting of: an alkali metal hydroxide or oxide, Ni-Mo oxides, Ni-Mo sulphides, Co-Mo oxides or Co-Mo sulphides, W-Mo oxides, W-Mo sulphides, preferably on alumina or zeolites, or any combination of these.
  • an alkali metal hydroxide or oxide Ni-Mo oxides, Ni-Mo sulphides, Co-Mo oxides or Co-Mo sulphides, W-Mo oxides, W-Mo sulphides, preferably on alumina or zeolites, or
  • Embodiment 9 is a process for producing very low sulfur fuel oil, the process including the steps of flowing a hydrocarbon feed into an aquaprocessing having an aquaprocessing catalyst disposed therein; contacting the hydrocarbon feed with the first catalyst at a temperature in the range of from 275 to 400 °C to produce an aquaprocessing effluent; separating the aquaprocessing effluent to form a first stream containing a hydrocarbon fraction having a boiling point below 350°C and a second stream containing a hydrocarbon fraction having a boiling point above 350°C, wherein the second stream contains fuel oil; and hydrotreating the second stream to remove sulfur to produce a hydrotreated second stream containing the very low sulfur fuel oil having containing from 0 to 50 ppm sulfur.
  • Embodiment 10 is the process of embodiment 9, further containing the step of feeding the second stream to a steam cracking unit; and steam cracking the second stream to produce olefins.
  • Embodiment 11 is the process of embodiment 1, further containing the step of flowing steam into the first aquaprocessing unit.
  • Embodiment 12 is the process of embodiment 9, wherein the first aquaprocessing unit contains a fixed bed reactor.
  • Embodiment 13 is the process of embodiment 9, wherein the first catalyst contains particulate and dissolved catalysts, preferably wherein the dissolved catalyst includes an organometallic compound having one or more of Ni, Mo, Co, W, Zr, preferably in the form of metal naphthenates and/or octanoates, and/or wherein the dispersed portion of the catalyst is a selection from the list consisting of: an alkali metal hydroxide or oxide, Ni-Mo oxides, Ni-Mo sulphides, Co-Mo oxides or Co-Mo sulphides, W-Mo oxides, W-Mo sulphides, preferably on alumina or zeolites, or any combination of these.
  • an alkali metal hydroxide or oxide Ni-Mo oxides, Ni-Mo sulphides, Co-Mo oxides or Co-Mo sulphides, W-Mo oxides, W-Mo sulphides, preferably on alumina or zeolites, or
  • Embodiment 14 is a process for steam cracking a feed produced by an aquaprocessing process, the process including the steps of flowing a hydrocarbon feed into an aquaprocessing having an aquaprocessing catalyst disposed therein; contacting the hydrocarbon feed with the first catalyst at a temperature in the range of from 275 to 400 °C to produce an aquaprocessing effluent having a boiling point in the range of 35°C to 400 °C; and feeding at least a first fraction of the aquaprocessing effluent to a steam cracker and steam cracking the first fraction to produce olefins.
  • Embodiment 15 is the process of any of the preceding embodiments, wherein the hydrocarbon feed further contains pyoil.
  • Embodiment 16 is the process of embodiment 15 wherein the pyoil is produced in a DPHG unit.
  • Embodiment 17 the process of any of the preceding embodiments, wherein the hydrocarbon feed contains one or more of the following: crude oil, plastics, oligomers from plastic pyrolysis, synthetic crude oil, crude oil cut, and hydrocarbons from plastics pyrolysis.
  • Embodiment 18 is a process for processing a hydrocarbon feed, the process including the steps of flowing a hydrocarbon feed into an aquaprocessing having a first catalyst disposed therein, wherein the hydrocarbon feed is a heavy feed from a vacuum distillation unit; contacting the hydrocarbon feed with the first catalyst at a temperature in the range of from 275 to 400 °C to produce an aquaprocessing effluent having a boiling point ranging from 35 to 650°C; separating the aquaprocessing effluent to form a first lights stream containing a hydrocarbon fraction having a boiling point of from 25 to 300°C, a first heavy stream containing a hydrocarbon fraction having a boiling point above 300°C, and a gaseous stream; separating the first lights stream into a second lights stream having a boiling point ranging from 70 to 140°C and a remaining lights fraction; feeding the second light stream to a catalytic naphtha reformer containing a second catalyst to produce aromatics by contacting the second lights stream with the second catalyst; and feeding
  • Embodiment 19 is the process of embodiment 18, wherein the gaseous stream is fed to a steam cracker.
  • Embodiment 20 is the process of embodiment 18, wherein the gaseous stream is separated to a stream containing ethane, a stream containing butane, and a stream containing propane.
  • Embodiment 21 is a process for coproduction of diesel, lube oil base stocks and high value chemicals in an integrated oil to chemicals complex, the process including the steps of flowing a hydrocarbon feed to a separation unit to produce a first light stream and a heavy cut; feeding the heavy cut into an aquaprocessing unit having an aquaprocessing catalyst disposed therein; contacting the heavy cut with the aquaprocessing catalyst at a temperature in the range from 275 to 400°C to produce an aquaprocessing effluent having a boiling point range from 35 to 650°C; separating the aquaprocessing effluent to form a first aquaprocessed stream containing a hydrocarbon fraction having a boiling point below 305°C, a second aquaprocessed stream containing a hydrocarbon fraction having a boiling point between 305 to 370°C and a third aquaprocessed stream having a boiling point greater than 370°C, wherein the second aquaprocessed stream contains diesel; and optionally hydrotreating the second stream to remove sulphur to produce a hydrotreated second
  • Embodiment 22 is the process according to embodiment 21, wherein the light stream is fed to a gas plant and a VDU naphtha stream with a boiling point up to 220°C is fed to a steam cracker.
  • Embodiment 23 is the process according to embodiment 22, wherein the light stream is fed to a gas plant which separates the light gases to a condensate naphtha stream which is fed to the steam cracker and a gas plant gas stream, wherein the gas plant gas stream is optionally separated into ethane and LPG, and optionally the ethane is fed to an ethane cracker and optionally the LPG is fed to an LPG steam cracker.
  • Embodiment 24 is the process according to embodiment 22, wherein the light stream is fed to a gas plant which separates the light gases to a condensate naphtha stream which is further fed to naphtha steam cracker and a gas stream separated further into ethane, propane and butanes which are fed to ethane cracker, propane cracker or propane dehydrogenation unit, butane cracker or butane dehydrogenation unit.
  • Embodiment 25 is the process according to embodiment 21, wherein first stream is further separated to yield a gaseous effluent which is fed to the gas plant, and optionally a remaining liquid effluent which is fed to a naphtha steam cracker.
  • Embodiment 26 is the process according to embodiment 21, wherein the third stream is recovered as a fuel oil stream.
  • Embodiment 27 is a process for coproduction of diesel and high value chemicals in an oil to chemicals complex, the process including the steps of flowing a hydrocarbon feed to a separation unit to separate into a light cut and a heavy cut; feeding the heavy cut into an aquaprocessing unit having an aquaprocessing catalyst disposed therein; contacting the heavy cut with the aquaprocessing catalyst at a temperature in the range from 275 to 400°C to produce an aquaprocessing effluent having a boiling point range from 35 to 650°C; separating the aquaprocessing effluent to form a first stream containing a hydrocarbon fraction having a boiling point below 305°C, a second stream containing a hydrocarbon fraction having a boiling point greater than 305°C, wherein the second stream is fed to a catalytic cracking unit to produce high value chemicals, saturated gases and residual liquids; feeding the light cut and first stream to steam cracker to produce high value
  • Embodiment 28 is a process according to embodiment 27, wherein the light cut contains light gaseous stream fed to a gas plant along with saturated gases from catalytic cracking unit and a remaining naphtha stream boiling up to 220°C fed to steam cracker.
  • Embodiment 29 is a process according to embodiment 27, wherein the light gaseous stream is fed to a gas plant which separates the light gases to a condensate naphtha stream which is further sent to steam cracker and a gas stream separated further into ethane and LPG and fed to ethane and LPG steam crackers respectively.
  • Embodiment 30 is a process according to embodiment 28, wherein the light gaseous stream is fed to a gas plant which separates the light gases to a condensate naphtha stream which is further fed to naphtha steam cracker and a gas stream separated further into ethane, propane and butanes which are fed to ethane cracker, propane cracker or propane dehydrogenation unit, butane cracker or butane dehydrogenation unit.
  • Embodiment 31 is the process according to embodiment 27, wherein the first stream is split into a gaseous effluent and the gaseous effluent is fed to the gas plant, and optionally a remaining liquid effluent which is fed to a naphtha steam cracker.
  • Embodiment 32 is the embodiment according to embodiments 21 and 27, wherein the first stream is split to produce a 70-140°C cut and a light liquid stream.
  • Embodiment 33 is the process according to embodiment 32 wherein the 70-140°C is fed to a catalytic naphtha reformer to produce BTX aromatics, and routing a saturated gas stream to common gas plant and a non-aromatic liquid stream.
  • Embodiment 34 is a process according to embodiment 32 wherein the remaining light liquid and a non-aromatic liquid stream are fed to naphtha steam cracker.
  • Embodiment 35 is a process according to any of the preceding embodiments, wherein the hydrocarbon feed is selected from crude oil, hydrogenated bio oils, oligomers derived from plastics synthetic crude oil and pyrolysis oils derived from plastics, unconverted oils from refinery, pyrolysis oils and heavy residues from steam crackers.
  • Embodiment 36 is a process according to embodiments 21 or 27, wherein the heavy cut is fed to the aquaprocessing unit and is optionally blended with bio oils or with a hydrocarbon stream containing oxygenated or other heteroatom containing streams before being fed into the aquaprocessing unit.
  • Embodiment 37 is a process according to embodiments 21 or 27, wherein the separation unit contains an atmospheric distillation unit and / or a vacuum distillation unit.
  • Embodiment 38 is a process according to embodiments 21 or 27, wherein the separation unit is a flash vessel.
  • Embodiment 39 is a process according to embodiments 21 or 27, wherein the separation unit is a stripping unit wherein the light cut is separated from the heavy cut with a stripping gas selected from the group consisting of hydrogen and saturated Cl to C4 gases.
  • Embodiment 40 is a process according to embodiments 21 or 27, wherein the aquaprocessing unit hydrocracks the hydrocarbon feed by contacting the hydrocarbon feed with a catalyst containing a particulate catalyst and/or dissolved catalyst in a reactor with or without presence of water along with recycle streams produced in the oil to chemicals complex and added hydrogen.
  • Embodiment 41 is a process according to embodiment 21 or 27, wherein the aquaprocessing unit is selected from the group consisting of a fixed bed reactor, an ebullated bed reactor, a slurry reactor and a jet loop reactor.
  • Embodiment 42 is the process according to embodiment 21 or 27, wherein the catalytic cracking unit is operated in a low severity mode, a high severity mode or a hydropyrolysis mode.

Abstract

A system and method for production of diesel and/or fuel oil products from a hydrocarbon feedstock is disclosed. The system includes an aquaprocessing unit in fluid communication with a vacuum distillation unit and processes the vacuum residue under conditions to produce the diesel and fuel oil.

Description

AOUAPROCESSING OF CRUDE AND HEAVY HYDROCARBON FEEDSTOCKS
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] None.
BACKGROUND OF THE INVENTION
A. Field of the Invention
[0002] The invention generally concerns systems and methods for producing diesel and low sulfur fuel oil or lube oil products from a hydrocarbon feedstock while also producing high value chemical products. A system can include an aquaprocessing unit coupled to a crude distillation unit (CDU) and/or a vacuum distillation unit (VDU) where vacuum residue (VR) from the VDU is fed to the aquaprocessing unit for processing under conditions to yield produce diesel, fuel oil and/or pitch. According to the method of the invention, VR is fed to an aquaprocessing unit and aquaprocessed under conditions that produce diesel, fuel oil and/or pitch. Pyoil may additionally be fed to the aquaprocessing unit, where it is aquaprocessed along with the VR to yield desirable products such as diesel and fuel oil. If necessary, the diesel and/or fuel oil is hydrotreated to remove sulfur to a desired level to meet commercial needs, such as to meet specifications for European Diesel or very low sulfur fuel oil.
B. Description of Related Art
[0003] Diesel fuel is an important fuel for the automotive and trucking industries. Fuel oil is an important heating fuel for commercial and residential use. Both diesel fuel and fuel oil are produced from crude oil, which may contain sulfur. Sulfur promotes fuel oxidation, which causes emissions that are undesirable as they are environmental pollutants. In order to meet emission standards, diesel and fuel oil should be low in sulfur content to reduce pollution and to meet current standards. Typically, sulfur is removed by hydrotreating.
[0004] Typically, diesel and heating oil have been prepared by subjecting various heavier crude oil cuts, such as vacuum residue, to catalytic hydrocracking processes. These hydrocracking processes are energy intensive and do not always provide sufficient yields of product. As demand for diesel and fuel oil products grows, and more efficient systems and processes for preparing diesel and fuel oil products are desired.
SUMMARY OF THE INVENTION
[0005] A discovery has been made that provides a solution to at least one of the problems associated with production of diesel and/or fuel oil.
[0006] In an aspect, the discovery can include a system that provides an aquaprocessing unit that is fluidly connected with a VDU to receive vacuum residue and process it under conditions suitable to produce diesel and/or fuel oil. The aquaprocessing unit may also have an inlet for receiving pyoil for processing along with, or instead of, the VR. This set-up can reduce costs associated with the use of the currently-used crackers and can also reduce the amount of energy needed to produce diesel and fuel oil. Aquaprocessing is the hydrocracking of hydrocarbons in the presence of (a) one or more catalysts and (b) a solvent to keep asphaltenes dissolved, at a temperature in the range of 280 to 550 °C and a pressure in the range of 40 to 200 barg. In embodiments of the invention, the aquaprocessing conditions can include a hydrogen to hydrocarbon ratio from 200 to 2000 NL/L of liquid feed and the aquaprocessing can be carried out with or without added steam.
[0007] In an aspect of the present invention, processes to produce diesel and/or fuel oil products are described. One process relates to producing low sulfur diesel. The process comprises the steps of flowing a hydrocarbon feed into an aquaprocessing unit having an aquaprocessing catalyst disposed therein; contacting the hydrocarbon feed with the first catalyst at a temperature in the range of from 275 to 400 °C to produce an aquaprocessing effluent having a boiling point ranging from 35 to 650°C; separating the aquaprocessing effluent to form a first stream including a hydrocarbon fraction having a boiling point below 305°C and a second stream including a hydrocarbon fraction having a boiling point above 305°C, wherein the second stream includes the diesel; and hydrotreating the second stream to remove sulfur to produce a hydrotreated second stream including the low sulfur diesel having containing 0 ppm to 50 ppm sulfur.
[0008] An aspect of the invention is related to a process for producing very low sulfur fuel oil, the method including the steps of flowing a hydrocarbon feed into an aquaprocessing having an aquaprocessing catalyst disposed therein; contacting the hydrocarbon feed with the first catalyst at a temperature in the range of from 275 to 400 °C to produce an aquaprocessing effluent; separating the aquaprocessing effluent to form a first stream including a hydrocarbon fraction having a boiling point below 350°C and a second stream including a hydrocarbon fraction having a boiling point above 350°C, wherein the second stream includes fuel oil having a boiling point of above 350 to 600°C; hydrotreating the second stream to remove sulfur to produce a hydrotreated second stream including the very low sulfur fuel oil having containing 0 to 50 ppm sulfur.
[0009] An aspect of the present invention relates to a process for steam cracking a feed produced by an aquaprocessing process. This process includes the steps of flowing a hydrocarbon feed into an aquaprocessing having an aquaprocessing catalyst disposed therein; contacting the hydrocarbon feed with the first catalyst at a temperature in the range of from 275 to 400 °C to produce an aquaprocessing effluent having a boiling point in the range of 35°C to 400 °C; and feeding at least a first fraction of the aquaprocessing effluent to a steam cracker and steam cracking the first fraction to produce olefins.
[0010] An aspect of the present invention relates to a process for processing a hydrocarbon feed, wherein the process includes the steps of flowing a hydrocarbon feed into an aquaprocessing unit having an aquaprocessing catalyst disposed therein, wherein the hydrocarbon feed is a heavy feed has a boiling point greater than 275 to 900°C, preferably 275 to 400°C, or preferably 500 to 900°C; contacting the hydrocarbon feed with the first catalyst at a temperature in the range of from 275 to 400°C to produce an aquaprocessing effluent having a boiling point ranging 35 to 400°C; separating the aquaprocessing effluent to form a first lights stream including a hydrocarbon fraction having a boiling point of from 25 to 300°C, a first heavy stream including a hydrocarbon fraction having a boiling point above 300°C, and a gaseous stream; separating the first lights stream into a second lights stream having a boiling point ranging from 70 to 140°C and a remaining lights fraction; feeding the second light stream to a catalytic naphtha reformer including a second catalyst under conditions to produce aromatics by contacting the second lights stream with the second catalyst at a temperature ranging from 35 to 400°C to produce an effluent; and feeding the remaining lights fraction to a first steam cracker or a first catalytic naphtha cracker including a fourth catalyst; wherein the first heavy stream is recycled to the aquaprocessing unit, or wherein the first heavy stream is saturated via hydrogenation with hydrogen and fed to the first steam cracker or a catalytic cracking unit including a fifth catalyst.
[0011] Other embodiments of the invention are discussed throughout this application. Any embodiment discussed with respect to one aspect of the invention applies to other aspects of the invention as well and vice versa. Each embodiment described herein is understood to be embodiments of the invention that are applicable to other aspects of the invention. It is contemplated that any embodiment or aspect discussed herein can be combined with other embodiments or aspects discussed herein and/or implemented with respect to any method or composition of the invention, and vice versa. Furthermore, compositions of the invention can be used to achieve methods of the invention.
[0012] The following includes definitions of various terms and phrases used throughout this specification.
[0013] The term “C# hydrocarbons”, wherein “#” is a positive integer, is meant to describe all hydrocarbons having # carbon atoms. Moreover, the term “C#+ hydrocarbons” is meant to describe all hydrocarbon molecules having # or more carbon atoms. Accordingly, the term “C9+ hydrocarbons” is meant to describe a mixture of hydrocarbons having 9 or more carbon atoms.
[0014] “Aquaprocessing” is the hydrocracking of hydrocarbons in the presence of (a) one or more aquaprocessing catalysts and (b) a solvent to keep asphaltenes dissolved, at a temperature in the range of 280 to 550 °C and a pressure in the range of 40 to 200 barg. In embodiments of the invention, the aquaprocessing conditions can include a hydrogen to hydrocarbon ratio from 200 to 2000 NL/L of liquid feed and the aquaprocessing can be carried out with or without added steam.
[0015] “Hydrocarbons” are generally defined as molecules formed primarily by carbon and hydrogen atoms. Hydrocarbons may also include other elements such as, but not limited to, halogens, metallic elements, nitrogen, oxygen, and/or sulfur. Hydrocarbon fluids may include, entrain, or be entrained in non-hydrocarbon fluids such as hydrogen, nitrogen, carbon monoxide, carbon dioxide, hydrogen sulfide, water, and/or ammonia. [0016] The terms “about” or “approximately” are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment, the terms are defined to be within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.
[0017] The terms “wt.%”, “vol.%”, or “mol.%” refers to a weight percentage of a component, a volume percentage of a component, or molar percentage of a component, respectively, based on the total weight, the total volume of material, or total moles, that includes the component. In a non-limiting example, 10 grams of component in 100 grams of the material is 10 wt.% of component.
[0018] The term “substantially” and its variations are defined to include ranges within 10%, within 5%, within 1%, or within 0.5%.
[0019] The terms “inhibiting” or “reducing” or “preventing” or “avoiding” or any variation of these terms, when used in the claims and/or the specification includes any measurable decrease or complete inhibition to achieve a desired result.
[0020] The term “effective,” as that term is used in the specification and/or claims, means adequate to accomplish a desired, expected, or intended result.
[0021] The use of the words “a” or “an” when used in conjunction with any of the terms “comprising,” “including,” “containing,” or “having” in the claims, or the specification, may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.”
[0022] The words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.
[0023] The systems and processes of the present invention can “comprise,” “consist essentially of,” or “consist of’ particular ingredients, components, compositions, etc. disclosed throughout the specification. With respect to the transitional phrase “consisting essentially of,” in one non- limiting aspect, a basic and novel characteristic of the systems and methods of the present invention are their abilities to produce olefin products (e.g., ethylene) in a cost and energy efficient manner by having an ethane steam cracker unit capable of receiving ethane from a mixed feed steam cracker unit and feeding the C2+ products produced by the ethane steam cracker unit to the mixed feed steam cracker unit.
[0024] Other objects, features and advantages of the present invention will become apparent from the following figures, detailed description, and examples. It should be understood, however, that the figures, detailed description, and examples, while indicating specific embodiments of the invention, are given by way of illustration only and are not meant to be limiting. Additionally, it is contemplated that changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. In further embodiments, features from specific embodiments may be combined with features from other embodiments. For example, features from one embodiment may be combined with features from any of the other embodiments. In further embodiments, additional features may be added to the specific embodiments described herein.
BRIEF DESCRIPTION OF THE DRAWINGS
[0025] Advantages of the present invention may become apparent to those skilled in the art with the benefit of the following detailed description and upon reference to the accompanying drawings.
[0026] FIG. 1 illustrates an embodiment of a system to produce diesel and/or fuel oil products from a hydrocarbon feed provided to an aquaprocessing unit.
[0027] FIG. 2 illustrates an embodiment of a system to produce diesel and/or fuel oil products from a hydrocarbon feed provided to an aquaprocessing unit and other processes operative with the system to yield additional hydrocarbon products.
[0028] While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings. The drawings may not be to scale. DETAILED DESCRIPTION OF THE INVENTION
[0029] A discovery has been made that provides a solution to at least one of the problems associated with steam cracking a mixed hydrocarbon feed. In one aspect, the mixed hydrocarbon feed can be fed to a mixed hydrocarbon steam cracking unit to produce petroleum products and ethane. The ethane can be provided to an independent ethane cracking unit to produce ethylene and/or a C2+ hydrocarbons stream, which can be recycled to the mixed hydrocarbon steam cracking unit. An advantage of this set-up is that the mixed hydrocarbon steam cracking unit can be operated at optimal conditions for C2+ cracking while the ethane steam cracking unit can be operated at optimal conditions to crack ethane. These and other non-limiting aspects of the present invention are discussed in further detail in the following sections with reference to the Figures.
[0030] Referring to FIG. 1, system 100 for producing diesel and/or fuel oil products is described. System 100 can include a vacuum distillation unit 102, an aquaprocessing unit 104, and a pygas hydrotreating (DPHG) unit 106. A hydrocarbon feed 108 enters vacuum distillation unit 102 and is separated into various heavy and light fractions, with the heaviest fraction being vacuum residue which is fed to aquaprocessing unit 104. The hydrocarbon feed will typically be crude oil, which may first be processed in a crude oil distillation unit (CDU).
[0031] Crude oil can be the petroleum extracted from geologic formations in its unrefined form. The term crude oil can also include petroleum that has been subjected to water-oil separations and/or gas-oil separation and/or desalting and/or stabilization. Non-limiting examples of crude oil include Arabian Heavy, Arabian Light, other Gulf crudes, Brent, North Sea crudes, North and West African crudes, Indonesian, Chinese crudes, West Texas crude, and mixtures thereof, but also shale oil, tar sands, gas condensates and bio-based oils. The crude oil used as feed to the process of the present invention preferably is conventional petroleum having an API gravity of more than 20° API as measured by the ASTM D287 standard. In one aspect, the crude oil used in the process of the present invention is a light crude oil having an API gravity of more than 30° API. In another aspect, the crude oil used in the process of the present invention can include Arabian Light Crude Oil. Arabian Light Crude Oil typically has an API gravity of between 32- 36° API and a sulfur content of between 1.5-4.5 wt. %. [0032] In aspects, the vacuum residue may be subjected to a solvent deasphalting step to remove asphaltenes prior to being fed into the aquaprocessing unit.
[0033] Other hydrocarbons may be included in the feed 108, including plastics, oligomers from plastic pyrolysis, synthetic crude oil or hydrocarbons from plastics pyrolysis or any combination of these can be co-processed with crude oil feeds in the aquaprocessing unit 104.
[0034] In the aquaprocessing unit 104, the vacuum residue and/or other hydrocarbon feed can be aquaprocessed under conditions sufficient to yield either or both diesel 112 and/or fuel oil 114. In a preferred aspect, the conditions are sufficient to produce diesel. In an aspect, the conditions are suitable to produce fuel oil.
[0035] Vacuum residue 110 can exit vacuum distillation unit 102 and enter aquaprocessing unit 104. In aquaprocessing unit 104, the vacuum residue, and optionally pyoil 118, is subjected to aquaprocessing in the presence of an aquaprocessing catalyst at a temperature of 275 °C to 400 °C (e.g., 300 °C, 325 °C, 350 °C, 375 °C, 400 °C, or any value or range there between) to yield an aquaprocessing effluent. At such a temperature and pressure the vacuum residue is not completely cracked so as to yield more diesel and/ or fuel oil products.
[0036] Referring to FIG. 2, system 200 for producing diesel and/or fuel oil products is described. System 200 can include a vacuum distillation unit 202, an aquaprocessing unit 204, and an DPHG unit 206. A hydrocarbon feed 208 enters vacuum distillation unit 202 and is separated into various heavy and light fractions, including a VDU lights fraction 209, a VDU naphtha stream 211, with the heaviest fraction being vacuum residue 210 which is fed to aquaprocessing unit 204. The hydrocarbon feed will typically be crude oil, which may first be processed in a crude oil distillation unit (CDU).
[0037] In aspects, the vacuum residue may be subjected to a solvent deasphalting step to remove asphaltenes prior to being fed into the aquaprocessing unit, or in the aquaprocessing unit.
[0038] Other hydrocarbons may be included in the feed 208, including plastics, oligomers from plastic pyrolysis, synthetic crude oil or hydrocarbons from plastics pyrolysis or any combination of these can be co-processed with crude oil feeds in the aquaprocessing unit 204. [0039] In the aquaprocessing unit 204, the vacuum residue and/or other hydrocarbon feed can be aquaprocessed under conditions sufficient to yield diesel 212 and, a aquaprocessed naphtha stream 203, a lights stream 205, and a very low sulfur fuel oil and/or pitch stream 207. In a preferred aspect, the conditions are sufficient to produce diesel. In an aspect, the conditions are suitable to produce fuel oil.
[0040] Vacuum residue 210 can exit vacuum distillation unit 202 and enter aquaprocessing unit 20404. In aquaprocessing unit 204, the vacuum residue, and optionally pyoil 218, is subjected to aquaprocessing at a temperature of 275 °C to 400 °C (e.g., 300 °C, 325 °C, 350 °C, 375 °C, 400 °C, or any value or range there between) and/or an appropriate pressure. At such a temperature and pressure the vacuum residue is not completely cracked so as to yield more diesel and/ or fuel oil products.
[0041] VDU naphtha stream 211 is fed to steam cracker 220, and aquaprocessed naphtha stream 203 is fed into steam cracker 220 or is combined with VDU naphtha stream 211 to form combined naphtha stream 221 which is fed into steam cracker 220.
[0042] The VDU light stream 209 and aquaprocessed lights stream 205 are fed to gas plant 222 are reacted under conditions to produce a gas plant lights stream 251 and fuel gas 223.
[0043] Gas plant lights stream 221 is fed to steam cracker 220, wherein, along with the naphtha stream 221 (or individual VDU naphtha stream 221 and aquaprocessed naphtha stream 203) are reacted under conditions to produce a hydrogen stream 253, an ethylene stream 224, a propylene stream 225 and a raw C4 stream 226. Steam cracker 220 also produces a pygas stream 227 which is fed to DPHG unit 206, which is processed in DPHG unit 206 to yield a bottom C9+ stream 228 and a C6-C8 hydrocarbon stream 229 which is directed to a BTX extraction unit 230. BTX extraction unit separates the various BTX components into a xylene stream 231, a benzene stream 232 and a toluene stream 233 which are recovered as product. A C5-C8 stream 252 is also produced by BTX extraction unit and is fed to steam cracker 220 for steam cracking.
[0044] Bottom C9+ stream 228 is mixed with a steam cracked C9+ stream 234 from steam cracker 220 to form pyoil stream 218 which is fed back into aquaprocessor 204 for further aquaprocessing. [0045] Aspects of the invention provide a process for producing low sulfur diesel by flowing a hydrocarbon feed into an aquaprocessing having an aquaprocessing catalyst disposed therein; contacting the hydrocarbon feed with the aquaprocessing catalyst at a temperature in the range of from 275 to 400 °C to produce an aquaprocessing effluent; separating the aquaprocessing effluent to form a first stream including a hydrocarbon fraction having a boiling point below 305°C and a second stream including a hydrocarbon fraction having a boiling point above 305°C, wherein the second stream includes the diesel; and hydrotreating the second stream to remove sulfur to produce a hydrotreated second stream including the low sulfur diesel having containing 0 to 50 ppm sulfur. The second stream may further include very low sulfur fuel oil containing 0 to 50 ppm sulfur. The process further includes the step of processing crude oil in a vacuum distillation unit to produce a vacuum distillation residue; wherein the hydrocarbon feed includes the vacuum distillation residue. The process may also include the step of separating the vacuum distillation product into a lights vacuum distillation fraction having a boiling point in a range of and a heavy vacuum distillation fraction having a boiling point range higher than that of the lights vacuum distillation fraction, and a naphtha range cut having a boiling point in a range of 35 to 400°C; and feeding the heavy vacuum distillation fraction from a bottom of the vacuum distillation unit to an aquaprocessing unit. The process may further include the step of feeding the second stream to a steam cracking unit; and steam cracking the second stream to produce olefins. The process may optionally also include the step of flowing steam into the first aquaprocessing unit. The first aquaprocessing unit includes a fixed bed reactor. The first catalyst is selected from
[0046] In aspects the invention relates to a process for producing very low sulfur fuel oil including the steps of flowing a hydrocarbon feed into an aquaprocessing having an aquaprocessing catalyst disposed therein; contacting the hydrocarbon feed with the first catalyst at a temperature in the range of from 275 to 400 °C to produce an aquaprocessing effluent; separating the aquaprocessing effluent to form a first stream including a hydrocarbon fraction having a boiling point below 350°C and a second stream including a hydrocarbon fraction having a boiling point above 350°C, wherein the second stream includes fuel oil; and hydrotreating the second stream to remove sulfur to produce a hydrotreated second stream including the very low sulfur fuel oil having containing from 0 to 50 ppm sulfur. The process may further include the step of feeding the second stream to a steam cracking unit; and steam cracking the second stream to produce olefins. The process may optionally also include the step of flowing steam into the first aquaprocessing unit. The first aquaprocessing unit includes a fixed bed reactor. The aquaprocessing catalyst may include a dissolved portion and a dispersed portion. The dissolved portion of the catalyst includes an organometallic compound having one or more of Ni, Mo, Co, W, Zr. The dissolved portion of the catalyst may include metal naphthenates and/or octanoates having hydrogenation activity. The dispersed portion of the catalyst is a selection from the list consisting of an alkali metal hydroxide or oxide, Ni-Mo oxides or sulphides, Co-Mo oxides or sulphides, W-Mo oxides or sulphides on alumina or zeolites or any combination of these having hydro-processing and/or hydrogen transfer activity.
[0047] Aspects also relate to a process for steam cracking a feed produced by an aquaprocessing process including the steps of flowing a hydrocarbon feed into an aquaprocessing having an aquaprocessing catalyst disposed therein; contacting the hydrocarbon feed with the first catalyst at a temperature in the range of from 275 to 400 °C to produce an aquaprocessing effluent having a boiling point in the range of 35°C to 400 °C; and feeding at least a first fraction of the aquaprocessing effluent to a steam cracker and steam cracking the first fraction to produce olefins.
[0048] Any of the above processes may include pyoil in the hydrocarbon feed to the aquaprocessing unit, or may separately provide the pyoil via a suitable inlet. The pyoil may be from an additional process in the system. For example, the pyoil is produced in a pygas hydrotreating unit (DPHG).
[0049] In aspects, any of the processes described herein may include one or more of the following in the hydrocarbon feed: crude oil, plastics, oligomers from plastic pyrolysis, synthetic crude oil, crude oil cut, and hydrocarbons from plastics pyrolysis. These may be in addition to, or instead of, vacuum residue and/or the pyoil.
[0050] Aspects also relate to a process for processing a hydrocarbon feed, the process including the steps of flowing a hydrocarbon feed into an aquaprocessing having an aquaprocessing catalyst disposed therein, wherein the hydrocarbon feed is optionally vacuum residue; contacting the hydrocarbon feed with the first catalyst at a temperature in the range of from 275 to 400 °C to produce an aquaprocessing effluent having a boiling point ranging 35 to 650 °C; separating the aquaprocessing effluent to form a first lights stream including a hydrocarbon fraction having a boiling point of from 25 to 305°C, a first heavy stream including a hydrocarbon fraction having a boiling point above 305°C, and a gaseous stream; separating the first lights stream into a second lights stream having a boiling point ranging from 70 to 140°C and a remaining lights fraction; feeding the second light stream to a catalytic naphtha reformer including a second catalyst to produce aromatics by contacting the second lights stream with the second catalyst at a temperature of from under conditions to produce aromatics; and feeding the remaining lights fraction to a first steam cracker including a steam cracking catalyst or a first catalytic naphtha cracker including a fourth catalyst at a temperature of from 350 to 900°C; wherein the first heavy stream is recycled to the first aquaprocessing unit, or wherein the first heavy stream is saturated via hydrogenation with hydrogen and fed to the first steam cracker or a catalytic cracking unit including a fifth catalyst. The gaseous stream is fed to a steam cracker. The gaseous stream may also be separated to a stream comprising ethane, a stream comprising butane, and a stream comprising propane.
[0051] Non-limiting embodiments of the invention will now be described. Embodiment l is a process for producing low sulfur diesel, the process including the steps of flowing a hydrocarbon feed into an aquaprocessing having an aquaprocessing catalyst disposed therein; contacting the hydrocarbon feed with the first catalyst at a temperature in the range of from 275 to 400 °C to produce an aquaprocessing effluent having a boiling point ranging from 35 to 650 °C; separating the aquaprocessing effluent to form a first stream containing a hydrocarbon fraction having a boiling point below 305°C and a second stream containing a hydrocarbon fraction having a boiling point above 305°C, wherein the second stream contains the diesel; and hydrotreating the second stream to remove sulfur to produce a hydrotreated second stream containing the low sulfur diesel having containing from 0 to 50 ppm sulfur. Embodiment 2 is the process of embodiment 1, wherein the second stream further contains very low sulfur fuel oil containing from 0 to 50 ppm sulfur. Embodiment 3 is the process of embodiment 1, wherein the process further contains the step of processing crude oil in a vacuum distillation unit to produce a vacuum distillation residue; wherein the hydrocarbon feed contains the vacuum distillation residue. Embodiment 4 is the process of embodiment 3, further including the steps of separating the vacuum distillation product into a lights vacuum distillation fraction a heavy vacuum distillation fraction having a boiling point higher than the lights vacuum distillation fraction and a naphtha range cut; and feeding the heavy vacuum distillation fraction from a bottom of the vacuum distillation unit to an aquaprocessing unit. Embodiment 5 is the process of embodiment 1, further including the step of feeding the second stream to a steam cracking unit; and steam cracking the second stream to produce olefins. Embodiment 6 is the process of embodiment 1, further including the step of flowing steam into the first aquaprocessing unit. Embodiment 7 is the process of embodiment 1, wherein the first aquaprocessing unit contains a fixed bed reactor. Embodiment 8 is the process of embodiment 1, wherein the first catalyst contains particulate and dissolved catalysts, preferably wherein the dissolved catalyst includes an organometallic compound having one or more of Ni, Mo, Co, W, Zr, preferably in the form of metal naphthenates and/or octanoates, and/or wherein the dispersed portion of the catalyst is a selection from the list consisting of: an alkali metal hydroxide or oxide, Ni-Mo oxides, Ni-Mo sulphides, Co-Mo oxides or Co-Mo sulphides, W-Mo oxides, W-Mo sulphides, preferably on alumina or zeolites, or any combination of these. Embodiment 9 is a process for producing very low sulfur fuel oil, the process including the steps of flowing a hydrocarbon feed into an aquaprocessing having an aquaprocessing catalyst disposed therein; contacting the hydrocarbon feed with the first catalyst at a temperature in the range of from 275 to 400 °C to produce an aquaprocessing effluent; separating the aquaprocessing effluent to form a first stream containing a hydrocarbon fraction having a boiling point below 350°C and a second stream containing a hydrocarbon fraction having a boiling point above 350°C, wherein the second stream contains fuel oil; and hydrotreating the second stream to remove sulfur to produce a hydrotreated second stream containing the very low sulfur fuel oil having containing from 0 to 50 ppm sulfur. Embodiment 10 is the process of embodiment 9, further containing the step of feeding the second stream to a steam cracking unit; and steam cracking the second stream to produce olefins. Embodiment 11 is the process of embodiment 1, further containing the step of flowing steam into the first aquaprocessing unit. Embodiment 12 is the process of embodiment 9, wherein the first aquaprocessing unit contains a fixed bed reactor. Embodiment 13 is the process of embodiment 9, wherein the first catalyst contains particulate and dissolved catalysts, preferably wherein the dissolved catalyst includes an organometallic compound having one or more of Ni, Mo, Co, W, Zr, preferably in the form of metal naphthenates and/or octanoates, and/or wherein the dispersed portion of the catalyst is a selection from the list consisting of: an alkali metal hydroxide or oxide, Ni-Mo oxides, Ni-Mo sulphides, Co-Mo oxides or Co-Mo sulphides, W-Mo oxides, W-Mo sulphides, preferably on alumina or zeolites, or any combination of these. Embodiment 14 is a process for steam cracking a feed produced by an aquaprocessing process, the process including the steps of flowing a hydrocarbon feed into an aquaprocessing having an aquaprocessing catalyst disposed therein; contacting the hydrocarbon feed with the first catalyst at a temperature in the range of from 275 to 400 °C to produce an aquaprocessing effluent having a boiling point in the range of 35°C to 400 °C; and feeding at least a first fraction of the aquaprocessing effluent to a steam cracker and steam cracking the first fraction to produce olefins. Embodiment 15 is the process of any of the preceding embodiments, wherein the hydrocarbon feed further contains pyoil. Embodiment 16 is the process of embodiment 15 wherein the pyoil is produced in a DPHG unit. Embodiment 17 the process of any of the preceding embodiments, wherein the hydrocarbon feed contains one or more of the following: crude oil, plastics, oligomers from plastic pyrolysis, synthetic crude oil, crude oil cut, and hydrocarbons from plastics pyrolysis. Embodiment 18 is a process for processing a hydrocarbon feed, the process including the steps of flowing a hydrocarbon feed into an aquaprocessing having a first catalyst disposed therein, wherein the hydrocarbon feed is a heavy feed from a vacuum distillation unit; contacting the hydrocarbon feed with the first catalyst at a temperature in the range of from 275 to 400 °C to produce an aquaprocessing effluent having a boiling point ranging from 35 to 650°C; separating the aquaprocessing effluent to form a first lights stream containing a hydrocarbon fraction having a boiling point of from 25 to 300°C, a first heavy stream containing a hydrocarbon fraction having a boiling point above 300°C, and a gaseous stream; separating the first lights stream into a second lights stream having a boiling point ranging from 70 to 140°C and a remaining lights fraction; feeding the second light stream to a catalytic naphtha reformer containing a second catalyst to produce aromatics by contacting the second lights stream with the second catalyst; and feeding the remaining lights fraction to a first steam cracker or a first catalytic naphtha cracker containing a naphtha catalytic cracking catalyst; wherein the first heavy stream is recycled to the first aquaprocessing unit, or wherein the first heavy stream is saturated via hydrogenation with hydrogen and fed to the first steam cracker or a catalytic cracking unit containing a fifth catalyst. Embodiment 19 is the process of embodiment 18, wherein the gaseous stream is fed to a steam cracker. Embodiment 20 is the process of embodiment 18, wherein the gaseous stream is separated to a stream containing ethane, a stream containing butane, and a stream containing propane. Embodiment 21 is a process for coproduction of diesel, lube oil base stocks and high value chemicals in an integrated oil to chemicals complex, the process including the steps of flowing a hydrocarbon feed to a separation unit to produce a first light stream and a heavy cut; feeding the heavy cut into an aquaprocessing unit having an aquaprocessing catalyst disposed therein; contacting the heavy cut with the aquaprocessing catalyst at a temperature in the range from 275 to 400°C to produce an aquaprocessing effluent having a boiling point range from 35 to 650°C; separating the aquaprocessing effluent to form a first aquaprocessed stream containing a hydrocarbon fraction having a boiling point below 305°C, a second aquaprocessed stream containing a hydrocarbon fraction having a boiling point between 305 to 370°C and a third aquaprocessed stream having a boiling point greater than 370°C, wherein the second aquaprocessed stream contains diesel; and optionally hydrotreating the second stream to remove sulphur to produce a hydrotreated second stream containing low sulphur diesel containing less than 50ppm sulphur; feeding the third aquaprocessed stream to a hydroisomerization and cracking unit to produce lube oil base stocks; feeding the light stream and the first aquaprocessed stream to steam cracker to produce olefins and residual pyrolysis oil. Embodiment 22 is the process according to embodiment 21, wherein the light stream is fed to a gas plant and a VDU naphtha stream with a boiling point up to 220°C is fed to a steam cracker. Embodiment 23 is the process according to embodiment 22, wherein the light stream is fed to a gas plant which separates the light gases to a condensate naphtha stream which is fed to the steam cracker and a gas plant gas stream, wherein the gas plant gas stream is optionally separated into ethane and LPG, and optionally the ethane is fed to an ethane cracker and optionally the LPG is fed to an LPG steam cracker. Embodiment 24 is the process according to embodiment 22, wherein the light stream is fed to a gas plant which separates the light gases to a condensate naphtha stream which is further fed to naphtha steam cracker and a gas stream separated further into ethane, propane and butanes which are fed to ethane cracker, propane cracker or propane dehydrogenation unit, butane cracker or butane dehydrogenation unit. Embodiment 25 is the process according to embodiment 21, wherein first stream is further separated to yield a gaseous effluent which is fed to the gas plant, and optionally a remaining liquid effluent which is fed to a naphtha steam cracker. Embodiment 26 is the process according to embodiment 21, wherein the third stream is recovered as a fuel oil stream. Embodiment 27 is a process for coproduction of diesel and high value chemicals in an oil to chemicals complex, the process including the steps of flowing a hydrocarbon feed to a separation unit to separate into a light cut and a heavy cut; feeding the heavy cut into an aquaprocessing unit having an aquaprocessing catalyst disposed therein; contacting the heavy cut with the aquaprocessing catalyst at a temperature in the range from 275 to 400°C to produce an aquaprocessing effluent having a boiling point range from 35 to 650°C; separating the aquaprocessing effluent to form a first stream containing a hydrocarbon fraction having a boiling point below 305°C, a second stream containing a hydrocarbon fraction having a boiling point greater than 305°C, wherein the second stream is fed to a catalytic cracking unit to produce high value chemicals, saturated gases and residual liquids; feeding the light cut and first stream to steam cracker to produce high value chemicals and residual pyrolysis oil; recycling the residual liquids and residual pyrolysis oil back to the aquaprocessing unit. Embodiment 28 is a process according to embodiment 27, wherein the light cut contains light gaseous stream fed to a gas plant along with saturated gases from catalytic cracking unit and a remaining naphtha stream boiling up to 220°C fed to steam cracker. Embodiment 29 is a process according to embodiment 27, wherein the light gaseous stream is fed to a gas plant which separates the light gases to a condensate naphtha stream which is further sent to steam cracker and a gas stream separated further into ethane and LPG and fed to ethane and LPG steam crackers respectively. Embodiment 30 is a process according to embodiment 28, wherein the light gaseous stream is fed to a gas plant which separates the light gases to a condensate naphtha stream which is further fed to naphtha steam cracker and a gas stream separated further into ethane, propane and butanes which are fed to ethane cracker, propane cracker or propane dehydrogenation unit, butane cracker or butane dehydrogenation unit. Embodiment 31 is the process according to embodiment 27, wherein the first stream is split into a gaseous effluent and the gaseous effluent is fed to the gas plant, and optionally a remaining liquid effluent which is fed to a naphtha steam cracker. Embodiment 32 is the embodiment according to embodiments 21 and 27, wherein the first stream is split to produce a 70-140°C cut and a light liquid stream. Embodiment 33 is the process according to embodiment 32 wherein the 70-140°C is fed to a catalytic naphtha reformer to produce BTX aromatics, and routing a saturated gas stream to common gas plant and a non-aromatic liquid stream. Embodiment 34 is a process according to embodiment 32 wherein the remaining light liquid and a non-aromatic liquid stream are fed to naphtha steam cracker. Embodiment 35 is a process according to any of the preceding embodiments, wherein the hydrocarbon feed is selected from crude oil, hydrogenated bio oils, oligomers derived from plastics synthetic crude oil and pyrolysis oils derived from plastics, unconverted oils from refinery, pyrolysis oils and heavy residues from steam crackers. Embodiment 36 is a process according to embodiments 21 or 27, wherein the heavy cut is fed to the aquaprocessing unit and is optionally blended with bio oils or with a hydrocarbon stream containing oxygenated or other heteroatom containing streams before being fed into the aquaprocessing unit. Embodiment 37 is a process according to embodiments 21 or 27, wherein the separation unit contains an atmospheric distillation unit and / or a vacuum distillation unit. Embodiment 38 is a process according to embodiments 21 or 27, wherein the separation unit is a flash vessel. Embodiment 39 is a process according to embodiments 21 or 27, wherein the separation unit is a stripping unit wherein the light cut is separated from the heavy cut with a stripping gas selected from the group consisting of hydrogen and saturated Cl to C4 gases. Embodiment 40 is a process according to embodiments 21 or 27, wherein the aquaprocessing unit hydrocracks the hydrocarbon feed by contacting the hydrocarbon feed with a catalyst containing a particulate catalyst and/or dissolved catalyst in a reactor with or without presence of water along with recycle streams produced in the oil to chemicals complex and added hydrogen. Embodiment 41 is a process according to embodiment 21 or 27, wherein the aquaprocessing unit is selected from the group consisting of a fixed bed reactor, an ebullated bed reactor, a slurry reactor and a jet loop reactor. Embodiment 42 is the process according to embodiment 21 or 27, wherein the catalytic cracking unit is operated in a low severity mode, a high severity mode or a hydropyrolysis mode.
[0052]
[0053] Although embodiments of the present application and their advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the embodiments as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the above disclosure, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein can be utilized. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.

Claims

1. A process for producing low sulfur diesel, the process comprising the steps of: flowing a hydrocarbon feed into an aquaprocessing having an aquaprocessing catalyst disposed therein; contacting the hydrocarbon feed with the first catalyst at a temperature in the range of from 275 to 400 °C to produce an aquaprocessing effluent having a boiling point ranging from 35 to 650 °C; separating the aquaprocessing effluent to form a first stream comprising a hydrocarbon fraction having a boiling point below 305°C and a second stream comprising a hydrocarbon fraction having a boiling point above 305°C, wherein the second stream comprises the diesel; and hydrotreating the second stream to remove sulfur to produce a hydrotreated second stream comprising the low sulfur diesel having containing from 0 to 50 ppm sulfur.
2. The process of claim 1, wherein the second stream further comprises very low sulfur fuel oil containing from 0 to 50 ppm sulfur.
3. The process of claim 1, wherein the process further comprises the step of processing crude oil in a vacuum distillation unit to produce a vacuum distillation residue; wherein the hydrocarbon feed comprises the vacuum distillation residue; and/or wherein the process further comprises the steps of separating the vacuum distillation product into a lights vacuum distillation fraction a heavy vacuum distillation fraction having a boiling point higher than the lights vacuum distillation fraction and a naphtha range cut; and feeding the heavy vacuum distillation fraction from a bottom of the vacuum distillation unit to an aquaprocessing unit.
4. The process of claim 1, further comprising the step of feeding the second stream to a steam cracking unit; and
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RECTIFIED SHEET (RULE 91 ) ISA/EP steam cracking the second stream to produce olefins.
5. The process of claim 1, further comprising the step of flowing steam into the first aquaprocessing unit, and/or wherein the first aquaprocessing unit comprises a fixed bed reactor.
6. The process of claim 1, wherein the first catalyst contains particulate and dissolved catalysts, preferably wherein the dissolved catalyst includes an organometallic compound having one or more of Ni, Mo, Co, W, Zr, preferably in the form of metal naphthenates and/or octanoates, and/or wherein the dispersed portion of the catalyst is a selection from the list consisting of an alkali metal hydroxide or oxide, Ni-Mo oxides, Ni-Mo sulphides, Co-Mo oxides or Co-Mo sulphides, W-Mo oxides, W-Mo sulphides, preferably on alumina or zeolites, or any combination of these.
7. A process for producing very low sulfur fuel oil, the process comprising the steps of: flowing a hydrocarbon feed into an aquaprocessing having an aquaprocessing catalyst disposed therein; contacting the hydrocarbon feed with the first catalyst at a temperature in the range of from 275 to 400 °C to produce an aquaprocessing effluent; separating the aquaprocessing effluent to form a first stream comprising a hydrocarbon fraction having a boiling point below 350°C and a second stream comprising a hydrocarbon fraction having a boiling point above 35O°C, wherein the second stream comprises fuel oil; and hydrotreating the second stream to remove sulfur to produce a hydrotreated second stream comprising the very low sulfur fuel oil having containing from 0 to 50 ppm sulfur.
8. The process of claim 7, further comprising the step of feeding the second stream to a steam cracking unit; and steam cracking the second stream to produce olefins; and/or further comprising the step of flowing steam into the first aquaprocessing unit; and/or wherein the first aquaprocessing unit comprises a fixed bed reactor
19
RECTIFIED SHEET (RULE 91 ) ISA/EP
9. The process of claim 7, wherein the first catalyst comprises particulate and dissolved catalysts, preferably wherein the dissolved catalyst includes an organometallic compound having one or more of Ni, Mo, Co, W, Zr, preferably in the form of metal naphthenates and/or octanoates, and/or wherein the dispersed portion of the catalyst is a selection from the list consisting of: an alkali metal hydroxide or oxide, Ni-Mo oxides, Ni-Mo sulphides, Co-Mo oxides or Co-Mo sulphides, W-Mo oxides, W-Mo sulphides, preferably on alumina or zeolites, or any combination of these.
10. A process for steam cracking a feed produced by an aquaprocessing process, the process comprising the steps of: flowing a hydrocarbon feed into an aquaprocessing having an aquaprocessing catalyst disposed therein; contacting the hydrocarbon feed with the first catalyst at a temperature in the range of from 275 to 400 °C to produce an aquaprocessing effluent having a boiling point in the range of 35°C to 400 °C; and feeding at least a first fraction of the aquaprocessing effluent to a steam cracker and steam cracking the first fraction to produce olefins.
11. The process of any of the preceding claims, wherein the hydrocarbon feed further comprises pyoil; and/or wherein the pyoil is produced in a DPHG unit; and/or wherein the hydrocarbon feed comprises one or more of the following: crude oil, plastics, oligomers from plastic pyrolysis, synthetic crude oil, crude oil cut, and hydrocarbons from plastics pyrolysis.
12. A process for processing a hydrocarbon feed, the process comprising the steps of: flowing a hydrocarbon feed into an aquaprocessing having a first catalyst disposed therein, wherein the hydrocarbon feed is a heavy feed from a vacuum distillation unit; contacting the hydrocarbon feed with the first catalyst at a temperature in the range of from 275 to 400 °C to produce an aquaprocessing effluent having a boiling point ranging from 35 to 650°C;
20
RECTIFIED SHEET (RULE 91 ) ISA/EP separating the aquaprocessing effluent to form a first lights stream comprising a hydrocarbon fraction having a boiling point of from 25 to 300°C, a first heavy stream comprising a hydrocarbon fraction having a boiling point above 300°C, and a gaseous stream; separating the first lights stream into a second lights stream having a boiling point ranging from 70 to 140°C and a remaining lights fraction; feeding the second light stream to a catalytic naphtha reformer comprising a second catalyst to produce aromatics by contacting the second lights stream with the second catalyst; and feeding the remaining lights fraction to a first steam cracker or a first catalytic naphtha cracker comprising a naphtha catalytic cracking catalyst; wherein the first heavy stream is recycled to the first aquaprocessing unit, or wherein the first heavy stream is saturated via hydrogenation with hydrogen and fed to the first steam cracker or a catalytic cracking unit comprising a fifth catalyst.
13. The process of claim 12, wherein the gaseous stream is fed to a steam cracker; and/or wherein the gaseous stream is separated to a stream comprising ethane, a stream comprising butane, and a stream comprising propane.
14. A process for coproduction of diesel, lube oil base stocks and high value chemicals in an integrated oil to chemicals complex, the process comprising the steps of: flowing a hydrocarbon feed to a separation unit to produce a first light stream and a heavy cut; feeding the heavy cut into an aquaprocessing unit having an aquaprocessing catalyst disposed therein; contacting the heavy cut with the aquaprocessing catalyst at a temperature in the range from 275 to 400°C to produce an aquaprocessing effluent having a boiling point range from 35 to 650°C; separating the aquaprocessing effluent to form a first aquaprocessed stream comprising a hydrocarbon fraction having a boiling point below 305°C, a second aquaprocessed stream comprising a hydrocarbon fraction having a boiling point between 305 to 370°C and a third
21
RECTIFIED SHEET (RULE 91 ) ISA/EP aquaprocessed stream having a boiling point greater than 370°C, wherein the second aquaprocessed stream comprises diesel; and optionally hydrotreating the second stream to remove sulphur to produce a hydrotreated second stream comprising low sulphur diesel containing less than 50ppm sulphur; feeding the third aquaprocessed stream to a hydroisomerization and cracking unit to produce lube oil base stocks; feeding the light stream and the first aquaprocessed stream to steam cracker to produce olefins and residual pyrolysis oil; and recycling the residual pyrolysis oil to the aquaprocessing unit.
15. The process according to claim 14, wherein the light stream is fed to a gas plant and a VDU naphtha stream with a boiling point up to 220°C is fed to a steam cracker.
16. The process according to claim 15, wherein the light stream is fed to a gas plant which separates the light gases to a condensate naphtha stream which is fed to the steam cracker and a gas plant gas stream, wherein the gas plant gas stream is optionally separated into ethane and LPG, and optionally the ethane is fed to an ethane cracker and optionally the LPG is fed to an LPG steam cracker.
17. The process according to claim 15, wherein the light stream is fed to a gas plant which separates the light gases to a condensate naphtha stream which is further fed to naphtha steam cracker and a gas stream separated further into ethane, propane and butanes which are fed to ethane cracker, propane cracker or propane dehydrogenation unit, butane cracker or butane dehydrogenation unit.
18. The process according to claim 14, wherein first stream is further separated to yield a gaseous effluent which is fed to the gas plant, and optionally a remaining liquid effluent which is fed to a naphtha steam cracker; and/or wherein the third stream is recovered as a fuel oil stream.
19. A process for coproduction of diesel and high value chemicals in an oil to chemicals complex, the process comprising the steps of:
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RECTIFIED SHEET (RULE 91 ) ISA/EP flowing a hydrocarbon feed to a separation unit to separate into a light cut and a heavy cut; feeding the heavy cut into an aquaprocessing unit having an aquaprocessing catalyst disposed therein; contacting the heavy cut with the aquaprocessing catalyst at a temperature in the range from 275 to 400°C to produce an aquaprocessing effluent having a boiling point range from 35 to 650°C; separating the aquaprocessing effluent to form a first stream comprising a hydrocarbon fraction having a boiling point below 305°C , a second stream comprising a hydrocarbon fraction having a boiling point greater than 3O5°C, wherein the second stream is fed to a catalytic cracking unit to produce high value chemicals, saturated gases and residual liquids; feeding the light cut and first stream to steam cracker to produce high value chemicals and residual pyrolysis oil; recycling the residual liquids and residual pyrolysis oil back to the aquaprocessing unit.
20. A process according to claim 19, wherein the light cut comprises light gaseous stream fed to a gas plant along with saturated gases from catalytic cracking unit and a remaining naphtha stream boiling up to 220°C fed to steam cracker.
21. A process according to claim 19, wherein the light gaseous stream is fed to a gas plant which separates the light gases to a condensate naphtha stream which is further sent to steam cracker and a gas stream separated further into ethane and LPG and fed to ethane and LPG steam crackers respectively.
22. A process according to claim 20, wherein the light gaseous stream is fed to a gas plant which separates the light gases to a condensate naphtha stream which is further fed to naphtha steam cracker and a gas stream separated further into ethane, propane and butanes which are fed to ethane cracker, propane cracker or propane dehydrogenation unit, butane cracker or butane dehydrogenation unit.
23. A process according to claim 19, wherein the first stream is split into a gaseous effluent and the gaseous effluent is fed to the gas plant, and optionally a remaining liquid effluent which is fed to a naphtha steam cracker.
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RECTIFIED SHEET (RULE 91 ) ISA/EP
24. A process according to claims 14 and 19, wherein the first stream is split to produce a 70- 140°C cut and a light liquid stream.
25. A process according to claim 24 wherein the 70-140°C is fed to a catalytic naphtha reformer to produce BTX aromatics, and routing a saturated gas stream to common gas plant and a nonaromatic liquid stream.
26. A process according to claim 24 wherein the remaining light liquid and a non-aromatic liquid stream are fed to naphtha steam cracker.
27. A process according to any of the preceding claims, wherein the hydrocarbon feed is selected from crude oil, hydrogenated bio oils, oligomers derived from plastics synthetic crude oil and pyrolysis oils derived from plastics, unconverted oils from refinery, pyrolysis oils and heavy residues from steam crackers.
28. A process according to claim 14 or 19, wherein the heavy cut is fed to the aquaprocessing unit and is optionally blended with bio oils or with a hydrocarbon stream containing oxygenated or other heteroatom containing streams before being fed into the aquaprocessing unit.
29. A process according to claim 14 or 19, wherein the separation unit comprises an atmospheric distillation unit and / or a vacuum distillation unit.
30. A process according to claim 14 or 19, wherein the separation unit is a flash vessel.
31. A process according to claim 14 or 19, wherein the separation unit is a stripping unit wherein the light cut is separated from the heavy cut with a stripping gas selected from the group consisting of hydrogen and saturated Cl to C4 gases.
32. A process according to claim 14 or 19, wherein the aquaprocessing unit hydrocracks the hydrocarbon feed by contacting the hydrocarbon feed with a catalyst comprising a particulate catalyst and/or dissolved catalyst in a reactor with or without presence of water along with recycle streams produced in the oil to chemicals complex and added hydrogen.
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RECTIFIED SHEET (RULE 91 ) ISA/EP
33. A process according to claim 14 or 19, wherein the aquaprocessing unit is selected from the group consisting of a fixed bed reactor, an ebullated bed reactor, a slurry reactor and a jet loop reactor.
34. A process according to claim 14 or 19, wherein the catalytic cracking unit is operated in a low severity mode, a high severity mode or a hydropyrolysis mode.
25
RECTIFIED SHEET (RULE 91 ) ISA/EP
PCT/EP2023/068754 2022-07-09 2023-07-06 Aquaprocessing of crude and heavy hydrocarbon feedstocks WO2024012991A1 (en)

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US20120251403A1 (en) * 2011-03-31 2012-10-04 Uop Llc Apparatus for producing diesel
US20160362609A1 (en) * 2014-02-25 2016-12-15 Saudi Basic Industries Corporation Process for converting mixed waste plastic (mwp) into valuable petrochemicals
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Title
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