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EP4267699A1 - Production de composés aromatiques btx et d'oléfines de gaz légères à partir de pétrole brut et d'huile de pyrolyse de matière plastique - Google Patents

Production de composés aromatiques btx et d'oléfines de gaz légères à partir de pétrole brut et d'huile de pyrolyse de matière plastique

Info

Publication number
EP4267699A1
EP4267699A1 EP21794981.7A EP21794981A EP4267699A1 EP 4267699 A1 EP4267699 A1 EP 4267699A1 EP 21794981 A EP21794981 A EP 21794981A EP 4267699 A1 EP4267699 A1 EP 4267699A1
Authority
EP
European Patent Office
Prior art keywords
stream
boiling point
cracking
aromatics
reforming
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21794981.7A
Other languages
German (de)
English (en)
Inventor
Ravichander Narayanaswamy
Alexander Stanislaus
Girish KORIPELLY
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SABIC Global Technologies BV
Original Assignee
SABIC Global Technologies BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SABIC Global Technologies BV filed Critical SABIC Global Technologies BV
Publication of EP4267699A1 publication Critical patent/EP4267699A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/04—Treatment 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
    • C10G35/09—Bimetallic catalysts in which at least one of the metals is a platinum group metal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/095—Catalytic reforming characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
    • C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/22—Separation of effluents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/06—Treatment 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/08—Treatment 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 reforming naphtha
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/34—Thermal 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
    • C10G9/36—Thermal 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1003—Waste materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics

Definitions

  • the invention generally relates to a process for producing Ce to Cx aromatics and optionally light gas olefins.
  • the invention relates to a process for producing Ce to Cs aromatics and light gas olefins from crude oil and/or pyrolysis oil using hydroprocessing.
  • Ce to Cs aromatics such as benzene, toluene, and xylene are important commodity chemicals with continuously increasing demand.
  • benzene, toluene, and/or xylene are used to make various polymers (e.g., polycarbonates, polyesters, nylons, and polyurethanes etc.) having multiple industrial uses.
  • Light gas olefins such as ethylene, propylene, and butylene are important raw materials for multiple end products like polymers, rubbers, plastics, octane booster compounds, etc.
  • Benzene, toluene, and xylene are typically prepared by reforming naphtha such as straight run naphtha from crude oil in a reformer.
  • naphtha such as straight run naphtha
  • a fraction e.g. about 10 to 20 wt.% of the crude oil is suitable for reforming and used to prepare benzene, toluene, and xylene.
  • naphthenes are more favorable to form aromatics by reforming
  • typical reformer feed from crude oil has relatively low naphthene content.
  • typically less than 25 wt.% of the reformer feed is naphthenic.
  • a solution can include positioning a hydroprocessing unit upstream to a reforming unit used for producing aromatics.
  • a single hydro processing unit can be used.
  • the use of the upstream hydroprocessing unit can: i) increase the amount of reformer feed per unit crude oil processed; ii) increase the amount of naphthenes suitable for producing to Cs aromatics by reforming; and/or iii) optionally increase the amount of steam cracker feed per unit crude oil processed.
  • hydroprocessing unit can reduce the amount of olefins in the reformer feed, which can serve to reduce the exothermicity in the reforming unit, which can help conserve energy and increase the efficiency of the reforming unit.
  • the stream comprising hydrocarbons having a boiling point 70 °C to 140 °C can be sent to the reformer unit to produce Ce to Cs aromatics (e.g., benzene, toluene, and/or xylene (BTX)).
  • Ce to Cs aromatics e.g., benzene, toluene, and/or xylene (BTX)
  • the stream comprising hydrocarbons having a boiling point less than 70 °C can be cracked (e.g., via steam cracking or catalytic cracking) to product light gas olefins.
  • Ce to Cs aromatics and/or light gas olefins can be produced from plastics (e.g., recycled mixed thermoplastic material) as a feed source.
  • the initial feed can include plastics (e g., recycled mixed thermoplastic material).
  • the plastics can be reactively extruded or melt cracked to form pyrolysis oil.
  • the pyrolysis oil can be separated into: (i) a stream comprising hydrocarbons having a boiling point less than 70 °C; (ii) a stream comprising hydrocarbons having a boiling point 70 °C to 140 °C; and (iii) a stream comprising hydrocarbons having a boiling point greater than 140 °C. At least a portion of the stream comprising hydrocarbons having a boiling point greater than 140 °C can be recycled back to the reactive extrusion or melt cracking process (e.g., the reaction process).
  • the stream comprising hydrocarbons having a boiling point 70 °C to 140 °C can be sent to a reformer unit to produce Cs to Cs aromatics (e.g., BTX).
  • the stream comprising hydrocarbons having a boiling point less than 70 °C or portions thereof can be, sent for steam reforming to produce hydrogen; or cracked in a catalytic cracking unit to produce light gas olefins; or sent to a gasoline pool; or any combination thereof.
  • Benefits of this process include not using a hydroprocessing unit (although such a unit can be used in the context of the present invention) and/or the use of recycled plastics to efficiently produce BTX and optionally olefins.
  • the stream containing hydrocarbons having a boiling point of 70 °C to 140 °C can contain chlorine, which can be beneficial in keeping the reformer catalyst active.
  • at least a portion of the chloride present in the stream comprising hydrocarbons having a boiling point of 70 °C to 140 °C can be sourced from the plastics.
  • Certain aspects are directed to a first process for producing Cs to Cs aromatics and optionally light gas olefins.
  • the first process can include any one of, any combination of, or all of the steps (a) to (e).
  • a first stream can be hydroprocessed to obtain a second stream.
  • the first stream can contain hydrocarbons from crude oil and/or pyrolysis oil.
  • the second stream can contain saturated hydrocarbons having boiling points less than 350 °C.
  • at least 70 wt.% of the hydrocarbons in the second stream can be saturated hydrocarbons having boiling points less than 350 °C.
  • the second stream can further contain aromatics.
  • step (b) the second stream can be separated to obtain a third stream containing hydrocarbons having boiling point less than 70 °C, a fourth stream containing hydrocarbons having boiling point 70 °C to 140 °C, and a fifth stream containing hydrocarbons having boiling point greater than 140 °C.
  • step (c) at least a portion of the fifth stream can be recycled to the hydroprocessing step (a).
  • step (d) the fourth stream can be reformed to obtain a sixth stream containing Cs to Cs aromatics.
  • the Cs to Cs aromatics can be benzene, toluene, and xylene, and the sixth stream can contain benzene, toluene, and xylene.
  • the third stream can be cracked e.g. steam cracked or catalytically cracked to obtain light gas olefins. Reforming in step (d) can also produce nonaromatics and non Cs to Cs aromatics (e.g., aromatic hydrocarbons other than benzene, toluene, and xylene).
  • a seventh stream containing at least a portion of the nonaromatics and non Cs to Cs aromatics produced in step (d) can be recycled to the hydroprocessing step (a).
  • a portion of the fifth stream can be cracked e.g. steam cracked or catalytically cracked with the third stream in step (e) to form the light gas olefins.
  • the hydroprocessing in step (a) can include hydrocracking and/or hydrotreating.
  • sulfur and/or nitrogen content of sulfur and/or nitrogen containing hydrocarbons can be reduced.
  • the hydrocracking process can include cracking of hydrocarbons in the presence of H2.
  • the hydroprocessing can be performed at a low pressure, such as at a pressure equal to or lower than 100 barg. Without wishing to be bound by theory, it is believed that lower operating pressure may lead to less investment cost and may have a beneficial impact on the economics of the process.
  • hydroprocessing conditions in step (a) can include a pressure of 30 barg to 100 barg; a temperature of 300 °C to 600 °C, preferably 350 °C to 500 °C; or weight hourly space velocity (WHSV) of 0.5 to 2 hr' 1 ; or any combinations thereof.
  • the hydroprocessing can be performed in presence of hydrogen (H2) with H2 to hydrocarbon (e.g. H2 and hydrocarbon fed to the hydroprocessing step) volume ratio of 200 Nm’/m 3 to 2000 Nm 3 /m 3 .
  • the hydroprocessing can be performed in presence of a catalyst.
  • the catalyst can contain a hydrocracking catalyst and/or a hydrotreating catalyst.
  • the hydrocracking catalyst can contain Ni and/or W. In some aspects, the hydrotreating catalyst can contain Co, Ni and/or Mo. In some aspects, the hydroprocessing can be performed in presence of a dissolved catalyst and/or a fixed bed catalyst. In some aspects, the dissolved catalyst can contain nickel (Ni) and/or molybdenum (Mo). In some aspects, the dissolved catalyst can contain metal naphthenates and/or octanoates. In some aspects, the dissolved catalyst can contain Ni octanoates, Ni naphthenates, Mo octanoates, or Mo naphthenates, or any combinations thereof.
  • Ni octanoates, Ni naphthenates, Mo octanoates, and/or Mo naphthenates independently can be in a hydrocarbon base.
  • the dissolved catalyst can be a catalyst solubilized in the feed and can form a homogeneous catalyst when mixed with feed (e.g. hydroprocessing feed).
  • no additional solvent can be used for dissolving the catalysts e.g. metal naphthenates and/or octanoates in the feed.
  • the fixed bed catalyst can contain one or more transition metal(s) on a support.
  • the one or more transition metal(s) can be cobalt (Co), Ni, Mo and/or tungsten (W).
  • the fixed bed catalyst can contain Co and Mo on a support; Ni and Mo on a support; Co, Ni, and Mo on a support; Ni and W on a support; or Ni, W, and Mo on a support, or any combinations thereof.
  • the fixed bed catalyst support can be alumina, silica, aluminosilicates or zeolite, or any combinations thereof.
  • the zeolite can be a X-type zeolite, Y-type or USY-type zeolite, mordenite, faujasite, nano-crystalline zeolite, MCM mesoporous material, SBA-15, silico-alumino phosphate, gallophosphate, titanophosphate, ZSM-5, ZSM- 11, ferrierite, heulandite, zeolite- A, erionite, and chabazite, or any combinations thereof.
  • the second stream can be separated into the third, fourth and fifth stream in step (b) by atmospheric distillation with boiling points cuts of 70 °C and 140 °C.
  • the third stream can contain a hydrocarbon fraction with upper boiling point cut of 70 °C, from the second stream.
  • the fourth stream can contain a hydrocarbon fraction with lower boiling point cut of 70 °C and an upper boiling point cut of 140 °C, from the second stream.
  • the fifth stream can contain a hydrocarbon fraction with lower boiling point cut of 140 °C, from the second stream.
  • the first stream can be obtained from crude oil.
  • the first stream can be obtained by atmospheric distillation of i) crude oil, or ii) crude oil and pyrolysis oil.
  • the atmospheric distillation can be performed in a crude distillation unit (CDU), with boiling points cut of 70 °C and 140 °C.
  • CDU crude distillation unit
  • a first hydrocarbon fraction having upper boiling point cut of 70 °C, a second hydrocarbon fraction having lower boiling point cut of 70 °C and upper boiling point cut of 140 °C, and a third hydrocarbon fraction having lower boiling point cut of 140 °C can be obtained.
  • the third hydrocarbon fraction can form the first stream and can be hydroprocessed e.g. in step (a).
  • the second hydrocarbon fraction can be reformed to form Ce to Cx aromatics.
  • an eighth stream containing the second hydrocarbon fraction can be reformed in step (d) with the fourth stream, to form the sixth stream and seventh stream.
  • the first hydrocarbon fraction or a portion of the first hydrocarbon fraction can be cracked e.g. steam cracked or catalytically cracked to form light gas olefins.
  • the first hydrocarbon fraction or a portion of the first hydrocarbon fraction can be hydroprocessed.
  • crude oil can be distilled in the CDU, and a ninth stream containing the first hydrocarbon fraction can optionally be cracked e.g.
  • crude oil and pyrolysis oil can be distilled in the CDU, and a ninth stream containing the first hydrocarbon fraction can be hydroprocessed in step (a) with the first stream, to form the second stream.
  • the pyrolysis oil can be obtained from plastics by reactive extrusion or by melt cracking, and can contain chlorides and olefins.
  • the first stream can contain condensate, naphtha, light crude oil, or a crude oil hydrocarbon fraction having an upper boiling point cut of 350 °C, whole crude oil, or any combinations thereof.
  • the first stream can contain pyrolysis oil.
  • the pyrolysis oil can be obtained from plastics by reactive extrusion or by melt cracking.
  • the reactive extrusion or melt cracking of the plastics can include depolymerizing the plastics at a depolymerization temperature sufficient to produce a hydrocarbonaceous wax stream, and catalytic cracking of the hydrocarbonaceous wax stream in presence of a cracking catalyst under cracking conditions sufficient to produce the pyrolysis oil, wherein the cracking conditions can include a cracking temperature that is lower than, equal to, or higher than the depolymerization temperature.
  • the depolymerization of the plastic can be performed in an extruder/twin screw reactor/auger.
  • Certain aspects are directed to a second process for producing Ce to Cs aromatics and optionally light gas olefins.
  • the second process can include any one of, any combination of, or all of steps (i), (ii), and (iii).
  • step (i) reactive extrusion or melt cracking of plastics can be performed to obtain pyrolysis oil.
  • step (ii) the pyrolysis oil can be separated to obtain a stream A containing hydrocarbons having boiling point less than 70 °C, a stream B containing hydrocarbons having boiling point 70 °C to 140 °C, and a stream C containing hydrocarbons having boiling point greater than 140 °C.
  • the stream B can be reformed to obtain a stream D containing Ce to Cs aromatics.
  • the Ce to Cs aromatics can be benzene, toluene and xylene and the stream D can contain benzene, toluene, and xylene.
  • the stream A can be sent to a gasoline pool.
  • the reactive extrusion or melt cracking of the plastics can include depolymerizing the plastics at a depolymerization temperature sufficient to produce a hydrocarbonaceous wax stream, and catalytic cracking of the hydrocarbonaceous wax stream in presence of a cracking catalyst under cracking conditions sufficient to produce the pyrolysis oil, wherein the cracking conditions can include a cracking temperature that is lower than, equal to, or higher than the depolymerization temperature.
  • the depolymerization of the plastics can be performed in an extruder/twin screw reactor/auger.
  • the pyrolysis oil can be separated into the streams A, B, and C by atmospheric distillation with boiling points cuts at 70 °C and 140 °C.
  • the stream A can contain a hydrocarbon fraction with upper boiling point cut of 70 °C, from the pyrolysis oil.
  • the stream B can contain a hydrocarbon fraction with lower boiling point cut of 70 °C and an upper boiling point cut of 140 °C, from the pyrolysis oil.
  • the C stream can contain a hydrocarbon fraction with lower boiling point cut of 140 °C, from the pyrolysis oil.
  • the stream C can be recycled to the hydrocarbonaceous wax catalytic cracking step. Reforming in step (iii) can also produce nonaromatics and non Ce to Cs aromatics (e.g. aromatic hydrocarbons other than benzene, toluene and xylene).
  • a stream E containing at least a portion of the non-aromatics and non Ce to Cs aromatics produced during reforming can be recycled to the hydrocarbonaceous wax catalytic cracking step.
  • a stream F containing a portion of a hydrogen (H2) containing gas from the reforming step (iii) can be recycled to the hydrocarbonaceous wax catalytic cracking step.
  • the reforming (e.g., in step (d) of the first process and in step (iii) of the second process) can be performed with processes and systems known in the art.
  • the reforming conditions can include a temperature of 400 °C to 600 °C, preferably 450 °C to 550 °C, and/or a pressure of 2 barg to 30 barg.
  • the reforming can be performed in presence of H2.
  • 112 to hydrocarbon (e.g., H2 and hydrocarbon fed to the reforming step) mole ratio during reforming can be 2: 1 and 9: 1.
  • the reforming can be performed in presence of a reforming catalyst.
  • the reforming catalyst can be a reforming catalyst known in the art.
  • the reforming catalyst can contain platinum (Pt) and rhenium (Re) on alumina, Pt on alumina, metal loaded zeolite, or any combinations thereof.
  • the metal loaded zeolite can contain one or more dehydrogenating metal(s) including but not limited to Pt, palladium (Pd), gallium (Ga) and/or nickel (Ni).
  • the reforming process can be semi-regenerative reforming process or continuous catalytic reforming process, and the reforming can be performed in a semi -regenerative reformer unit or continuous catalytic reformer unit.
  • the cracking (e.g., in optional step (e) of the first process) can be steam cracking or catalytically cracking.
  • the steam cracking can be performed using dilution steam, with processes and systems known in the art.
  • the steam cracking conditions can include a temperature of 750 °C to 900 °C, a pressure of atmospheric pressure to 6 barg, at residence time of 50 ms to 1 s or less, or any combinations thereof.
  • the catalytic cracking can be performed in a fluidized bed catalytic cracking (FCC) unit or a fixed bed catalytic cracking unit.
  • the catalytic cracking conditions can include a temperature of 500 °C to 800 °C, a pressure of atmospheric pressure to 10 barg, a contact time of less than 5s, or any combinations thereof.
  • the plastics from which the pyrolysis oil can be obtained from plastic containing waste, such as post-consumer plastic containing waste.
  • the plastics can contain chlorides and at least a portion of the chlorides can be sent to the reforming step (e g., step (d) of the first process and step (iii) of the second process) through the process steps described herein.
  • the chloride can increase the activity of the reforming catalyst.
  • chloride can be fed to the reforming step (e.g., to step (d) of the first process and to step (iii) of the second process) at a concentration 0.1 ppm to 15 ppm.
  • wt.% refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume, or the total moles of material that includes the component.
  • 10 moles of component in 100 moles of the material is 10 mol.% of component.
  • FIG. l is a schematic of an example of the present invention to produce Ce to Cs aromatics and optionally light gas olefins.
  • FIG. 2 is a schematic of an embodiment of the present invention to produce Ce to Cs aromatics and optionally light gas olefins using the system of FIG. 1, system 100.
  • FIG. 3 is a schematic of a second embodiment of the present invention to produce Ce to Cs aromatics and optionally light gas olefins using the system of FIG. 1, system 100.
  • FIG. 4 is a schematic of a third embodiment of the present invention to produce Ce to Cs aromatics and optionally light gas olefins using the system of FIG. 1, system 100.
  • FIG. 5 is a schematic of a second example of the present invention to produce Ce to Cs aromatics and optionally light gas olefins.
  • the solution can include using a hydroprocessing unit configured to hydroprocess hydrocarbons at a pressure below 100 barg.
  • the hydroprocessing unit can be positioned upstream to a reformer used for producing aromatics and/or to a cracking unit e g. a steam cracker or catalytic cracking unit used for producing light olefins.
  • use of the upstream hydroprocessing unit can increase naphthenic content of the reformer feed, such as to 30 wt.% or above, increase the mono aromatics in reformer feed, and/or enrich the reformer feed for producing aromatics especially C>> to Cs aromatics.
  • the higher aromatics (2 rings or higher, or aromatics with side chain) can be converted to mono aromatics or naphthenes in the hydroprocessing unit, increasing naphthenic content of the reformer feed.
  • Use of the upstream hydroprocessing unit also increases the amount of hydrocarbon being reformed, and decrease olefin content in the reformer feed.
  • amount of hydrocarbon being reformed can be increased by increasing the amount of 70 to 140 °C boiling stream which can be fed to the reformer through upgrading of heavy ends of crude oil at the hydroprocessing unit.
  • the use of the upstream hydroprocessing unit may not be used.
  • Ce to Cs aromatics and optionally light gas olefins can be produced from pyrolysis oil obtained from plastics, such as waste plastics. Benefits of this process include the use of recycled plastics to efficiently produce BTX and optionally olefins.
  • the units shown in the figures can include one or more heating and/or cooling devices (e.g., insulation, electrical heaters, jacketed heat exchangers in the wall) or controllers (e.g., computers, flow valves, automated values, etc.) that can be used to control temperatures and pressures of the processes. While only one unit is usually shown, it should be understood that multiple units can be housed in one unit.
  • a reactor shown or described unless otherwise mentioned can be a fixed bed reactor, moving bed reactor, trickle-bed reactor, rotating bed reactor, slurry reactor or fluidized bed reactor.
  • the system 100 can include a hydroprocessing unit 120, a separation unit 122, a reforming unit 124 and an optional cracking unit 126.
  • the optional cracking unit 126 can be steam cracking unit or a catalytic cracking unit
  • a first stream 101 containing hydrocarbons from crude oil and/or pyrolysis oil can be fed to the hydroprocessing unit 120.
  • the first stream 101 can be hydroprocessed to obtain a hydroprocessed product.
  • a second stream 102 containing the hydroprocessed product can exit the hydroprocessing unit 120 and can be fed to the separation unit 122.
  • the second stream can be separated into a third stream 103, a fourth stream 104, and a fifth stream 105.
  • the third stream 103 can contain a hydrocarbon fraction having an upper boiling point cut of 70 °C.
  • the fifth stream 104 can contain a hydrocarbon fraction having lower boiling point cut of 70 °C and upper boiling point cut of 140 °C.
  • the fifth stream 105 can contain a hydrocarbon fraction having lower boiling point cut of 140 °C.
  • the third stream 103 can be fed to the optional cracking unit 126 and can be cracked e.g. via steam cracking or catalytic cracking to form light gas olefins.
  • a light gas olefins stream 127 containing the light gas olefins can exit the cracking unit 126.
  • At least a portion of the fifth stream 105 can be recycled to the hydroprocessing unit 120 and can be hydroprocessed.
  • the 105 can be sent to the cracking unit 126 and can be cracked e g. via steam cracking or catalytic cracking to produce light gas olefins.
  • the third stream 103 and the optional fifth stream portion can be fed to cracking unit 126 as separate streams or can be combined and fed as a combined stream (not shown).
  • the fourth stream 104 can be fed to the reforming unit 124 and reformed to form Ce to Cx aromatics.
  • a sixth stream 106 containing Ce to Cs aromatics can exit the reforming unit 124. Reforming in the reforming unit 124 can also produce non-aromatics and non-Ce to Cs aromatics (e.g. aromatics other than Ce to Cs aromatics).
  • a seventh stream 107 containing at least a portion of the non-aromatics and non- Ce to Cs aromatics from the reforming unit 124 can be recycled to the hydroprocessing unit 120 and can be hydroprocessed.
  • the first stream 101 can be obtained by atmospheric distillation of crude oil.
  • the system 200 can include a crude distillation unit (CDU) 230 and the system 100.
  • a stream 232 containing crude oil can be fed to the CDU 230.
  • the crude oil can be separated through atmospheric distillation to form the first stream 101, an eighth stream 208 and a ninth stream 209.
  • the first stream 101, in system 200 can contain a hydrocarbon fraction having lower boiling point cut of 140 °C, separated from crude oil in the CDU 230.
  • the first stream can be fed to the hydroprocessing unit 120 of the system 100, and can be processed in the system 100 as described above, e.g., for FIG. 1.
  • the eighth stream 208 can contain a hydrocarbon fraction having lower boiling point cut of 70 °C and upper boiling point cut of 140 °C, separated from crude oil in the CDU 230.
  • the eight stream 208 can be fed to the reforming unit 124 of the system 100, and can be reformed to obtain C to Cs hydrocarbons.
  • the eighth stream 208 and the fourth stream 104 can be fed to the reforming unit 124 separately or as a combined stream.
  • the ninth stream 209 can contain a hydrocarbon fraction having upper boiling point cut of 70 °C, separated from crude oil in the CDU 230.
  • the ninth stream 209 can be fed to the optional cracking unit 126 of the system 100, and can be cracked e.g. via steam cracking or catalytic cracking to obtain light gas olefins.
  • the ninth stream 209, the third stream 103, optional fifth stream portion can be fed to the optional cracking unit 126 separately or at any combinations.
  • the first stream 101 can be obtained by atmospheric distillation of crude oil and pyrolysis oil.
  • the pyrolysis oil can be plastic pyrolysis oil, e.g., can be obtained from plastics.
  • FIG. 3 a system and process for producing Ce to Cs aromatics and optionally light gas olefins using system 100 according to a second embodiment of the present invention is described.
  • the system 300 can include a plastics depolymerization unit 342, a catalytic cracking unit 344, a CDU 330, and the system 100.
  • Pyrolysis oil can be produced from plastics using the plastics depolymerization unit 342 and the catalytic cracking unit 344.
  • Plastics 346 can be fed to the plastic depolymerization unit 342.
  • plastics can be depolymerized to form hydrocarbonaceous wax.
  • the hydrocarbonaceous wax 348 from the depolymerization unit 342 can be fed to the catalytic cracking unit 344.
  • the hydrocarbonaceous wax can be cracked in presence of a cracking catalyst to produce the pyrolysis oil.
  • the pyrolysis oil 350 from the catalytic cracking unit 344, and a stream 332 containing crude oil can be fed to the CDU 330.
  • the pyrolysis oil and crude oil can be fed to the CDU as separate feeds or as a combined feed.
  • crude oil and pyrolysis oil mixture can be separated through atmospheric distillation to form the first stream 101, an eighth stream 308 and a ninth stream 309.
  • the first stream 101 in system 300, can contain a hydrocarbon fraction having lower boiling point cut of 140 °C, separated from crude oil and pyrolysis oil mixture in the CDU 330.
  • the first stream 101 can be fed to the hydroprocessing unit 120 of the system 100, and can be processed in the system 100 as described above, e.g., for FIG. 1.
  • the eighth stream 308 can contain a hydrocarbon fraction having lower boiling point cut of 70 °C and upper boiling point cut of 140 °C, separated from crude oil and pyrolysis oil in the CDU 330.
  • the eighth stream 308 can be fed to the reforming unit 124 of the system 100 and can be reformed to obtain C>, to Cs hydrocarbons.
  • the eighth stream 308 and the fourth stream 104 can be fed to the reforming unit 124 separately or as a combined stream.
  • the ninth stream 309 can contain a hydrocarbon fraction having upper boiling point cut of 70 °C, separated from crude oil and pyrolysis oil in the CDU 330.
  • the ninth stream 309 can be fed to the hydroprocessing unit 120 of the system 100.
  • the ninth stream 309 and the first stream 101 can be fed to the hydroprocessing unit 120 separately or as a combined feed.
  • the plastics depolymerization unit 342, and the catalytic cracking unit 344 are not a part of the system 300, and pyrolysis oil, e.g. produced using a separate system and process, along with crude oil can be fed to the CDU.
  • the first stream 101 can contain pyrolysis oil.
  • the pyrolysis oil can be plastic pyrolysis oil, e.g., can be obtained from plastics.
  • the system 400 can include a plastics depolymerization unit 442, a catalytic cracking unit 444, and the system 100.
  • Pyrolysis oil can be produced from plastics using the plastics depolymerization unit 442 and the catalytic cracking unit 444.
  • Plastics 446 can be fed to the plastics depolymerization unit 442.
  • plastics can be depolymerized to form hydrocarbonaceous wax.
  • the hydrocarbonaceous wax 448 from the depolymerization unit 442 can be fed to the catalytic cracking unit 444.
  • the hydrocarbonaceous wax can be cracked in presence of a cracking catalyst to produce the pyrolysis oil.
  • the pyrolysis oil from catalytic cracking unit 444 can be fed to the system 100, via stream 101 and can be processed as described above, e.g., in FIG. 1.
  • System 500 can include a plastics depolymerization unit 502, a catalytic cracking unit 504, a separation unit 506, and a reforming unit 508.
  • Plastics 501 can be fed to the plastic depolymerization unit 502.
  • plastics can be depolymerized to form hydrocarbonaceous wax.
  • the hydrocarbonaceous wax 503 from the depolymerization unit 502 can be fed to the catalytic cracking unit 504.
  • the hydrocarbonaceous wax can be cracked in presence of a cracking catalyst to produce pyrolysis oil.
  • a stream 505 containing the pyrolysis oil from the catalytic cracking unit 504 can be fed to the separation unit 506.
  • the stream 505 can be separated into a stream A 510, a stream B 511, and a stream C 512.
  • the stream A 510 can contain a hydrocarbon fraction having upper boiling point cut of 70 °C, separated from pyrolysis oil in the separation unit 506.
  • the stream B 511 can contain a hydrocarbon fraction having lower boiling point cut of 70 °C and upper boiling point cut of 140 °C, separated from pyrolysis oil in the separation unit 506.
  • the stream C 512 can contain a hydrocarbon fraction having lower boiling point cut of 140 °C, separated from pyrolysis oil in the separation unit 506.
  • the stream C 512 can be recycled to the catalytic cracking unit 504 and can be catalytically cracked to produce pyrolysis oil.
  • the stream B 511 can be fed to the reforming unit 508 and can be reformed to obtain Cr> to Cs aromatics.
  • a stream D 513 containing Cs to Cs aromatics can exit the reforming unit 508. Reforming in the reforming unit 508 can also produce non-aromatics and non- Ce to Cs aromatics (e.g. aromatics other than Ce to Cs aromatics).
  • a stream E 514 containing at least a portion of the non-aromatics and non- Ce to Cs aromatics from the reforming unit 508 can be recycled to the catalytic cracking unit 504 and can be catalytically cracked to produce pyrolysis oil.
  • a stream F 515 containing H2 containing gas from the reforming unit 508 can be recycled to the catalytic cracking unit 504.
  • the H2 containing gas from the reforming unit can contain at least a portion of the H2 added and/or H2 produced during reforming.
  • the stream A 510 can be sent to and/or mixed with a gasoline pool, e.g. gasoline pool of a refinery.
  • Hydroprocessing in the hydroprocessing unit 120 can include hydrotreating, and/or hydrocracking of the feed.
  • the hydrocarbon feed (e.g., introduced via streams 101, 105, 107, and/or 309) in the unit 120 can be hydroprocessed in presence of a dissolved catalyst and a fixed bed catalyst to form the hydroprocessed product.
  • Hydroprocessing in the unit 120 can be performed at a low pressure, such as at a pressure below 100 barg.
  • the hydroprocessing conditions in unit 120 can include: i) a pressure of 30 barg to 100 barg, or at least any one of, equal to any one of, or between any two of 30, 40, 50, 60, 70, 80, 90 and 100 barg; ii) a temperature 300 °C to 600 °C, preferably 350 °C to 500 °C, or at least any one of, equal to any one of, or between any two of 300, 350, 400, 450, 500, 550 and 600 °C; or iii) a weight hourly space velocity (WHSV) of 0.5 to 2 hr' 1 , or at least any one of, equal to any one of, or between any two of 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, and 2 hr' 1 , or any combinations thereof.
  • WHSV weight hourly space velocity
  • Hydroprocessing can be performed in presence of hydrogen (H2).
  • H2 can be fed to the hydroprocessing unit 120 via one or more of the hydrocarbon feed streams (e.g., 101, 105, 107, and/or 309) and/or separately.
  • H2 and hydrocarbon e.g., introduced via stream(s) 101, 105, 107, and/or 309 can be fed to the hydroprocessing unit 120 at volume ratio of 200 Nm 3 : l m 3 to 2000 Nm 3 : l m 3 , or at least any one of, equal to any one of, or between any two of 200: 1, 300:1, 400: 1, 500: 1, 600: 1, 700: 1, 800: 1, 900: 1, 1000: 1, 1100: 1, 1200: 1, 1300: 1, 1400: 1, 1500: 1, 1600: 1, 1700: 1, 1800: 1, 1900: 1, and 2000: 1 Nm 3 : m 3 .
  • the dissolved catalyst can contain Ni and/or Mo. In some aspects, the dissolved catalyst can contain metal octanoates, and/or naphthenates. In some aspects, the dissolved catalyst can contain Ni octanoates, Ni naphthenates, Mo octanoates, or Mo naphthenates, or any combinations thereof. In some aspects, Ni octanoates, Ni naphthenates, Mo octanoates, and/or Mo naphthenates independently can be in a hydrocarbon base. In some aspects, the dissolved catalyst can be a catalyst solubilized in the feed and can form a homogeneous catalyst when mixed with feed (e.g. hydroprocessing feed).
  • feed e.g. hydroprocessing feed
  • no additional solvent can be used for dissolving the catalysts e.g. metal naphthenates and/or octanoates in the feed.
  • the metal octanoates and/or naphthenates can be present in a liquid hydrocarbon of the feed, as dissolved organic salts.
  • the fixed bed catalyst can include Co, Ni, Mo and/or W on a support.
  • the fixed bed catalyst can contain Co and Mo on a support; Ni and Mo on a support; Co, Ni, and Mo on a support; Ni and W on a support; or Ni, W, and Mo on a support, or any combinations thereof.
  • the fixed bed catalyst support can be alumina, silica, aluminosilicates or zeolite or any combinations thereof.
  • the zeolite can be a X-type zeolite, Y-type or USY-type zeolite, mordenite, faujasite, nano-crystalline zeolite, MCM mesoporous material, SBA-15, silico-alumino phosphate, gallophosphate, titanophosphate, ZSM-5, ZSM- 11, ferrierite, heulandite, zeolite- A, erionite, and chabazite, or any combinations thereof.
  • the reforming unit e.g., 124 and/or 508
  • hydrocarbons can be reformed to form Ce to Cx aromatic hydrocarbons, such as benzene, toluene, and xylene.
  • the reforming conditions in unit e.g., 124 and/or 508 can include a temperature of 400 °C to 600 °C, preferably 450 °C to 550 °C, or at least any one of, equal to any one of, or between any two of 400, 450, 500, 550, and 600 °C and/or a pressure of 2 barg to 30 barg or at least any one of, equal to any one of, or between any two of 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28 and 30 barg.
  • Reforming can be performed in presence of H2.
  • H2 can be fed to the reforming unit, through the one or more hydrocarbon feed streams to the reforming unit (e.g., stream 104 for unit 124; stream 511 for unit 508), and/or separately.
  • the H2 and hydrocarbons can be fed to the reforming unit at a mole ratio of 2: 1 to 9: 1 or at least any one of, equal to any one of, or between any two of 2: 1, 3: 1, 4:1, 5:1, 6:1, 7:1, 8:1, and 9:1.
  • Reforming can be performed in presence of a reforming catalyst.
  • the reforming catalyst can contain Pt and Re on alumina; Pt on alumina; metal loaded zeolite; or any combinations thereof.
  • the metal loaded zeolite can contain one or more dehydrogenating metal including but not limited to Pt, Pd, Ga and/or Ni.
  • Reforming in units 124, 508 can be performed according to systems and processes known in the art.
  • the reforming process can be semi -regenerative reforming process or continuous catalytic reforming process, and reforming unit (e.g., 124 and/or 508) can be a semi-regenerative reforming unit or a continuous catalytic reforming unit.
  • the reforming catalyst can be included in the semi-regenerative reforming unit as fixed bed catalyst and in the continuous catalytic reformer unit as a moving bed catalyst.
  • the reforming catalyst can be regenerated according to methods known in the art.
  • the reforming unit e g., 124 and/or 508), can include multiple reactors, such as 3 or more reactors. The hydrocarbon feed to the reactors can be heated prior to feeding to the reactors.
  • the optional cracking unit 126 can be a steam cracking unit or a catalytic cracking unit.
  • the hydrocarbon feed to the cracking unit 126 e.g., introduced via streams 103, 209, optional portion of 105 to unit 126) can be cracked, e g. via steam cracking or catalytic cracking to form light gas olefins.
  • the light gas olefins can include ethylene, propylene and/or butylene.
  • the hydrocarbon feed can be steam cracked in presence of steam, such as dilution steam.
  • the steam cracking conditions in the cracking unit 126 can include i) a temperature of 750 °C to 900 °C or at least any one of, equal to any one of, or between any two of 750, 775, 800, 825, 850, 875 and 900 °C; ii) a pressure of atmospheric pressure to 6 barg, or at least any one of, equal to any one of, or between any two of atmospheric pressure, 2 barg, 3 barg, 4 barg, 5 barg and 6 barg; iii) or a residence time of 0.05 s to 1 s, or at least any one of, equal to any one of, or between any two of 0.05, 0.08, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 and 1 s; or any combinations thereof.
  • the catalytic cracking conditions in the cracking unit 126 can include i) a temperature of 500 °C to 800 °C, or at least any one of, equal to any one of, or between any two of 500, 525, 550, 575, 600, 625, 650, 675, 700, 725, 750, 775, and 800 °C; ii) a pressure of atmospheric pressure to 10 barg or at least any one of, equal to any one of, or between any two of atmospheric pressure, 2 barg, 3 barg, 4 barg, 5 barg, 6 barg, 7 barg, 8 barg, 9 barg and 10 barg; iii) a contact time of less than 5s; or any combinations thereof.
  • Pyrolysis oil can be produced by reactive extrusion/melt cracking of plastics, using the plastics depolymerization unit (e.g., 342, 442, and/or 502) and the catalytic cracking unit (e.g., 344, 444, and/or 504).
  • plastics depolymerization unit e.g., 342, 442, and/or 502
  • catalytic cracking unit e.g., 344, 444, and/or 504
  • the plastics feed (e.g., 346, 446, and/or 501) can be a mixed plastic feed, and can contain one or more of polyolefins (e g., polyethylenes, ethylene alpha-olefin copolymers, polypropylenes or like), polystyrenes, polyesters (e.g., poly alkylene terephthalates), polyvinyl chloride, and polyamides (e.g., nylon, polyphthalamides or like).
  • the plastics can be obtained from plastics containing waste, such as plastics containing post-consumer waste.
  • the plastic feed can be depolymerized to form hydrocarbonaceous wax.
  • the average molecular weight of the hydrocarbonaceous wax e.g., of the compounds in the hydrocarbonaceous wax
  • the depolymerization can be performed in presence of a catalyst.
  • the catalyst can include a liquid catalyst and/or a solid catalyst.
  • the liquid catalyst can contain one or more organometallic compounds, such octanoates and/or naphthenates of a transition metal, such as Ni, Mo, Co, or W.
  • the liquid catalyst can be a catalyst dissolved in the plastic melt.
  • the liquid catalyst can be a homogeneous catalyst in the plastic melt.
  • the solid catalyst can contain an inorganic oxide, aluminosilicate, zeolite, MCM mesoporous material, SBA-15, a silico-alumino phosphate, gallium phosphate, titanophosphate, or a molecular sieve, or combinations thereof.
  • the zeolite can be ZSM-5, an X-type zeolite, a Y-type zeolite, a USY- zeolite, mordenite, faujasite, or nano-crystalline zeolite, or any combinations thereof.
  • the solid catalyst can be a heterogeneous catalyst in the plastic melt.
  • the solid catalyst can remain in solid state in the plastic melt.
  • the depolymerization unit (342, 442, and/or 502) can include an extruder. The plastics and catalysts can be fed to the extruder using one or more feeders, e.g., from a throat hopper and/or any side feeders.
  • the plastics and catalysts can be fed to the extruder, e.g., to a barrel of the extruder, separately or at any combinations, e.g., blended combinations.
  • the extruder can have a single screw, left handed screw, right handed screw, neutral screw, kneading screw, multiple screws, intermeshing co-rotating or counter rotating screws, non-intermeshing co-rotating or counter rotating screws, reciprocating screws, screws with pins, screws with screens, barrels with pins, rolls, rams, helical rotors, co-kneaders, disc-pack processors, various other types of extrusion equipment, or combinations comprising at least one of the foregoing.
  • the plastics feed in the extruder barrel can be heated with one or more heaters arranged along the length of the extruder barrel. In the extruder barrel the plastics feed can be heated, melted, and depolymerized to form the hydrocarbonaceous wax. In some aspects, the plastics feed in the extruder barrel can be depolymerized at a temperature of 300 to 500 °C, or at least any one of, equal to any one of, or between any two of 300, 320, 340, 360, 380, 400, 420, 440, 460, 480, and 500 °C. The residence time of the plastics in the extruder can be less than an hour such as 1 min to 15 min.
  • the extruder can contain one or more vents configured to introduce and/or withdraw one or more gases into and/or from the extruder barrel.
  • the plastic melt and/or hydrocarbonaceous wax can be extruded from the extruder through a die.
  • the hydrocarbonaceous wax from the extruder of the depolymerization unit can be fed to the catalytic cracking unit.
  • the hydrocarbonaceous wax can be catalytically cracked in presence of a cracking catalyst to form pyrolysis oil.
  • the cracking catalyst can contain a zeolite and/or a metal loaded zeolite.
  • the zeolite can be ZSM-5.
  • metal can be a transition metal, such as Mg, Ni, and/or Co.
  • the hydrocarbonaceous wax in the catalytic cracking unit (e.g., 344, 444, and/or 504) can be catalytically cracked in a fixed bed reactor or a fluidized bed reactor.
  • the catalytic cracking of the hydrocarbonaceous wax (e.g., in the catalytic cracking unit 344, 444, and/or 504) can be performed at a temperature lower than, equal to, or higher than the temperature at which plastics feed was depolymerized to form the hydrocarbonaceous wax (e.g., in the depolymerization unit 342, 442, and/or 502).
  • the catalytic cracking conditions in the catalytic cracking unit 344, 444, and/or 504 can include a temperature of 350 to 500 °C, or at least any one of, equal to any one of, or between any two of 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, and 500 °C, a pressure of 1 to 6 bara, or any combinations thereof.
  • the average molecular weight of the pyrolysis oil (e.g., of the compounds in the pyrolysis oil) can be at least 3 times lower than the average molecular weight of the hydrocarbonaceous wax (e.g., of the compounds in the hydrocarbonaceous wax).
  • the pyrolysis oil can contain paraffins, isoparaffins, olefins, naphthenes, and aromatic hydrocarbons.
  • the plastics feed can contain chloride containing plastics such as polyvinyl chloride.
  • a portion of the chlorides from the plastics feed can be fed to the reformer unit (e g , 124 and/or 508) through the process steps described herein.
  • chloride can increase the activity of the reforming catalyst.
  • chloride can be fed to the reformer unit 124, 508 at a concentration of 0.1 ppm to 15 ppm, or at least any one of, equal to any one of, or between any two of 0. 1 , 1 , 2, 4, 6, 8, 10, 12, 14 and 15 ppm.
  • the second stream 102 can contain saturated hydrocarbons having boiling point less than 350 °C. In some aspects, at least 70 wt.% of the hydrocarbons in the second stream 102 can be saturated hydrocarbons having boiling point less than 350 °C.
  • the second stream can contain: i) 10 wt.% to 40 wt.%, or at least any one of, equal to any one of, or between any two of 10, 15, 20, 25, 30, 35, and 40 wt.% of naphthenes; ii) 2 wt.% to 20 wt.%, or at least any one of, equal to any one of, or between any two of 2, 3, 4, 6, 8, 10, 12, 14, 16, 18 and 20 wt.% of aromatics; and iii) paraffins and isoparaffins with total concentration of 50 to 85 wt.% or at least any one of, equal to any one of, or between any two 50, 55, 60, 65, 70, 75, 80 and 85 wt.%, based on the total weight of the second stream, n some aspects, the olefin content of the second stream 102 can be less than 8 wt.%, or less than 5 wt.%, or less than 3 wt.%, or less than 1 wt.
  • the fourth stream 104 and the stream B 511 can contain hydrocarbons having boiling points from 70 °C to 140 °C.
  • he fourth stream 104 can contain: i) 25 wt.% to 50 wt.%, or at least any one of, equal to any one of, or between any two of 25, 30, 35, 40, 45 and 50 wt.% of naphthenes; ii) 10 wt.% to 35 wt.%, or at least any one of, equal to any one of, or between any two of 10, 15, 20, 25, 30 and 35 wt.% of aromatics; and iii) paraffins and isoparaffins with total concentration of 30 to 55 wt.% or at least any one of, equal to any one of, or between any two 30, 35, 40, 45, 50, and 55 wt.%, based on the total weight of the fourth stream respectively.
  • the olefin content of the fourth stream 104 can be less than 8 wt.%, or less than 5 wt.%, or less than 3 wt.% or less than 1 wt.%, or the fourth stream 104 can be essentially free of olefins.
  • the composition of the stream B 511 can be similar to the fourth stream 104.
  • the third stream 103 and the stream A 510 can contain hydrocarbons having boiling points below 70 °C.
  • the third stream 103 can contain paraffins and isoparaffins with total concentration of 90 to 100 wt.% or at least any one of, equal to any one of, or between any two 90, 95, 96, 97, 98, 99, 99.3, 99.5, 99.8, 99.9 and 100 wt.%, based on the total weight of the third stream, respectively.
  • the olefin content of the third stream 103 can be less than 8 wt.%, or less than 5 wt.%, or less than 3 wt.% or less than 1 wt.%, or the third stream can be essentially free of olefins.
  • the aromatics content of the third stream 103 can be less than 8 wt.%, or less than 5 wt.%, or less than 3 wt.% or less than 1 wt.%, or the third stream can be essentially free of aromatics.
  • the composition of the stream A 510 can be similar to the third stream 103.
  • the fifth stream 105 and the stream C 512 can contain hydrocarbons having boiling points above 140 °C.
  • the ethylene, propylene and/or butylene from the light gas olefins streams, (127), can be purified/separated by one or more steps to obtain separated streams containing polymer grade ethylene, propylene and/or butylene.
  • the benzene, toluene and xylene from the sixth stream 106, and/or the stream D 513 can be purified/separated by one or more steps to obtain separated streams containing benzene, toluene and xylene.
  • the systems and processes described herein can also include various equipment that is not shown and is known to one of skill in the art of chemical processing. For example, some controllers, piping, computers, valves, pumps, heaters, thermocouples, pressure indicators, mixers, heat exchangers, and the like may not be shown.
  • a hydrocarbon fraction having an upper boiling point cut of 350 °C from crude oil was hydroprocessed at 380 °C, 60 barg, 1 h' 1 and H hydrocarbon feed ratio 400 Nm 3 /m 3 and in presence of a hydroprocessing catalyst (a combination of a hydrocracking catalyst Ni/W and a hydrotreating catalyst Co, Ni, Mo) to obtain a hydroprocessed stream.
  • a hydroprocessing catalyst a combination of a hydrocracking catalyst Ni/W and a hydrotreating catalyst Co, Ni, Mo
  • the hydroprocessed stream was distilled in an atmospheric column and was separated into a first hydrocarbon fraction, fraction 1 , having upper boiling point cut of 70 °C, a second hydrocarbon fraction, fraction 2, having lower boiling point cut of 70 °C and upper boiling point cut of 140 °C, and a third hydrocarbon fraction, fraction 3, having lower boiling point cut of 140 °C.
  • Paraffins, isoparaffins, olefins, naphthenes and aromatics (PIONA) compositions of the hydrocarbon fractions 1, 2 and 3, based on the total weight of the hydroprocessed stream, are provided in Table 1.
  • the hydrocarbon fraction 1 was steam cracked to obtain light gas olefins.
  • the hydrocarbon fraction 2 was reformed in a naphtha reformer to obtain benzene, toluene and xylene.
  • the hydrocarbon fraction 2 had more naphthenes, compared to two commonly used reformer feed (Table 2).
  • higher amounts of aromatics e.g., benzene, toluene, and xylene
  • hydrocarbon fraction 1 was completely paraffinic and was without aromatics and olefins, providing a good feed for the steam cracking/catalytic cracking.
  • Table 2 Typical PIONA composition of feed to the naphtha reformer.
  • West Texas blend crude oil with an end boiling point of 750 °C was hydroprocessed at 450 °C, 40 barg, 1 h' 1 and I /hydrocarbon feed ratio 400 Nm 3 /m 3 and in presence of a hydroprocessing catalyst (a combination of a hydrocracking catalyst Ni/W and a hydrotreating catalyst Co, Ni, Mo) to obtain a hydroprocessed stream.
  • the hydroprocessed stream was distilled in an atmospheric column and was separated into a first hydrocarbon fraction, fraction 4, having upper boiling point cut of 70 °C, a second hydrocarbon fraction, fraction 5, having lower boiling point cut of 70 °C and upper boiling point cut of 140 °C, and a third hydrocarbon fraction, fraction 6, having lower boiling point cut of 140 °C.
  • PIONA compositions of the hydrocarbon fractions 4 and 5, based on the total weight of the hydroprocessed stream, are provided in Table 3.
  • the hydrocarbon fraction 4 was steam cracked to obtain light gas olefins.
  • the hydrocarbon fraction 5 was reformed in a naphtha reformer to obtain benzene, toluene and xylene. 19.7 wt.% and 31 wt.% of the hydroprocessed stream was fractionated into the fractions 4 and 5, respectively, and the remaining amount was fractionated into the fraction 6.
  • the hydrocarbon fraction 5 was primarily paraffinic and naphthenic, ⁇ 70 wt.% upon normalization, providing a good feed for reforming.
  • hydrocarbon fraction 5 31 wt.% of hydrocarbon fraction 5 was naphthenic, providing a good reforming feed for forming benzene, toluene and xylene. Olefin content of hydrocarbon fraction 4 was low, and was predominantly paraffinic, -94.6% upon normalization, providing a good feed for steam cracking/catalytic cracking.
  • a commercial pyrolysis oil having boiling point range 85 °C to 470 °C was hydroprocessed at 400 °C, 60 barg, 1 h' 1 and Fb/hydrocarbon feed ratio 400 NmW and in presence of a hydroprocessing catalyst (a combination of a hydrocracking catalyst Ni/W and a hydrotreating catalyst Co, Ni, Mo) to obtain a hydroprocessed stream.
  • a hydroprocessing catalyst a combination of a hydrocracking catalyst Ni/W and a hydrotreating catalyst Co, Ni, Mo
  • the hydroprocessed stream was distilled in an atmospheric column and was separated into a first hydrocarbon fraction, fraction 7, having upper boiling point cut of 70 °C, a second hydrocarbon fraction, fraction 8, having lower boiling point cut of 70 °C and upper boiling point cut of 140 °C, and a third hydrocarbon fraction, fraction 9, having lower boiling point cut of 140 °C.
  • PIONA compositions of the hydrocarbon fractions 7, 8 and 9, based on the total weight of the hydroprocessed stream, are provided in Table 4
  • the hydrocarbon fraction 7 was steam cracked to obtained light gas olefins.
  • the hydrocarbon fraction 8 was reformed in a naphtha reformer to obtain benzene, toluene and xylene.
  • the hydrocarbon fraction 9 was recycled to the hydroprocessing step.
  • hydrocarbon fraction 8 43.6 wt.%, 39 wt.% and 17.3 wt.% of the fraction 8 was paraffinic, naphthenic and aromatic respectively. Compared to typical reforming feed (Table 2), hydrocarbon fraction 8 had more naphthenes, thus was more suitable for producing benzene, toluene and xylene by reforming. Further, as can be seen from table 4, hydrocarbon fraction 7 was completely paraffinic and was without aromatics and olefins, providing a good feed for the steam cracker/catalytic cracking.
  • Embodiment 1 is a process for selectively producing Ce to Cx aromatics and optionally light gas olefins.
  • the process includes hydroprocessing a first stream containing hydrocarbons from crude oil and/or pyrolysis oil to obtain a second stream containing saturated hydrocarbons having boiling point less than 350 °C.
  • the process further includes separating the second stream to obtain a third stream containing hydrocarbons having boiling point less than 70 °C, a fourth stream containing hydrocarbons having boiling point 70 °C to 140 °C, and a fifth stream containing hydrocarbons having boiling point greater than 140 °C.
  • the process still further includes recycling at least a portion of the fifth stream to the hydroprocessing step (a).
  • the process also includes reforming the fourth stream to obtain a sixth stream containing Ce to Cx aromatics.
  • the process includes optionally cracking the third stream and/or a portion of the fifth stream to obtain light gas olefins.
  • Embodiment 2 is the process of embodiment 1, wherein at least 70 wt.% of the second stream contains the saturated hydrocarbons having boiling point less than 350 °C.
  • Embodiment 3 is the process of any of embodiments 1 or 2, wherein reforming step d) further includes obtaining a seventh stream containing non-aromatics and non Ce to Cx aromatics and optionally recycling at least a portion of the seventh stream to the hydroprocessing step (a).
  • Embodiment 4 is the process of any of embodiments 1 to 3, wherein the hydroprocessing conditions in step (a) include a pressure lower than 100 barg, preferably 30 barg to 100 barg, a temperature 300 °C to 600 °C, weight hourly space velocity 0.5 to 2 hr' 1 , or H2 : hydrocarbon volume ratio of 200 Nm 3 :l m 3 to 2000 Nm 3 : l m 3 of liquid feed, or any combinations or all thereof.
  • Embodiment 5 is the process of any of embodiments 1 to 4, wherein the hydroprocessing in step (a) is performed using a dissolved catalyst containing Ni and/or Mo, and a fixed bed catalyst containing Co, Mo, Ni, W, or any combinations thereof on a support.
  • Embodiment 6 is the process of any of embodiments 1 to 5, wherein the reforming conditions in step (b) include a temperature of 450 °C to 550 °C, a pressure of 2 barg to 30 barg, or H2 : hydrocarbon mole ratio of 2:1 to 9: 1, or any combinations or all thereof.
  • Embodiment 7 is the process of any of embodiments 1 to 6, wherein the reforming in step (d) is performed using a reforming catalyst containing Pt-Re on alumina, Pt on alumina, metal loaded zeolite, or a combinations thereof.
  • Embodiment 8 is the process of any of embodiments 1 to 7, wherein the pyrolysis oil is obtained from plastic.
  • Embodiment 9 is the process of any of embodiments 1 to 8, wherein the pyrolysis oil is obtained from the plastic by depolymerizing the plastic at a depolymerization temperature sufficient to produce a hydrocarbonaceous wax stream, and cracking the hydrocarbonaceous wax stream in the presence of a cracking catalyst under cracking conditions sufficient to produce the pyrolysis oil, wherein the cracking conditions include a cracking temperature that is higher than, or equal to, or lower than the depolymerization temperature.
  • Embodiment 10 is the process of any of embodiments 1 to 9, wherein the first stream contains hydrocarbons having boiling point above 140 °C separated from the crude oil and/or the pyrolysis oil by atmospheric distillation.
  • Embodiment 11 is the process of any of embodiments 1 to 10, wherein the atmospheric distillation further produces a eighth stream containing hydrocarbons having boiling points of 70 °C to 140 °C, and the process further includes reforming the eighth stream.
  • Embodiment 12 is the process of any of embodiments 1 to 11, wherein eighth stream is reformed with the fourth stream to form the sixth stream and the seventh stream.
  • Embodiment 13 is the process of any of embodiments 1 to 12, wherein the atmospheric distillation further produces a ninth stream containing hydrocarbons having boiling point below 70 °C.
  • Embodiment 14 is the process of any of embodiments 1 to 3, wherein the ninth stream is cracked with the third stream to produce the light gas olefins or is sent to the hydroprocessing step.
  • Embodiment 15 is the process of any of embodiments 1 to 14, wherein the first stream contains pyrolysis oil.
  • Embodiment 16 is the process of any of embodiments 1 to 15, wherein the first stream contains condensate, naphtha, light crude oil, or a crude oil hydrocarbon fraction having an upper boiling point cut of 350 °C or whole crude oil, or any combinations or all thereof.
  • Embodiment 17 is a process for selectively producing Ce to Cx aromatics and optionally light gas olefins from plastics.
  • the process includes: a) performing reactive extrusion or melt cracking of plastics to form pyrolysis oil; b) separating the pyrolysis oil to obtain a stream A containing hydrocarbons having boiling point less than 70 °C, a stream B containing hydrocarbons having boiling point 70 °C to 140 °C, and a stream C containing hydrocarbons having boiling point greater than 140 °C; c) reforming the stream B to obtain a stream D containing Cr> to Cs aromatics; and d) optionally mixing the stream A to a gasoline pool of a refinery.
  • Embodiment 18 is the process of embodiment 17, wherein the reactive extrusion or melt cracking of plastics includes depolymerizing of the plastic at a depolymerization temperature sufficient to produce a hydrocarbonaceous wax stream; and catalytic cracking the hydrocarbonaceous wax stream in presence of a cracking catalyst under cracking conditions sufficient to produce the pyrolysis oil, wherein the cracking conditions include a cracking temperature that is higher than, or equal to, or lower than the depolymerization temperature.
  • Embodiment 19 is the process of any of embodiments 17 to 18, further including recycling the stream C to the catalytic cracking step.
  • Embodiment 20 is the process of any of embodiments 17 to 19, wherein at least a portion of hydrogen containing gases, non-aromatics, and non Ce to Cx aromatics obtained from reforming in step (c) is recycled to the catalytic cracking step.

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Abstract

L'invention concerne un procédé de production de composés aromatiques en C6 à C8 et éventuellement d'oléfines de gaz légères à partir de pétrole brut et/ou d'huile de pyrolyse. Le procédé peut comprendre l'hydrotraitement d'un premier flux contenant des hydrocarbures à partir de pétrole brut et/ou d'huile de pyrolyse pour obtenir un deuxième flux contenant des hydrocarbures saturés ayant un point d'ébullition inférieur à 350 °C, la séparation du deuxième flux pour obtenir un troisième flux contenant des hydrocarbures ayant un point d'ébullition inférieur à 70 °C, un quatrième flux contenant des hydrocarbures ayant un point d'ébullition de 70 °C à 140 °C, et un cinquième flux contenant des hydrocarbures ayant un point d'ébullition supérieur à 140 °C, le recyclage d'au moins une partie du cinquième flux vers l'étape d'hydrotraitement, le reformage du quatrième flux pour obtenir un sixième flux contenant des composés aromatiques en C6 à C8, et éventuellement le craquage du troisième flux pour obtenir des oléfines de gaz légères.
EP21794981.7A 2020-12-28 2021-10-12 Production de composés aromatiques btx et d'oléfines de gaz légères à partir de pétrole brut et d'huile de pyrolyse de matière plastique Pending EP4267699A1 (fr)

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WO2024030741A1 (fr) * 2022-08-03 2024-02-08 Eastman Chemical Company Reformage catalytique de raffinat et de naphta contenant des matières recyclées à partir de distillation atmosphérique
US11945771B1 (en) * 2022-11-01 2024-04-02 Chevron Phillips Chemical Company Lp Catalyzed depolymerization of a chemically complex feedstock
US20240352352A1 (en) * 2023-04-19 2024-10-24 Sk Innovation Co., Ltd. Method and system for producing refined hydrocarbons from waste plastic pyrolysis oil
US20240352360A1 (en) * 2023-04-19 2024-10-24 Sk Innovation Co., Ltd. Method and system for producing refined hydrocarbons from waste plastics
US20240352332A1 (en) * 2023-04-19 2024-10-24 Sk Innovation Co., Ltd. Method and system for producing refined hydrocarbons from waste plastics
US20240352331A1 (en) * 2023-04-19 2024-10-24 Sk Innovation Co., Ltd. Method and system for producing refined hydrocarbons and solid coke from waste plastics
WO2024219941A1 (fr) * 2023-04-19 2024-10-24 Sk Innovation Co., Ltd. Procédé et système de production d'hydrocarbures raffinés à partir de déchets plastiques
US20240352347A1 (en) * 2023-04-19 2024-10-24 Sk Innovation Co., Ltd. Method and system for producing refined hydrocarbons from waste plastics

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US20240301302A1 (en) 2024-09-12

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