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WO2016142808A1 - Processus intégré de conversion de déchets plastiques en produits pétrochimiques finaux - Google Patents

Processus intégré de conversion de déchets plastiques en produits pétrochimiques finaux Download PDF

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Publication number
WO2016142808A1
WO2016142808A1 PCT/IB2016/051136 IB2016051136W WO2016142808A1 WO 2016142808 A1 WO2016142808 A1 WO 2016142808A1 IB 2016051136 W IB2016051136 W IB 2016051136W WO 2016142808 A1 WO2016142808 A1 WO 2016142808A1
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WO
WIPO (PCT)
Prior art keywords
hydrocarbon stream
stream
treated
hydrocarbon
catalyst
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Application number
PCT/IB2016/051136
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English (en)
Inventor
Ravichander Narayanaswamy
Krishna Kumar Ramamurthy
Alexander Stanislaus
Mohammad JAVEED
Original Assignee
Sabic Global Technologies, B.V.
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Application filed by Sabic Global Technologies, B.V. filed Critical Sabic Global Technologies, B.V.
Priority to US15/085,402 priority Critical patent/US20160264885A1/en
Publication of WO2016142808A1 publication Critical patent/WO2016142808A1/fr

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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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/07—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
    • C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
    • 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
    • C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • 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
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/301—Boiling range

Definitions

  • the present disclosure relates to the treatment of hydrocarbon streams resulting from pyrolysis of waste plastics for use in downstream processes.
  • Waste plastics contain polyvinylchloride (PVC).
  • PVC polyvinylchloride
  • pyrolysis oils are off -spec for use as a feedstock for steam crackers because steam cracker feed specifications require chloride levels less than 3 ppm, olefin content less than 1 wt%, and boiling end point requirements of 370 °C.
  • a process for converting waste plastics to a high value product comprising converting the waste plastics to a hydrocarbon stream in a liquid phase, contacting the hydrocarbon stream with a hydroprocessing catalyst in the presence of hydrogen to yield a hydrocarbon product comprising Ci to C4 gases and C5+ liquid hydrocarbons, recovering the C5+ liquid hydrocarbons in a treated hydrocarbon stream from the hydrocarbon product, and feeding the treated hydrocarbon stream or a blended hydrocarbon stream comprising the treated hydrocarbon stream to a steam cracker to yield the high value product, wherein the treated hydrocarbon stream or blended hydrocarbon stream meets steam cracker feed requirements for chloride content, olefin content, and boiling end point.
  • Figure 1 illustrates a hydroprocessing system for converting plastic waste to a high value product by simultaneously dechlorinating chloride compounds, hydrogenating olefins, and hydrocracking heavy hydrocarbon molecules contained in a hydrocarbon stream which contains a pyrolysis oil to levels suitable for introduction to a steam cracker.
  • Figure 2 is a graph of the boiling point distribution for a liquid product of a low severity pyrolysis process, showing temperature versus mass percent.
  • Figure 3 is a graph of a staged catalyst sulphiding protocol, showing temperature versus time.
  • references throughout the specification to "an embodiment,” “embodiments,” “another embodiment,” “other embodiments,” “alternative embodiments,” “additional embodiments,” “some embodiments,” and so forth e.g., the use of “additionally” and/or “alternatively” in the context of describing one or more embodiments
  • a particular element e.g., feature, structure, property, and/or characteristic
  • the described element(s) can be combined in any suitable manner in the various embodiments.
  • Embodiments of the process include converting the waste plastics to a hydrocarbon stream in a liquid phase, converting the waste plastics to a pyrolysis light gas stream containing Q to C4 hydrocarbons, contacting the hydrocarbon stream with a hydroprocessing catalyst in the presence of hydrogen (H 2 ) to yield a hydrocarbon product, recovering a treated hydrocarbon stream comprising C5+ hydrocarbons from the hydrocarbon product, recovering a hydroprocessed light gas stream from the hydrocarbon product, feeding the treated hydrocarbon stream or a blended hydrocarbon stream comprising the treated hydrocarbon stream to a steam cracker to yield the high value product, feeding the pyrolysis light gas stream to the steam cracker, feeding the hydroprocessed light gas stream to the steam cracker, or combinations thereof.
  • the treated hydrocarbon stream or blended hydrocarbon stream meets steam cracker feed requirements.
  • the pyrolysis light gas stream may be fed to the steam cracker directly, or after treating the pyrolysis light gas stream in a scrubbing unit to yield a treated pyrolysis light gas stream which is subsequently fed to the steam cracker.
  • the hydroprocessed light gas stream may be fed to the steam cracker directly, or after treating the hydroprocessed light gas stream in a scrubbing unit to yield a treated hydroprocessed light gas stream which is subsequently fed to the steam cracker. Converting the waste plastics to a hydrocarbon stream in a liquid phase and converting the waste plastics to a pyrolysis light gas stream containing Q to C4 hydrocarbons may occur simultaneously via pyrolysis of the waste plastics.
  • Figure 1 illustrates a hydroprocessmg system 100 for converting plastic waste to a high value product by simultaneously dechlorinating chloride compounds, hydrogenating olefins, and hydrocracking heavy hydrocarbon molecules contained in a hydrocarbon stream 12 which contains a pyrolysis oil (e.g., plastic pyrolysis oil, tire pyrolysis oil) to levels suitable for introduction to a steam cracker 30.
  • the system 100 includes a pyrolysis unit 10, a hydroprocessmg reactor 20, a separator 30, and a steam cracker 40. Waste plastic is either placed in the pyrolysis unit 10 or fed to the pyrolysis unit 10 via waste plastic stream 1.
  • the plastic waste stream is converted via pyrolysis reactions to pyrolysis gases and a liquid pyrolysis oil.
  • the pyrolysis gases flow from the pyrolysis unit 10 via a pyrolysis light gas stream 16 directly to the steam cracker 40 or to a scrubbing unit 50.
  • the liquid pyrolysis oil flows from the pyrolysis unit 10 via hydrocarbon stream 12.
  • the hydrocarbon stream 12 feeds to the hydroprocessmg reactor 20, and the reaction product effluent of the hydroprocessmg reactor 20 flows from the hydroprocessmg reactor 20 in the hydrocarbon product stream 22 to the separator 30.
  • a treated product (e.g., in gas or liquid form) is recovered from the hydrocarbon product stream 22 and flows from the separator 30 via treated hydrocarbon stream 32, with one or more of sulphur-containing gases and chlorine-containing gases flowing from the separator 30 in hydroprocessed light gas stream 36.
  • to C 4 hydrocarbon gases which are generated in the hydroprocessing reactor 20 may flow directly to a separator 30, where the Q to C4 hydrocarbon gases are recovered in a hydroprocessed light gas stream 36 for flow directly to the steam cracker 40, to a scrubbing unit 50, or a combination of direct flow to the steam cracker 40 and flow to the scrubbing unit 50 (e.g., a portion of the pyrolysis light gas stream bypasses the scrubbing unit).
  • Embodiments of the disclosure contemplate a second hydroprocessmg reactor and a second separator may be placed in between separator 30 and treated hydrocarbon stream 32.
  • the treated product flowing from the separator 30 in treated hydrocarbon stream 32 may contain residual sulphur, and the second hydroprocessing reactor/second separator combination may treat the treated product flowing from the separator 30 to completely remove the sulphur such that a second treated product flowing in the treated hydrocarbon stream 32 from the second separator contains less than 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0.1 ppmw S based on total weight of the treated hydrocarbon stream 32.
  • d to C 4 hydrocarbon gases generated in the second hydroprocessing reactor may flow from the second hydroprocessing reactor in a second hydroprocessed light gas stream. Similar to the hydroprocessed light gas stream 36 flowing from the separator 30, the second hydroprocessed light gas stream may flow from a second separator directly to the steam cracker 40, to the scrubbing unit 50, or a combination of direct flow to the steam cracker 40 and flow to the scrubbing unit 50 (e.g., a portion of the pyrolysis light gas stream bypasses the scrubbing unit).
  • the treated product in the treated hydrocarbon stream 32 may flow directly (e.g., without any separations or fractionations of the treated hydrocarbon stream 32) or via blended hydrocarbon stream 38 (e.g., without any separations or fractionations of the treated hydrocarbon stream 32 and blended hydrocarbon stream 38) to a steam cracker 40, from which high value products flow in stream 42.
  • Waste plastics which are loaded into or fed to the pyrolysis unit 10 via waste plastic stream 1 may include post-consumer waste plastics.
  • waste plastics which can be used include chlorinated plastics (e.g., chlorinated polyethylene), polyvinylchloride, non-chlorinated plastics (e.g., polyethylene, polystyrene, polypropylene, copolymers, etc.), or mixtures thereof.
  • Waste plastics as disclosed herein also include used tires.
  • Waste plastics in the pyrolysis unit 10 are subjected to a pyrolysis process to convert the waste plastics to one or more pyrolysis oils which flow from the pyrolysis unit 10 via hydrocarbon stream 12.
  • the pyrolysis processes in the pyrolysis unit 10 may be low severity or high severity. Low severity pyrolysis processes may occur at a temperature of 300 °C to 450 °C, may produce pyrolysis oils rich in mono- and di- olefins as well as a significant amount of aromatics, and may include chloride compounds in amounts which cause the hydrocarbon stream 12 to have the chloride compound concentrations disclosed herein.
  • High severity pyrolysis processes may occur at a temperature of 450 °C to 750 °C and may produce pyrolysis oils rich in aromatics.
  • the liquid product of the high severity processes may include chloride compounds which cause the hydrocarbon stream 12 to have the chloride compound concentrations disclosed herein.
  • the pyrolysis unit 10 may be one or more vessels configured to convert waste plastics into gas phase and liquid phase products (e.g., simultaneously).
  • the one or more vessels may contain one or more beds of inert material or pyrolysis catalyst comprising sand, zeolite, or combinations thereof.
  • the pyrolysis catalyst is capable of transferring heat to the components subject to the pyrolysis process in the pyrolysis unit 10.
  • the pyrolysis process may be divided into a first stage which is performed in the first vessel and in a second stage fluidly connected downstream of the first stage which is performed in the second vessel.
  • the first stage may utilize thermal cracking of the waste plastics, and the second stage may utilize catalytic cracking of the waste plastics to yield the hydrocarbon stream 12 flowing from the second stage.
  • the first stage may utilize catalytic cracking of the waste plastics, and the second stage may utilize thermal cracking of the waste plastics to yield the hydrocarbon stream 12 flowing from the second stage.
  • the pyrolysis unit 10 may include one or more equipment configured to convert waste plastics into gas phase and liquid phase products.
  • the one or more equipment may or may not contain any inert material or pyrolysis catalyst as described above. Examples of such equipment include one or more of heated extruders, heated rotating kiln, heated tank-type reactors, empty heated vessels, enclosed heated surfaces where plastic flows down along the wall and cracks, vessels surrounded by ovens or furnaces or other equipment offering a heated surface to assist in cracking.
  • a head space purge gas is utilized in all or a portion of the pyrolysis stage(s) (conversion of waste plastics to a liquid phase and/or gas phase products) to enhance cracking of plastics, produce valuable products, provide a feed for steam cracking, or combinations thereof.
  • the head space purge gas may include can utilize hydrogen (H 2 ), nitrogen (N 2 ), steam, product gases, or combinations thereof. The use of a head space purge gas assists in the dechlorination in the pyrolysis unit
  • the use of hydrogen in the pyrolysis unit 10 has beneficial effects of i) reducing the coke lay down as a result of cracking, ii) keeps catalyst used (if any) in the process in an active condition, iii) improves removal of chloride from stream 1 such that the hydrocarbon stream 12 from pyrolysis unit 10 is substantially dechlorinated with respect to waste plastic stream 1 which minimizes the chloride removal requirement in hydroprocessing reactor 20, iv) reduces diolefins in hydrocarbon stream 12, v) helps operate the pyrolysis unit 10 at reduced temperatures for same levels of conversion of waste plastic stream 1 in the pyrolysis unit 10, or combinations of i) -v).
  • the hydrocarbon stream 12 generally includes one or more pyrolysis oils (e.g., plastic pyrolysis
  • the hydrocarbon stream 12 may include one or more pyrolysis oils as described above which is blended with a heavier oil (e.g., a naphtha or diesel, via spiking stream 14).
  • a heavier oil e.g., a naphtha or diesel
  • blending the treated hydrocarbon stream 32 with a non-chlorinated stream 34 as described for embodiments below may additionally occur; alternatively, the subsequent blending may not occur.
  • the hydrocarbon stream 12 may be spiked with the one or more sulphides, via a spiking stream 14 (discussed in more detail below).
  • Examples of the components which may be included in the hydrocarbon stream 12 include paraffins (n-paraffin, i-paraffin, or both), olefins, naphthenes, aromatic hydrocarbons, or combinations thereof.
  • the group of hydrocarbons may be collectively referred to as a PONA feed (paraffin, olefin, naphthene, aromatics) or PIONA feed (n-paraffin, i- paraffin, olefin, naphthene, aromatics).
  • any paraffin may be included in the hydrocarbon stream 12.
  • paraffins which may be included in the hydrocarbon stream 12 include, but are not limited to, Ci to C22 n-paraffins and i-paraffins.
  • the concentration of paraffins in the hydrocarbon stream 12 may be less than 10 wt% based on the total weight of the hydrocarbon stream 12.
  • the concentration of paraffins in the hydrocarbon stream 12 may be 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, or more based on the total weight of the hydrocarbon stream 12.
  • embodiments include paraffins of carbon numbers up to 22, the disclosure is not limited to carbon number 22 as an upper end-point of the suitable range of paraffins, and the paraffins can include higher carbon numbers, e.g., 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, and higher.
  • at least a portion of the paraffins in the hydrocarbon stream 12 comprises at least a portion of the heavy hydrocarbon molecules.
  • any olefin may be included in the hydrocarbon stream 12.
  • olefins which may be included in hydrocarbon stream 12 include, but are not limited to, C 2 to C 10 olefins and combinations thereof.
  • the concentration of olefins in the hydrocarbon stream 12 may be less than 10 wt% based on the total weight of the hydrocarbon stream 12.
  • the concentration of olefins in the hydrocarbon stream 12 may be 10 wt%, 20 wt%, 30 wt%, 40 wt% or more based on the total weight of the hydrocarbon stream 12.
  • At least a portion of the one or more olefins in the hydrocarbon stream 12 comprise at least a portion of the heavy hydrocarbon molecules.
  • none of the heavy hydrocarbon molecules in the hydrocarbon stream 12 are olefins.
  • embodiments include olefins of carbon numbers up to 10, the disclosure is not limited to carbon number 10 as an upper end-point of the suitable range of olefins, and the olefins can include higher carbon numbers, e.g., 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, and higher.
  • the hydrocarbon stream 12 comprises no olefins.
  • Any naphthene may be included in the hydrocarbon stream 12.
  • naphthenes include, but are not limited to, cyclopentane, cyclohexane, cycloheptane, and cyclooctane.
  • the concentration of naphthenes in the hydrocarbon stream 12 may be less than 10 wt% based on the total weight of the hydrocarbon stream 12.
  • the concentration of naphthenes in the hydrocarbon stream 12 may be 10 wt%, 20 wt%, 30 wt%, 40 wt% or more based on the total weight of the hydrocarbon stream 12.
  • embodiments include naphthenes of carbon numbers up to 8, the disclosure is not limited to carbon number 8 as an upper end-point of the suitable range of naphthenes, and the naphthenes can include higher carbon numbers, e.g., 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, and higher.
  • at least a portion of the naphthenes in the hydrocarbon stream 12 comprise at least a portion of the heavy hydrocarbon molecules.
  • Aromatic hydrocarbons suitable for use in the hydrocarbon stream 12 include, but are not limited to, benzene, toluene, xylenes, ethyl benzene, or combinations thereof.
  • the concentration of aromatic hydrocarbons in the hydrocarbon stream 12 may be less than 10 wt% based on the total weight of the hydrocarbon stream 12.
  • the concentration of aromatic hydrocarbons in the hydrocarbon stream 12 may be 10 wt%, 20 wt%, 30 wt%, 40 wt% or more based on the total weight of the hydrocarbon stream 12.
  • embodiments include aromatic hydrocarbons of carbon numbers up to 8, the disclosure is not limited to carbon number 8 as an upper end-point of the suitable range of aromatic hydrocarbons, and the aromatic hydrocarbons can include higher carbon numbers, e.g., 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, and higher.
  • the aromatic hydrocarbons carbon number is as high as 22.
  • at least a portion of the aromatics in the hydrocarbon stream 12 comprise at least a portion of the heavy hydrocarbon molecules.
  • the hydrocarbon stream 12 comprises no aromatic hydrocarbons.
  • embodiments of the processes disclosed herein contemplate hydrocracking of molecules, and in particular, heavy hydrocarbon molecules of the hydrocarbon stream 12.
  • the pyrolysis oils comprises heavy hydrocarbon molecules (e.g., also referred to as heavy ends of the pyrolysis oils). Hydrocracking of the heavy ends of the pyrolysis oils to meet steam cracker 40 specifications is contemplated.
  • the concentration of heavy hydrocarbon molecules in the hydrocarbon stream 12 may be less than 10 wt% based on the total weight of the hydrocarbon stream 12.
  • the concentration of the heavy hydrocarbon molecules in the hydrocarbon stream 12 may be 10 wt% to 90 wt% based on the total weight of the hydrocarbon stream 12.
  • the heavy hydrocarbon molecules may include paraffins, i-paraffins, olefins, naphthenes, aromatic hydrocarbons, or combinations thereof.
  • the heavy hydrocarbon molecules may include C 16 and larger hydrocarbons. Greater than 5, 10, 15, 20, 25, 30 wt% or more of the heavy hydrocarbon molecules in the hydrocarbon stream 12 is hydrocracked when the hydrocarbon stream 12 is contacted with the hydroprocessing catalyst in the hydroprocessing reactor 20.
  • Chloride compounds which may be included in the hydrocarbon stream 12 include, but are not limited to, aliphatic chlorine-containing hydrocarbons, aromatic chlorine-containing hydrocarbons, and other chlorine -containing hydrocarbons.
  • Examples of chlorine-containing hydrocarbons include, but are not limited to, 1-chlorohexane (C 6 H 13 C1), 2-chloropentane (C 5 H U C1), 3 -chloro-3 -methyl pentane (C 6 H 13 C1), (2- chloroethyl) benzene (CgHgCl), chlorobenzene (CgH 5 Cl), or combinations thereof.
  • the concentration of chloride compounds in the hydrocarbon stream 12 may be 5 ppm, 6 ppm, 7 ppm, 8 ppm, 9 ppm, 10 ppm, 15 ppm, 20 ppm, 30 ppm, 40 ppm, 50 ppm, 100 ppm, 200 ppm, 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm, 1,000 ppm, 1,100 ppm, 1,200 ppm, 1,300 ppm, 1,400 ppm, 1,500 ppm, 1,600 ppm, 1,700 ppm, 1,800 ppm, 1,900 ppm, 2,000 ppm or more based on the total weight of the hydrocarbon stream 12.
  • Sulphides which may be included in the hydrocarbon stream 12 include sulphur-containing compounds.
  • a sulphiding agent such as dimethyl disulphide (C 2 H 6 S 2 ), dimethyl sulphide (C 2 3 ⁇ 4S), mercaptans (R-SH), carbon disulphide (CS 2 ), hydrogen sulphide (H 2 S), or combinations thereof may be used as the sulphide in the hydrocarbon stream 12.
  • one or more sulphides e.g., dimethyl disulphide (C 2 H 6 S 2 ), dimethyl sulphide (C 2 H 6 S 2 ), mercaptans (R-SH), carbon disulphide (CS 2 ), hydrogen sulphide (H 2 S), or combinations thereof
  • the hydrocarbon stream 12 e.g., the hydrocarbon stream 12 is "spiked" with one or more sulphides
  • the hydrocarbon stream 12 is "spiked" with one or more sulphides
  • the one or more sulphides are added to the hydrocarbon stream 12 in an amount such that a sulphur content of the hydrocarbon stream 12, after sulphide addition, is about 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt% or more based on the total weight of the hydrocarbon stream 12.
  • the spiking stream 14 may include components tailored for spiking such as hexadecane and dimethyl disulphide; alternatively, the spiking stream 14 may be a heavier oil (e.g., naphtha, diesel, or both) which already contains sulphide compounds (or to which sulphides are spiked to achieve the sulphur content disclosed herein) and which is blended with the hydrocarbon stream 12 to achieve the sulphur content described above.
  • a heavier oil e.g., naphtha, diesel, or both
  • one or more sulphides are present in the hydrocarbon stream as a result of upstream processing from which the hydrocarbon stream 12 flows.
  • the hydrocarbon stream 12 may contain one or more sulphides in an amount such that a sulphur content of the hydrocarbon stream 12, without sulphide spiking, is about 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt% or more based on the total weight of the hydrocarbon stream 12.
  • the hydrocarbon stream 12 may contain one or more sulphides in an amount insufficient for sulphiding (e.g., less than 5,000, 4,000, 3,000, 2,000, 1,000, 900, 800, 700, 600, 500, 400, 300, 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 5, or 1 ppm) the hydroprocessing catalyst contained in the hydroprocessing reactor 20 (the catalyst is discussed in more detail below), and spiking stream 14 is utilized to raise the concentration of the one or more sulphides in the hydrocarbon stream to such that a sulphur content of the hydrocarbon stream 12, after sulphide addition, is about 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt% or more based on the total weight of the hydrocarbon stream 12.
  • sulphides in an amount insufficient for sulphiding
  • the sulphur content of the hydrocarbon stream 12, after sulphide addition using spiking stream 14, is up to about 3 wt% based on the total weight of the hydrocarbon stream 12. In another embodiment, the sulphur content of the hydrocarbon stream 12, without sulphide addition using spiking stream 14, is up to about 3 wt% based on the total weight of the hydrocarbon stream 12.
  • the hydroprocessing reactor 20 is configured to dechlorinate, hydrogenate, and hydrocrack components of the hydrocarbon stream 12 fed to the hydroprocessing reactor 20.
  • the hydrocarbon stream 12 is contacted with the hydroprocessing catalyst in the presence of hydrogen to yield a hydrocarbon product in stream 22.
  • the hydrocarbon stream 12 may be contacted with the hydroprocessing catalyst in upward flow, downward flow, radial flow, or combinations thereof, with or without a staged addition of hydrocarbon stream 12, spiking stream 14, a H 2 stream 24, or combinations thereof.
  • the components of the hydrocarbon stream 12 may be in the liquid phase, a liquid- vapor phase, or a vapor phase while in the hydroprocessing reactor 20.
  • the hydroprocessing reactor 20 may facilitate any reaction of the components of the hydrocarbon stream 12 in the presence of, or with, hydrogen. Reactions may occur as the addition of hydrogen atoms to double bonds of unsaturated molecules (e.g., olefins, aromatic compounds), resulting in saturated molecules (e.g., paraffins, i-paraffins, naphthenes). Additionally, reactions in the hydroprocessing reactor 20 may cause a rupture of a bond of an organic compound, resulting in "cracking" of a hydrocarbon molecule into two or more smaller hydrocarbon molecules, or resulting in a subsequent reaction and/or replacement of a heteroatom with hydrogen.
  • unsaturated molecules e.g., olefins, aromatic compounds
  • saturated molecules e.g., paraffins, i-paraffins, naphthenes
  • Examples of reactions which may occur in the hydroprocessing reactor 20 include, but are not limited to, the hydrogenation of olefins, removal of heteroatoms from heteroatom-containing hydrocarbons (e.g., dechlorination), hydrocracking of large paraffins or i-paraffins to smaller hydrocarbon molecules, hydrocracking of aromatic hydrocarbons to smaller cyclic or acyclic hydrocarbons, conversion of one or more aromatic compounds to one or more cycloparaffins, isomerization of one or more normal paraffins to one or more i-paraffins, selective ring opening of one or more cycloparaffins to one or more i-paraffins, or combinations thereof.
  • contacting the hydrocarbon stream 12 with the hydroprocessing catalyst in the presence of hydrogen yields a hydrocarbon product comprising Q to C4 gases and C5+ (C5 and heavier) liquid hydrocarbons.
  • the separator 30 recovers the C5+ liquid hydrocarbons in the treated hydrocarbon stream 32.
  • the d to C 4 gases can be recovered in hydroprocessed light gas stream 36.
  • the hydroprocessing reactor 20 may be any vessel configured to contain the hydroprocessing catalyst disclosed herein.
  • the vessel may be configured for gas phase, liquid phase, vapor- liquid phase, or slurry phase operation.
  • the hydroprocessing reactor 20 may include one or more beds of the hydroprocessing catalyst in fixed bed, fluidized bed, moving bed, ebullated bed, slurry bed, or combinations thereof, configuration.
  • the hydroprocessing reactor 20 may be operated adiabatically, isothermally, nonadiabatically, non-isothermally, or combinations thereof.
  • the reactions of this disclosure may be carried out in a single stage or in multiple stages.
  • the hydroprocessing reactor 20 can be two reactor vessels fluidly connected in series, each having one or more catalyst beds of the hydroprocessing catalyst.
  • two or more stages for hydroprocessing may be contained in a single reactor vessel.
  • the first stage may dechlorinate and hydrogenate components of the hydrocarbon stream 12 to yield a first hydrocarbon product having a first level of chloride compounds and olefins.
  • the first hydrocarbon product may flow from the first stage to the second stage, where other components of the first hydrocarbon product are dechlorinated and hydrogenated to yield a second hydrocarbon product stream (stream 22 in Figure 1) having a second level of chloride compounds and olefins.
  • the second hydrocarbon stream may then be treated as described herein for stream 22.
  • the hydroprocessing reactor 20 may comprise one or more vessels.
  • the sulphur present in the hydrocarbon stream 12 is removed as H 2 S to provide a reduced level of sulphur acceptable for downstream processing in steam crackers and refinery units.
  • hydrogen may feed to the hydroprocessmg reactor 20 in stream 24.
  • the rate of hydrogen addition to the hydroprocessmg reactor 20 is generally sufficient to achieve the hydrogen-to- hydrocarbon ratios disclosed herein.
  • the disclosed hydroprocessmg reactor 20 may operate at various process conditions. For example, contacting the hydrocarbon stream 12 with the hydroprocessing catalyst in the presence of hydrogen may occur in the hydroprocessing reactor 20 at a temperature of 100 °C to 450 °C; alternatively, 100 °C to 350 °C; or alternatively, 260 °C to 350 °C. Contacting the hydrocarbon stream 12 with the hydroprocessing catalyst in the presence of hydrogen may occur in the hydroprocessing reactor 20 at a pressure of 1 barg to 200 barg; or alternatively, 20 barg to 60 barg.
  • WHSV weight hourly space velocity
  • H 2 /HC hydrogen-to-hydrocarbon
  • dechlorination using the hydroprocessing catalyst as described herein is performed in the hydroprocessing reactor 20 without the use of chlorine sorbents, without addition of Na 2 C03 in an effective amount to function as a dechlorinating agent, or both.
  • the hydroprocessing catalyst may be any catalyst used for hydrogenation (e.g., saturation) of olefins and aromatic hydrocarbons (e.g., a commercially available hydrotreating catalyst).
  • the hydroprocessing catalyst is a cobalt and molybdenum catalyst (Co-Mo catalyst) on an alumina support.
  • the hydroprocessing catalyst is a nickel and molybdenum catalyst (Ni-Mo catalyst) on an alumina support or tungsten and molybdenum catalyst (W -Mo catalyst) on an alumina support.
  • catalyst embodiments may include platinum and palladium catalyst (Pt-Pd catalyst) on an alumina support, nickel sulphides suitable for slurry processing, molybdenum sulphides suitable for slurry processing, nickel and molybdenum sulphides, or combinations thereof.
  • Pt-Pd catalyst platinum and palladium catalyst
  • contacting the hydrocarbon stream 12 with the hydroprocessing catalyst acts to activate the hydroprocessing catalyst by sulphiding and to acidify the hydroprocessing catalyst by chlorinating. Continuously contacting the hydroprocessing catalyst with the hydrocarbon stream 12 containing the one or more sulphides, the one or more chloride compounds, or both, may maintain the catalyst activity on a continuous basis.
  • the hydroprocessing catalyst is activated and/or the activity is maintained by sulphiding the hydroprocessing catalyst in-situ.
  • the hydroprocessing catalyst may be sulphided (i.e., activated) and/or sulphiding (i.e., maintaining the catalyst activity) of the hydroprocessing catalyst may be performed (e.g., maintaining the hydroprocessing catalyst in sulphided form is accomplished) by continuously contacting the hydrocarbon stream 12 containing one or more sulphides with the hydroprocessing catalyst.
  • the one or more sulphides may be included in the hydrocarbon stream 12 in an amount such that the sulphur content of the hydrocarbon stream 12 is about 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, or 5 wt% based on the total weight of the hydrocarbon stream 12.
  • the hydroprocessing catalyst may be sulphided (i.e., activated) by contacting a catalyst activating stream 26 containing one or more sulphides with the hydroprocessing catalyst for a period of time (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9 or more hours) sufficient to activate the hydroprocessing catalyst (before contacting the hydrocarbon stream 12 with the hydroprocessing catalyst).
  • the catalyst activating stream 26 may include a hydrocarbon carrier for the one or more sulphides, such as hexadecane.
  • the one or more sulphides may be included in the catalyst activating stream 26 in an amount such that the sulphur content of the catalyst activating stream 26 is about 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt% or more based on the total weight of the catalyst activating stream 26.
  • flow of the catalyst activating stream 26 may be discontinued, and sulphiding (i.e., maintaining the catalyst activity) of the hydroprocessing catalyst may be maintained (e.g., maintaining the hydroprocessing catalyst in sulphided form is accomplished) by continuously contacting the hydrocarbon stream 12 containing one or more sulphides with the hydroprocessing catalyst.
  • the one or more sulphides may be included in the hydrocarbon stream 12 in an amount such that the sulphur content of the hydrocarbon stream 12 is about 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, or 5 wt% based on the total weight of the hydrocarbon stream 12.
  • sulphiding and maintaining the catalyst in sulphided form may use two different concentrations of sulphur content in the hydrocarbon stream 12.
  • the one or more sulphides may be included (e.g., provided via spiking stream 14) in the hydrocarbon stream 12 in an amount such that the sulphur content of the hydrocarbon stream 12 is about 2 wt% based on the total weight of the hydrocarbon stream 12 for sulphiding, and the one or more sulphides may be maintained (e.g., via spiking stream 14) in the hydrocarbon stream 12 in an amount such that the sulphur content of the hydrocarbon stream 12 is about 2 wt% based on the total weight of the hydrocarbon stream 12 for maintaining the hydroprocessing catalyst in the sulphided form.
  • the one or more sulphides may be included in the catalyst activating stream 26 in an amount such that the sulphur content of the catalyst activating stream 26 is about 3 wt% based on the total weight of the catalyst activating stream 26 for sulphiding, and the one or more sulphides may be included (e.g., via spiking stream 14) in the hydrocarbon stream 12 in an amount such that the sulphur content of the hydrocarbon stream 12 is about 2 wt% based on the total weight of the hydrocarbon stream 12 for maintaining the hydroprocessing catalyst in the sulphided form.
  • catalyst activity is also maintained by chloriding the hydroprocessing catalyst.
  • the hydroprocessing catalyst is chlorided using the one or more chloride compounds provided to the hydroprocessing catalyst by the hydrocarbon stream 12.
  • the one or more chloride compounds which contribute to acidification of the hydroprocessing catalyst may be included in the hydrocarbon stream 12 in concentrations disclosed herein.
  • the hydrocarbon product stream 22 may contain one or more olefins in a concentration of less than 1 wt% based on the total weight of the hydrocarbon product stream 22. It is also contemplated that the concentration of aromatic hydrocarbons in the hydrocarbon product stream 22 is less than the concentration of aromatic hydrocarbons in the hydrocarbon stream 12 due to hydrogenation of at least a portion of the aromatic hydrocarbons in the hydroprocessing reactor 20. For example, aromatic hydrocarbons may be present in the hydrocarbon product stream 22 in a concentration of less than 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 wt% based on the total weight of the hydrocarbon product stream 22.
  • the reaction product flows as effluent from the hydroprocessing reactor 20 in the hydrocarbon product stream 22 to the separator 30.
  • Separator 30 may be any vessel which can recover a treated hydrocarbon stream 32 from the hydrocarbon product stream 22 which is fed to the separator 30.
  • the treated hydrocarbon stream 32 may be recovered by separating a treated product (e.g., liquid product or gas product) from sulphur and chlorine-containing gas in the separator 30, and flowing the treated product in the treated hydrocarbon stream 32 from the separator 30.
  • a treated product e.g., liquid product or gas product
  • the separator 30 is a condenser which operates at conditions which condense a portion of the hydrocarbon product stream 22 into the treated product (e.g., liquid product or treated liquid product) while leaving sulphur and chlorine-containing compounds in the gas phase.
  • the treated liquid product flows from the separator 30 in treated hydrocarbon stream 32, and the sulphur and chlorine -containing gas flows from the separator 30 via hydroprocessed light gas stream 36.
  • the treated liquid product may comprise C 3 ⁇ 4 + (C 3 ⁇ 4 and heavier) liquid hydrocarbons.
  • the separator 30 is a scrubbing unit containing a caustic solution (e.g., a solution of sodium hydroxide in water) which removes (e.g., via reaction, adsorption, absorption, or combinations thereof) sulphur and chlorine -containing gases from the hydrocarbon product stream 22 to yield the treated product which flows from the separator 30 via treated hydrocarbon stream 32 while the Q to C 4 hydrocarbons and sulphur and chlorine-containing compounds are removed from the separator 30 via hydroprocessed light gas stream 36.
  • the treated liquid product may comprise C 3 ⁇ 4 + (C 3 ⁇ 4 and heavier) liquid hydrocarbons.
  • the separator 30 is a condenser in communication with one or more stages of a gas-liquid separator, followed by a scrubbing unit containing a caustic solution.
  • the condenser may operate at conditions which condense a portion of the hydrocarbon product stream 22 into a mid-treated product (e.g., liquid product or treated liquid product) while leaving sulphur and chlorine- containing compounds in the gas phase which then flow into the scrubbing unit to provide a sulphur-free and chlorine -free stream of Q to C4 hydrocarbon gases.
  • the mid-treated product may comprise C 5 + (C 5 and heavier) liquid hydrocarbons.
  • the mid-treated liquid product flows from the condenser to the one or more stages of gas-liquid separator and experiences a pressure reduction (e.g., via a valve or other pressure reducing device known in the art with the aid of this disclosure) which creates an effluent gas (e.g., via flashing) which flows to the scrubbing unit from the one or more stages of gas-liquid separator for further removal of sulphur and chlorine-containing compounds from the liquid hydrocarbons.
  • the treated product flowing in treated hydrocarbon stream 32 flows from the final/last stage of the gas-liquid separator of the separator 30 to the steam cracker 40 via stream 32. Sulphur and chlorine-containing compounds in the gas products are scrubbed in the scrubbing unit of the separator 30 and flow from the separator 30 in hydroprocessed light gas stream 36.
  • the treated hydrocarbon stream 32 includes one or more chloride compounds in a concentration of less than 5 ppm, 4 ppm, 3 ppm, 2 ppm, 1 ppm, or 0.5 ppm based on a total weight of the treated hydrocarbon stream 32.
  • the one or more chloride compounds in the treated hydrocarbon stream 32 may be the same as some or all of the one or more chloride compounds in the hydrocarbon stream 12; alternatively, it is contemplated that only some of the one or more chloride compounds in the treated hydrocarbon stream 32 are the same as only some of the one or more chloride compounds in the hydrocarbon stream 12; alternatively, it is contemplated that none of the one or more chloride compounds in the treated hydrocarbon stream 32 are the same as the one or more chloride compounds in the hydrocarbon stream 12.
  • the treated hydrocarbon stream 32 includes the one or more olefins in a concentration which is less than a concentration of the one or more olefins in the hydrocarbon stream 12 due to hydrogenation of at least a portion of the one or more olefins from the hydrocarbon stream 12 while the hydrocarbon stream 12 is contacted with the hydroprocessing catalyst in the hydroprocessing reactor 20.
  • the treated hydrocarbon stream 32 includes the one or more olefins in a concentration which is less than a concentration of the one or more olefins in the hydrocarbon stream 12 due to hydrogenation and hydrocracking of at least a portion of the one or more olefins from the hydrocarbon stream 12 while the hydrocarbon stream 12 is contacted with the hydroprocessing catalyst in the hydroprocessing reactor 20.
  • the one or more olefins are present in the treated hydrocarbon stream 32 in a concentration of less than 1 wt% based on the total weight of the treated hydrocarbon stream 32.
  • the treated hydrocarbon stream 32 includes one or more paraffins, and the concentration of the one or more olefins is less than 1 wt% based on the total weight of the treated hydrocarbon stream 32. It is also contemplated that the concentration of aromatic hydrocarbons in the treated hydrocarbon stream 32 is less than the concentration of aromatic hydrocarbons in the hydrocarbon stream 12 due to hydrogenation of at least a portion of the aromatic hydrocarbons in the hydroprocessing reactor 20. For example, aromatic hydrocarbons may be present in the treated hydrocarbon stream 32 in a concentration of less than 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 wt% based on the total weight of the treated hydrocarbon product stream 32.
  • the treated hydrocarbon stream 32 may have a reduced concentration of heavy hydrocarbon molecules compared to the concentration of heavy hydrocarbon molecules in the hydrocarbon stream 12 due to hydrocracking of at least a portion of the heavy hydrocarbon molecules from the hydrocarbon stream 12 while the hydrocarbon stream 12 is contacted with the hydroprocessing catalyst.
  • the treated hydrocarbon stream 32 may comprise none of the heavy hydrocarbon molecules form the hydrocarbon stream 12 due to hydrocracking of the heavy hydrocarbon molecules in the hydroprocessing reactor 20. Due to hydrocracking of heavy hydrocarbon molecules when the hydrocarbon stream 12 is contacted with the hydroprocessing catalyst in the hydroprocessing reactor 20, the treated hydrocarbon stream 32 may have a boiling end point of 370 °C.
  • the treated hydrocarbon stream 32 may be fed directly to the steam cracker 40.
  • the treated hydrocarbon stream 32 may be blended with a non-chlorinated hydrocarbon stream 34 to yield a blended hydrocarbon stream 38 (streams 34 and 38 having dashed lines to denote the alternative embodiment) having a concentration of one or more chlorides which is less than 3 ppm based on a total weight of the blended hydrocarbon stream 38.
  • the blended hydrocarbon stream 38 may be fed to the steam cracker 40.
  • Steam cracker 40 generally has feed specification requirements. First, the steam cracker 40 requires the concentration of chloride compounds in the feed to the steam cracker 40 to be less than 3 ppm. Second, the steam cracker 40 requires the concentration of olefins in a stream fed to the steam cracker 40 to be less than 1 wt%. Third, the steam cracker 40 requires the boiling end point of the stream fed to the steam cracker 40 to be 370 °C. The steam cracker 40 cracks molecules or cleaves at elevated temperatures carbon- carbon bonds of the components in the treated hydrocarbon stream 32 or blended hydrocarbon stream 38 in the presence of steam to yield high value products such as ethylene, propylene, butene, butadiene, aromatic compounds, or combinations thereof.
  • the steam cracker 40 cracks molecules or cleaves at elevated temperatures carbon-carbon bonds of the components in the treated light gas product (e.g., of treated pyrolysis light gas stream 52 and/or treated hydroprocessed light gas stream 54) in the presence of steam to yield high value products such as ethylene, propylene, butene, butadiene, aromatic compounds, or combinations thereof.
  • the high value products may flow from the steam cracker 40 via stream 42.
  • the pyrolysis gases in the pyrolysis light gas stream 16, the Q to C4 gases in the hydroprocessed light gas stream 36, or both may flow to a scrubbing unit 50.
  • the scrubbing unit 50 may be the same scrubbing unit used in embodiments of the separator 30 which include a scrubbing unit, or the scrubbing unit 50 may be in addition to any scrubbing unit included in the separator 30.
  • the scrubbing unit 50 may contain a caustic solution (e.g., a solution of sodium hydroxide in water) which removes (e.g., via reaction, adsorption, absorption, or combinations thereof) sulphur and chlorine -containing gases from the stream (e.g., pyrolysis light gas stream 16 and/or hydroprocessed light gas stream 36) fed to the scrubbing unit 50 and yield a treated light gas product (e.g., treated pyrolysis light gas stream 52, treated hydroprocessed light gas stream 54, or a single treated light gas stream which combines the treated hydroprocessed product and treated pyrolysis product) which flows from the scrubbing unit 50 to the steam cracker 40.
  • the removed compounds (sulphur and/or chlorine containing gases) may flow from the scrubbing unit 50 in stream 56.
  • the treated pyrolysis light gas stream 52 may include one or more sulphide and/or chloride compounds in a concentration of less than 5 ppm, 4 ppm, 3 ppm, 2 ppm,
  • the treated hydroprocessed light gas stream 54 may include one or more sulphide and/or chloride compounds in a concentration of less than 5 ppm, 4 ppm, 3 ppm,
  • the foregoing describes a system 100 which implements one or more embodiments of an integrated process for the conversion of waste plastics to high value products.
  • the integrated processes allow for operation with a single hydroprocessing reactor 20 which provides simultaneous hydrogenation, dechlorination, and hydrocracking of components of a hydrocarbon stream 12 to specifications which meet steam cracker 40 requirements.
  • Examples provided below demonstrate the various embodiments of the pyrolysis process for generating a pyrolysis oil or hydrocarbon stream, not limited by the equipment used. These examples are for high severity pyrolysis process carried out at temperatures of 450 °C to 750 °C, low severity pyrolysis process carried out at 300 °C to 450 °C, hydrogen or hydrogen donor assisted (hydropyrolysis) processes carried out at both the above severities as well as use of a catalyst recipe and a combination of sand and catalyst as a catalyst recipe. Though these examples are provided for fluidized beds where in the heat transfer and catalyst/feed contact are good, directionally the same type of results can be obtained with other types of pyrolysis equipment as described herein.
  • hydrocracking of olefins and heavy hydrocarbon molecules contained in a hydrocarbon stream occurs using a hydroprocessing catalyst at the conditions disclosed herein.
  • the olefins are hydrogenated in addition to being hydrocracked.
  • chloride compounds contained in the hydrocarbon stream are removed.
  • simultaneous hydrogenation, dechlorination, and hydrocracking of a hydrocarbon stream components is achieved in a single hydroprocessing step, with the treated hydrocarbon product being capable of feeding to a steam cracker having the feed requirements specified herein, without further separations or fractionations of the treated hydrocarbon product.
  • simultaneous hydrogenation, dechlorination, and hydrocracking is achieved by continuously contacting a hydrocarbon stream having one or more sulphides and one or more chloride compounds at the concentrations disclosed herein with the hydroprocessing catalyst in the presence of hydrogen at the operating conditions disclosed herein. That is, catalyst activity can be initiated and/or maintained simultaneously with the simultaneous hydrogenation, dechlorination, and hydrocracking by using hydrocarbon streams of the compositions disclosed herein which feed to a hydroprocessing reactor.
  • Hydrocracking according to the embodiments disclosed herein can occur over the operating pressures disclosed herein for hydroprocessing reactor 20, including those low pressures demonstrated in the examples.
  • Embodiments of the processes disclosed herein meet the feed boiling end point of 370 °C required for steam crackers.
  • the disclosed embodiments demonstrate that about 30 wt% of the heavy hydrocarbon molecules of a hydrocarbon stream can undergo hydrocracking at the conditions disclosed herein.
  • the hydrocarbon stream contains plastic and/or tire pyrolysis oil, the heavier ends of the pyrolysis oil are hydrocracked.
  • Increased levels of paraffins due to the hydrocracking ability of the processes disclosed herein can result in a higher production of propylene in steam crackers.
  • LPG gases are not liberated in the disclosed processes until the temperature of the one or more catalyst beds in the hydroprocessing reactor 20 reaches about 400 °C. Gas product formation is minimized, which is useful for existing plants which are constrained on the gas flow rate to the gas compressor section. In the disclosed embodiments, the production of methane and ethane is also low.
  • Dechlorination according to the embodiments disclosed herein can occur over the operating temperature ranges disclosed herein for the hydroprocessing reactor 20, including operating temperatures in the low-end of the temperature ranges disclosed herein. Removal of chloride compounds to less than 1 ppm occurs at temperatures below 350 °C. Moreover, achieving sub-ppm chloride compound concentrations is possible with initial chloride content in the hydrocarbon stream 12 of 1,000 ppm or more. Moreover still, removal of chloride compounds is effective for different types and classes of chlorides present in the hydrocarbon stream 12. When the hydroprocessing reaction is conducted at temperatures at or above 350 °C, it has been found that the treated hydrocarbon product contains 3ppm or higher chloride content. In such cases, the treated hydrocarbon product stream can be blended as described herein with a non-chlorinated stream 34 in such proportions to make the combined blended hydrocarbon stream 38 meet the steam cracker feed specifications.
  • Operation at low temperatures also has an added advantage of corrosion mitigation of the reactor metallurgy.
  • corrosion rates start to increase at reactor temperatures over 300 °C. It has been found that the efficiency of dechlorination according to the disclosed embodiments is good at reactor temperatures below 350 °C, and the dechlorination process works with a sulphided Co-Mo catalyst on an alumina support even as low as 260 °C, with the chlorides in the treated product being less than 1 ppm.
  • the metallurgy corrosion issue is mitigated and longer equipment life is possible while achieving dechlorination to levels desirable for feed to steam cracker 40.
  • the disclosed embodiments also demonstrate olefins in the hydrocarbon product are reduced typically to less than 1 wt% of the treated hydrocarbon stream 32 from a feed olefin concentration of 20 wt% or more in the hydrocarbon stream 12.
  • the disclosed embodiments achieve the pyrolysis of plastics and also the requirements of chloride content, olefin content, and boiling end point of the feed for a steam cracker.
  • Examples 1 to 6 were conducted in a fixed bed reactor located inside a 3 -zone split-tube furnace.
  • the reactor internal diameter was 13.8 mm and had concentrically located bed thermowell of 3 mm outer diameter.
  • the reactor was 48.6 cm long.
  • Commercial hydroprocessing catalyst of Co-Mo on alumina (8 g bone dry weight) was broken along the length to particles of 1.5 mm long and diluted with SiC in the ratio of 60 % SiC to 40 % catalyst to give a mean particle diameter of 0.34 mm. This was done to avoid slip through of the chlorides due to wall slip or channeling in the small diameter reactor.
  • Pre-heating bed and post-catalyst inert beds was provided in the form of 1mm glass beads.
  • the catalyst bed temperature was controlled to isothermal by varying the controlled furnace zone skin temperatures.
  • the catalyst was sulphided using 3 wt% S in hexadecane (S was introduced as dimethyl disulphide).
  • Liquid feed i.e., the hydrocarbon stream
  • H 2 gas was fed using a mass flow controller.
  • the reactor effluent (i.e., the hydrocarbon product) gases were cooled to condense out the liquids (i.e., the treated hydrocarbon stream in the form of a liquid product) under pressure while allowing non-condensed gases (e.g., containing chloride(s), chlorine, hydrogen sulphide, or combinations thereof) to separate.
  • non-condensed gases e.g., containing chloride(s), chlorine, hydrogen sulphide, or combinations thereof
  • the pressure of the liquids was reduced and effluent gas flow was measured using a drum-type wet gas meter.
  • the effluent gas flow was analyzed using a refinery gas analyzer (a custom gas analyzer from M/s AC Analytical BV).
  • the liquid product olefin content was determined using a Detailed Hydrocarbon Analyzer GC (DHA) and a boiling point characterization was obtained using a SIMDIS GC.
  • the liquid product chloride content was measured using a Chlora M-series analyzer (monochromatic wavelength dispersive X-ray Fluorescence technique, ASTM D7536).
  • Example 1 a hydrocarbon feed mixture was prepared by mixing 30 wt% n-hexadecane, 10 wt% i-octane, 20 wt% 1-decene, 20 wt% cyclohexane, and 20 wt% ethyl benzene. Dimethyl disulphide, 2- chloropentane, 3-chloro-3-methyl pentane, 1-chlorohexane, (2-chloroethyl) benzene, and chlorobenzene were then added to give 205 ppm organic chlorides and a sulphur content of 2 wt% S in the combined feed mixture.
  • This combined feed mixture was used as the hydrocarbon stream which was contacted with the hydroprocessing catalyst in the packed bed reactor as mentioned above in the presence of H 2 at conditions of 280 °C reactor temperature, 60 barg reactor pressure, 0.92 hr 1 WHSV, and 414 NL/L H 2 /HC flow ratio.
  • the liquid product i.e., the treated hydrocarbon stream
  • the normalized composition of liquid product as measured by DHA was paraffins (26.24 wt%), i-paraffins (17.28 wt%), olefins (0 wt%), naphthenes (33.61 wt%), and aromatics (22.88 wt%).
  • This 22 wt% hexadecane unaccounted in DHA composition is added to the liquid product analyzed by DHA (DHA composition multiplied by 0.78 fraction that was injected into DHA) and the resulting composition of the liquid product is 42.47 wt% paraffins, 13.48 wt% i-paraffins, 0 wt% olefins, 26.21 wt% naphthenes and 17.84 wt% aromatics.
  • the chloride content of the liquid product was 0.09 ppmw.
  • Example 1 demonstrates it is possible to simultaneously dechlorinate, hydrogenate, and hydrocrack a PIONA hydrocarbon stream containing heavy hydrocarbon molecules (e.g., hexadecane), a chloride content of more than 200 ppm, and an olefin content of 20 wt% (calculated based on the feed excluding chloride and sulphides) such that a portion of the heavy hydrocarbon molecules are hydrocracked, chloride content is reduced to less than 1 ppm, and olefins are completely removed (0 wt% in the liquid product).
  • heavy hydrocarbon molecules e.g., hexadecane
  • olefin content e.g., olefin content of 20 wt% (calculated based on the feed excluding chloride and sulphides)
  • Example 1 additionally demonstrates olefins are hydrocracked in addition to being hydrogenated.
  • Example 2 explores the effect of operating pressure on hydrocracking performance.
  • a hydrocarbon feed mixture was prepared by mixing 30 wt% n-hexadecane, 10 wt% i-octane, 20 wt% 1-decene, 20 wt% cyclohexane, and 20 wt% ethyl benzene.
  • Dimethyl disulphide, 2-chloropentane, 3 -chloro-3 -methyl pentane, 1-chlorohexane, (2-chloroethyl) benzene, and chlorobenzene were then added to give 205 ppm organic chlorides and a sulphur content of 2 wt% S in the combined feed mixture.
  • This combined feed mixture was used as a hydrocarbon stream which was contacted with the sulphided hydroprocessing catalyst in the packed bed reactor as mentioned above in the presence of H 2 at conditions of 300 °C reactor temperature, 0.92 hr "1 WHSV, and 414 NL/L H 2 /HC flow ratio.
  • Three different pressure conditions were studied: 60 barg for Example 2A, 20 barg for Example 2B, and 10 barg for Example 2C.
  • the liquid products (i.e., the treated hydrocarbon streams) for each of Examples 2A to 2C were analyzed using SIMDIS, and the results are shown below:
  • Example 2A (60 barg) contained 0.183 wt% olefins
  • Example 2B (20 barg) contained 0.047 wt%
  • Example 2C (10 barg) contained 0 wt% olefins. At lower pressures, a significant increase in aromatics is observed.
  • Example 2 demonstrates it is possible to simultaneously dechlorinate and hydrocrack a PIONA hydrocarbon stream containing heavy hydrocarbon molecules (e.g., hexadecane) and a chloride content of more than 200 ppmw such that a portion of the heavy hydrocarbon molecules are hydrocracked and chloride content is reduced to less than 1 ppmw for all pressures tested.
  • heavy hydrocarbon molecules e.g., hexadecane
  • Example 3 a hydrocarbon feed mixture was prepared to contain 30 wt% n-hexadecane, 10 wt% i-octane, 20 wt% 1-decene, 20 wt% cyclohexane and 20 wt% ethyl benzene. To this the organic chlorides mentioned in Example 2 above were added along with dimethyl disulphide to give 205 ppm organic chlorides and 2 wt% S in the mixture.
  • This feed was used as a hydrocarbon stream which was contacted with the sulphided hydroprocessing catalyst in the packed bed reactor as mentioned above in the presence of H 2 at conditions of 260 °C reactor temperature, 60 barg reactor pressure, 0.92 hr "1 WHSV and 414 NL/L H 2 /HC flow ratio.
  • the liquid product i.e., the treated hydrocarbon stream
  • Example 3 demonstrates the effective removal of chloride compounds from a hydrocarbon stream at very low temperatures.
  • Example 4 a feed was prepared by mixing plastic pyrolysis oil (36.3 g) with n-hexadecane (240 g), and then adding dimethyl disulphide (the sulphide) and 1-chlorohexane (the chloride compound) to give a sulphur content of 2.34 wt% and 836 ppmw chloride in the feed.
  • This feed was used as a hydrocarbon stream which was contacted with the hydroprocessing catalyst in the packed bed reactor as mentioned above in the presence of H 2 under several operating conditions as provided in the table below:
  • Example 4 demonstrates it is possible to dechlorinate a hydrocarbon stream containing plastic pyrolysis oil and having chloride compounds from a chloride content of more than 800 ppmw chlorides to less than 5 ppmw in the liquid product.
  • the chloride content of the liquid product i.e., the treated hydrocarbon stream
  • Example 4 demonstrates removal of chloride compounds to chloride contents less than 3 ppmw, and even sub-ppm levels.
  • Example 5 a hydrocarbon feed mixture was prepared by mixing 30 wt% n-hexadecane, 10 wt% i-octane, 20 wt% 1-decene, 20 wt% cyclohexane, and 20 wt% ethyl benzene. Dimethyl disulphide, 2- chloropentane, 3-chloro-3-methyl pentane, 1-chlorohexane, (2-chloroethyl) benzene, and chlorobenzene were then added to give 1,100 ppmw organic chlorides and a sulphur content of 2 wt% S in the combined feed mixture.
  • This combined feed mixture was used as the hydrocarbon stream which was contacted with the hydrogenating catalyst in the packed bed reactor as mentioned above in the presence of H 2 at conditions of 300 °C reactor temperature, 40 barg reactor pressure, 0.92 hr "1 WHSV, and 414 NL/L H 2 /HC flow ratio.
  • the liquid product contained 0.23 ppmw chlorides and paraffins of 22.569 wt%, i-paraffins of 19.752 wt%, olefins of 0.114 wt%, naphthenes of 33.242 wt%, aromatics of 23.7 wt%, unknowns of 0.16 wt% and heavies of 0.463 wt% as per DHA analysis. This again demonstrates the dechlorination of liquid at much higher chloride concentrations.
  • DHA Group type analysis of the liquid product by carbon number (in wt%) is as below:
  • the yield of liquid products was 95.5wt% of the total products.
  • the balance was gas products.
  • Example 6 a n-hexadecane feed mixture was prepared by mixing n-hexadecane with dimethyl disulphide, 2-chloropentane, 3 -chloro-3 -methyl pentane, 1-chlorohexane, (2-chloroethyl) benzene, and chlorobenzene to give 1,034 ppmw of chlorides and 2 wt% Sulphur in the feed.
  • This combined feed mixture was used as the hydrocarbon stream which was contacted with the hydrogenating catalyst in the packed bed reactor as mentioned above in the presence of H 2 at conditions of 300 °C reactor temperature, 40 barg reactor pressure, 0.92 hr "1 WHSV, and 414 NL/L H 2 /HC flow ratio.
  • the liquid product contained 0.3 ppmw chlorides and paraffins of 22.569 wt%, i-paraffins of 19.752 wt%, olefins of 0.114 wt%, naphthenes of 33.242 wt%, aromatics of 23.7 wt%, unknowns of 0.16 wt% and heavies of 0.463 wt% as per DHA analysis. This again demonstrates the dechlorination of liquid at high chloride concentrations to sub-ppm levels.
  • DHA Group type analysis of the liquid product by carbon number (in wt%) is as below and indicates conversion of n-hexadecane to various PIONA components:
  • Example 7 shows a high severity operation for the pyrolysis unit 10.
  • the mixed plastics feed had the following composition:
  • the reaction temperature at start of reaction was 670 °C.
  • the one-minute average bed temperatures achieved was 569.6 °C.
  • the Catalyst/Feed (C/F) ratio was 6.
  • Huidization N 2 gas flow rate used was 175N cc/min.
  • Overall aromatic and liquid i-paraffin product yields in liquid product boiling below 240 °C were 31.6 wt% and 5.76 wt%, respectively. Their respective concentrations in the liquid product boiling below 240 °C was 74.72 wt% and 13.22 wt%.
  • the yield of light gas olefins, i.e., the sum of yields of ethylene, propylene and butenes was 32.69 wt%, and the total yield of gas products was 45.17 wt%.
  • Example 8 shows a high severity operation for the pyrolysis unit 10, operated in a hydrogen- assisted hydropyrolysis mode.
  • An amount of 1.5 g of mixed plastics was mixed with 9 g of a catalyst mixture comprising 62.5 wt% spent FCC catalyst and 37.5 wt% ZSM-5 zeolite catalyst.
  • the combined mixture was then fed to the fluidized bed reactor described in Example 7 above.
  • the plastic feed was in the form of a 200 micron plastic powder.
  • a mixture of 10% H 2 in N 2 was employed as the carrier gas at a flow rate of 175 N cc/min.
  • the yield of light gas olefins per unit amount of coke deposited on the catalyst is higher in the case of hydropyrolysis. This implies that more light gas olefins would be produced in a circulating fluid catalytic cracking type of unit. In these units, performance is compared on a constant coke yield basis. This is because the amount of coke burnt off in the regenerator is limited by the air availability in the regenerator and as a result the regenerated catalyst returned back to the riser would have more or less coke on it which would in turn affect its activity in the riser. [00106] The total aromatics as well as C -C $ aromatics yield per unit amount of coke deposited is also higher in the case of hydropyrolysis. This implies in hydropyrolysis more aromatic products would be produced in a circulating fluid catalytic cracking type of unit.
  • Example 9 shows a low severity pyrolysis operation.
  • the experimental set up consisted of a stainless steel reactor pot followed by a fixed bed (tubular) reactor packed with ZSM-5 zeolite extrudates and the outlet of this tubular reactor was connected to a stainless steel condenser/receiver tank.
  • the reactor pot was heated using heating tapes with temperature controller.
  • An amount of 100 g of mixed plastic as per composition provided in Example 7 was charged along with ZSM-5 zeolite catalyst powder of 75 microns average particle size into the reactor and the heating was started.
  • the reactor temperature was maintained constant at 450 °C for a period of 1 hr.
  • Experiment 1 Equivalent to 5 wt% of the feed was the catalyst charged in the tubular reactor and 5 wt% equivalent catalyst was charged in the reactor pot (i.e. 10 wt% of catalyst overall).
  • Experiment 2 Equivalent to 5 wt% of the feed was the catalyst charged in the tubular reactor and 15 wt% equivalent catalyst was charged in the reactor pot (i.e. 20 wt% catalyst overall).
  • Figure 2 shows the boiling point distribution of the liquid product obtained indicated that 95 wt% of the liquid product boiled below 370 °C.
  • Example 10 demonstrates a low severity pyrolysis with PVC present in the feed.
  • An amount of 100 g of mixed plastic feed as per the composition provided in Example 7 above was mixed with 2 wt% of ZSM-5 zeolite catalyst powder and heated in a round bottom flask fitted with a condenser. The round bottom flask was maintained at 360 °C for 1 hour. The liquid product had 60 ppmw chlorides.
  • a similar experiment conducted with head space purging of the round bottom flask with N 2 gas provided a liquid product with no detectable chloride content. Chloride content in the liquid products was determined by fusing liquid products in NaOH followed by extraction in water and measurement of the resultant aqueous solution chloride content using ion chromatography. This example also demonstrates the possibility of head space purging in a pyrolysis unit to enhance dechlorination.
  • Example 11 demonstrates a low severity pyrolysis process in a fluidized bed.
  • An amount of 1.5 g of mixed plastic feed as per composition provided in Example 7 was mixed with 9.05 g of a catalyst mixture containing 62.5 wt% of FCC spent catalyst and 37.5 wt% of ZSM-5 Zeolite catalyst. This combined mixture was charged into the fluidized bed reactor described in Example 7. Before charging of feed and catalyst mixture the reactor was at a temperature of 450 °C. The reactor temperature decreased as the feed was charged and later increased to the set point of 450 °C. Data provided below also captures the temperature profile in the reactor bed as a function of time.
  • the 1 min, 6 min, and 10 min average bed temperatures were 333 °C, 369 °C, and 395 °C, respectively.
  • the 1 min average represents the average reaction temperature severity when most temperature changes occur in the reactor.
  • the 6 min average represents the temperature severity when the reactor temperature has recovered and reached the previously set value. Most of the conversion in the low severity case was expected to have been completed at the 6 min average.
  • the data below shows that the liquid product is highly aromatic, the heavier than 370 °C boiling material is only about 2 wt%, and more than 90 wt% of the liquid product boils below 350 °C.
  • Example 12 demonstrates how a steam cracker is used in combination with pyrolysis and hydroprocessing unit.
  • Gases (C -C4) from a pyrolysis unit and hydroprocessing facility are fed to gas crackers.
  • Liquids from the hydroprocessing facility are fed to liquid steam crackers.
  • Example 13 demonstrates a process for sulphiding a hydroprocessing catalyst.
  • the particular steps of the process are shown in Figure 3.
  • the time of 0 hours (zero time) in Figure 3 corresponds to a time after the hydroprocessing catalyst is introduced into the hydroprocessing reactor.
  • the hydroprocessing reactor (having previously been loaded with the hydroprocessing catalyst) was purged with hydrogen for 30 to 60 minutes at a set operating pressure (e.g., 40 to 60 barg).
  • the set operating pressure was maintained by venting the reactor when the pressure of the reactor during hydrogen purging increased above the set operating pressure (e.g., due to a hydrogen source pressure greater than the set operating pressure).
  • the sulphiding feed was then introduced into the reactor using a high pressure pump against the set reactor pressure at a weight hourly space velocity (WHSV) of 3 hr "1 (on bone-dry catalyst basis).
  • the sulphiding feed (e.g., for use in spiking stream 14 of Figure 1) was prepared by mixing n-hexadecane with dimethyl disulphide in appropriate quantity to give 3 wt% sulphur based on total weight of the sulphiding feed.
  • n-hexadecane is used for the sulphiding feed.
  • straight-run naphtha, diesel, or vacuum gas oils can also be used.
  • Figure 3 indicates the hydroprocessing catalyst was soaked with a sulphiding feed without a flow of hydrogen in the reactor and at ambient temperature for a period of 3 hours (ending at time 3.5 hours after zero time in Figure 3). Catalyst soaking provides for complete wetting of the hydroprocessing catalyst; however, soaking is optional. Liquid was drained from the bottom of a downstream gas liquid separator.
  • the hydroprocessing reactor bed temperature was raised to 250 °C at a rate of 30 °C per hour with a flow of H 2 at a ratio of 200NL H 2 /L liquid feed. As shown in Figure 3, the temperature was increased from a time of 3.5 hours to a time of 10.8 hours after zero time.
  • the hydroprocessing reactor bed temperature was then held at 250 °C for a period of 8 hours. As shown in Figure 3, the temperature was held from a time of 10.8 hours to a time of 18.8 hours after zero time.
  • the bed temperature was further increased to 320 °C to 350 °C at a rate of 20 °C per hour without any temperature overshoot at the final temperature. As shown in Figure 3, the temperature was increased from a time of 18.8 hours to a time of 22.3 hours after zero time.
  • the hydroprocessing reactor bed temperature was then maintained at 320 °C to 350 °C for a period of 8 hours. As shown in Figure 3, the temperature was maintained at 320 °C to 350 °C from a time of 22.3 hours to a time of 30.0 hours after zero time.
  • a first embodiment which is a process for converting waste plastics to a high value product comprising:
  • hydrocarbon product comprising Q to C4 gases and C5+ liquid hydrocarbons
  • treated hydrocarbon stream or blended hydrocarbon stream meets steam cracker feed requirements for chloride content, olefin content, and boiling end point.
  • a second embodiment which is the process of the first embodiment, wherein the hydrocarbon stream comprises one or more chloride compounds in a concentration of 5 ppm or more based on a total weight of the hydrocarbon stream, wherein the treated hydrocarbon stream comprises the one or more chloride compounds in a concentration of less than 5 ppm based on a total weight of the treated hydrocarbon stream.
  • a third embodiment which is the process of the second embodiment, wherein the treated hydrocarbon stream comprises the one or more chloride compounds in a concentration of less than 1 ppm based on the total weight of the treated hydrocarbon stream.
  • a fourth embodiment which is the process of any one of the second through the third embodiments, wherein the hydrocarbon stream comprises the one or more chloride compounds in a concentration of greater than 200 ppmw based on a total weight of the hydrocarbon stream.
  • a fifth embodiment which is the process of any one of the first through the fourth embodiments, wherein the hydrocarbon stream comprises one or more olefins, wherein the treated hydrocarbon stream comprises the one or more olefins in a concentration of less than 1 wt.% based on the total weight of the treated hydrocarbon stream.
  • a sixth embodiment which is the process of the fifth embodiment, wherein the one or more olefins are present in the hydrocarbon stream in a concentration of 20 wt% or more based on the total weight of the hydrocarbon stream.
  • a seventh embodiment which is the process of any one of the fifth through the sixth embodiments, wherein the concentration of the one or more olefins in the treated hydrocarbon stream is less than the concentration of the one or more olefins in the hydrocarbon stream due to hydrogenation of at least a portion of the one or more olefins from the hydrocarbon stream during the step of contacting.
  • An eighth embodiment which is the process of any one of the fifth through the seventh embodiments, wherein the concentration of the one or more olefins in the treated hydrocarbon stream is less than the concentration of the one or more olefins in the hydrocarbon stream due to hydrogenation and hydrocracking of at least a portion of the one or more olefins from the hydrocarbon stream during the step of contacting.
  • a ninth embodiment which is the process of any one of the first through the eighth embodiments, wherein the hydrocarbon stream comprises heavy hydrocarbon molecules.
  • a tenth embodiment which is the process of the ninth embodiment, further comprising:
  • hydrocracking at least a portion of the heavy hydrocarbon molecules during the step of contacting.
  • An eleventh embodiment which is the process of any one of the ninth to the tenth embodiments, wherein the treated hydrocarbon stream comprises at least a portion of the heavy hydrocarbon molecules, wherein a concentration of the heavy hydrocarbon molecules in the treated hydrocarbon stream is less than a concentration of the heavy hydrocarbon molecules in the hydrocarbon stream due to hydrocracking of at least a portion of the heavy hydrocarbon molecules from the hydrocarbon stream during the step of contacting.
  • a twelfth embodiment which is the process of any one of the ninth through the eleventh embodiments, wherein the treated hydrocarbon stream comprises none of the heavy molecules due to hydrocracking of the heavy hydrocarbon molecules from the hydrocarbon stream during the step of contacting.
  • a thirteenth embodiment which is the process of any one of the ninth through the twelfth embodiments, wherein the hydrocarbon stream further comprises one or more olefins, wherein at least a portion of the one or more olefins comprises at least a portion of the heavy molecules.
  • a fourteenth embodiment which is the process of any one of the ninth through the thirteenth embodiments, wherein the hydrocarbon stream further comprises paraffins, wherein at least a portion of the paraffins comprises at least a portion of the heavy molecules.
  • a fifteenth embodiment which is the process of any one of the first through the fourth, the ninth through the twelfth, and the fourteenth embodiments, wherein the hydrocarbon stream comprises no olefins.
  • a sixteenth embodiment which is the process of any one of the ninth through the fifteenth embodiments, wherein none of the heavy molecules are olefins.
  • a seventeenth embodiment which is the process of any one of first through sixteenth embodiments, wherein the treated hydrocarbon stream has a boiling end point of 370 °C.
  • An eighteenth embodiment which is the process of any one of the ninth through the seventeenth embodiments, wherein the at least a portion of the heavy hydrocarbon molecules which are hydrocracked during the step of contacting is greater than 5 wt% based on the weight of heavy hydrocarbon molecules in the hydrocarbon stream.
  • a nineteenth embodiment which is the process of any one of the ninth through the eighteenth embodiments, wherein a concentration of the heavy hydrocarbon molecules in the hydrocarbon stream is 10 wt% to 90 wt% based on the total weight of the hydrocarbon stream.
  • a twentieth embodiment which is the process of any one of the of the ninth through the nineteenth embodiments, wherein the heavy hydrocarbon molecules comprise Ci and larger hydrocarbons.
  • a twenty-first embodiment which is the process of the twentieth embodiment, wherein the Ci and larger hydrocarbons comprise paraffins, i-paraffins, olefins, naphthenes, aromatic compounds, or combinations thereof.
  • a twenty-second embodiment which is the process of any one of the first through the twenty-first embodiments, wherein the hydrocarbon stream is one or more of a plastic pyrolysis oil and a tire pyrolysis oil.
  • a twenty-third embodiment which is the process of any one of the first through the twenty- second embodiments, further comprising:
  • a catalyst activating stream comprising one or more sulphides with the hydroprocessing catalyst.
  • a twenty-fourth embodiment which is the process of the twenty-third embodiment, wherein the one or more sulphides of the catalyst activating stream are present in an amount such that a sulphur content of the catalyst activating stream is about 0.5 wt% to about 5 wt% based on the total weight of the catalyst activating stream.
  • a twenty-fifth embodiment which is the process of any one of the first through the twenty-fourth embodiments, wherein the hydrocarbon stream further comprises one or more sulphides.
  • a twenty-sixth embodiment which is the process of the twenty-fifth embodiment, wherein the one or more sulphides of the hydrocarbon stream are present in an amount such that a sulphur content of the hydrocarbon stream is about 0.5 wt% to about 5 wt% based on the total weight of the hydrocarbon stream.
  • a twenty-seventh embodiment which is the process of any one of the first through the twenty- sixth embodiments, wherein the step of contacting is performed at a temperature of 100 °C to 450 °C.
  • a twenty-eighth embodiment which is the process of any one of the first through the twenty- seventh embodiments, wherein the step of contacting is performed at a temperature of 100 °C to 350 °C.
  • a twenty-ninth embodiment which is the process of any one of the first through the twenty- eighth embodiments, wherein the step of contacting is performed at a temperature of 260 °C to 350 °C.
  • a thirtieth embodiment which is the process of any one of the first through the twenty-ninth embodiments, wherein the step of contacting is performed at a weight hourly space velocity of 0.1 to 10 hr "1 .
  • a thirty-first embodiment which is the process of any one of the first through the thirtieth embodiments, wherein the step of contacting is performed at a hydrogen to hydrocarbon ratio of 10 to 3,000 NL/L.
  • a thirty-second embodiment which is the process of any one of the first through the thirty-first embodiments, wherein the step of contacting is performed at a pressure of 1 to 200 barg.
  • a thirty-third embodiment which is the process of any one of the first through the thirty-second embodiments, wherein the treated hydrocarbon stream comprises the one or more chloride compounds in a concentration of less than 3 ppm based on a total weight of the treated hydrocarbon stream, and wherein the treated hydrocarbon stream is fed directly to the stream cracker.
  • a thirty-fourth embodiment which is the process of any one of the first through the thirty-third embodiments, further comprising:
  • the blended hydrocarbon stream comprising the one or more chloride compounds in a concentration of less than 3 ppm based on a total weight of the blended hydrocarbon stream, wherein the blended hydrocarbon stream is fed to the steam cracker.
  • a thirty-fifth embodiment which is the process of any one of the first through the thirty-fourth embodiments, wherein the hydroprocessing catalyst comprises cobalt and molybdenum on an alumina support, nickel and molybdenum on an alumina support, tungsten and molybdenum on an alumina support, or nickel and molybdenum sulphides.
  • a thirty-sixth embodiment which is the process of the thirty-fifth embodiment, wherein contacting the hydrocarbon stream with the hydroprocessing catalyst comprises:
  • a thirty-seventh embodiment which is the process of the thirty-sixth embodiment, wherein the one or more sulphides are contained in or added to the hydrocarbon stream in an amount such that a sulphur content of the hydrocarbon stream is about 0.5 wt% to about 5 wt% based on the total weight of the hydrocarbon stream.
  • a thirty-eighth embodiment which is the process of the first through the thirty-seventh embodiments, wherein the high value products are ethylene, propylene, butene, butadiene, aromatic compounds, or combinations thereof.
  • a thirty-ninth embodiment which is the process of any one of the first through the thirty-eighth embodiments, wherein the step of converting comprises:
  • waste plastics to a pyrolysis process to produce one or more plastic pyrolysis oil in the hydrocarbon stream.
  • a fortieth embodiment which is the process of the thirty-ninth embodiment, wherein the pyrolysis process occurs at a temperature of 250 °C to 450 °C.
  • a forty-first embodiment which is the process of any one of the thirty-ninth through the fortieth embodiments, wherein the pyrolysis process occurs at a temperature of 450 °C to 750 °C.
  • a forty-second embodiment which is the process of any one of the thirty-ninth through the forty- first embodiments, wherein the step of subjecting the waste plastics to a pyrolysis process utilizes a catalyst comprising zeolite, sand, or both.
  • a forty-third embodiment which is the process of any one of the thirty-ninth through the forty- second embodiments, wherein the step of subjecting comprises a first stage and a second stage fluidly connected downstream of the first stage, wherein the first stage utilizes thermal cracking of the waste plastics and the second stage utilizes catalytic cracking of the waste plastics to yield the hydrocarbon stream flowing from the second stage.
  • a forty-fourth embodiment which is the process of any one of the thirty-ninth through the forty- third embodiments, wherein the step of subjecting comprises a first stage and a second stage fluidly connected downstream of the first stage, wherein the first stage utilizes catalytic cracking of the waste plastics and the second stage utilizes thermal cracking of the waste plastics to yield the hydrocarbon stream flowing from the second stage.
  • a forty-fifth embodiment which is the process of any one of the first through the forty-fourth embodiments, wherein recovering a treated hydrocarbon stream from the hydrocarbon product comprises: separating a treated product from a sulphur and chlorine-containing gas in a separator; and
  • a forty-sixth embodiment which is the process of any one of the first through the forty-fifth embodiments, wherein no hydrogen halides and no halogenated organic compounds are recycled to the hydroprocessing reactor.
  • a forty-seventh embodiment which is the process of any one of the first through the forty-sixth embodiments, wherein the step of contacting is performed without use of chlorine sorbents.
  • a forty-eighth embodiment which is the process of any one of the first through the forty-seventh embodiments, wherein the step of contacting is performed without the presence of Na 2 C0 3 in an effective amount to function as a dechlorinating agent.
  • a forty-ninth embodiment which is the process of any one of the first through the forty-eighth embodiments, wherein the hydroprocessing reactor is configured to operate in the slurry phase.
  • a fiftieth embodiment which is the process of any one of the first through the forty-ninth embodiments, wherein the step of contacting includes simultaneous i) dechlorination of the hydrocarbon stream such that the treated hydrocarbon stream comprises one or more chloride compounds in a concentration less than 1 ppm based on the total weight of the treated hydrocarbon stream, ii) hydrogenation of the hydrocarbon stream such that the treated hydrocarbon stream comprises one or more olefins in a concentration less than 1 wt% based on the total weight of the treated hydrocarbon stream, and iii) reduction of heavy hydrocarbon molecules of the hydrocarbon stream.
  • a fifty-first embodiment which is the process of any one of the first through the fiftieth embodiments, wherein 2 wt% or less of the hydrocarbon stream in a liquid phase boils above 370 °C.
  • a fifty-second embodiment which is the process of any one of the first through the fifty-first embodiments, wherein the step of converting the waste plastics to a hydrocarbon stream in a liquid phase utilizes hydrogen.
  • a fifty-third embodiment which is the process of any one of the first through the fifty-second embodiments, further comprising:
  • a fifty-fourth embodiment which is the process of the fifty-third embodiment, wherein the Ci to C4 pyrolysis gases are treated to remove sulphur and chlorine-containing gases before the Ci to C4 pyrolysis gases are fed to the steam cracker.
  • a fifty-fifth embodiment which is the process of any one of the fifty-third through the fifty-fourth embodiments, wherein the step of converting the waste plastics to the hydrocarbon stream and the step of converting the waste plastics to Ci to C4 pyrolysis gases occurs simultaneously via pyrolysis of the waste plastics.
  • a fifty-sixth embodiment which is the process of any one of the first through the fifty-fifth embodiments, wherein converting the waste plastics to a hydrocarbon stream in a liquid phase is performed in the presence of a head space purge gas fed to a pyrolysis unit, wherein the head space purge gas comprises hydrogen, nitrogen, steam, product gases, or combinations thereof.

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Abstract

L'invention concerne un processus intégré de conversion de déchets plastiques en produits de grande valeur. Le processus intégré permet la mise en oeuvre d'un réacteur d'hydrotraitement permettant l'hydrogénation, la déchloration et l'hydrocraquage simultanés de constituants d'un flux d'hydrocarbures selon des spécifications satisfaisant à des exigences d'un vapocraqueur.
PCT/IB2016/051136 2015-03-10 2016-03-01 Processus intégré de conversion de déchets plastiques en produits pétrochimiques finaux WO2016142808A1 (fr)

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WO2018127817A1 (fr) * 2017-01-05 2018-07-12 Sabic Global Technologies, B.V. Conversion de déchets plastiques en propylène et cumène
CN110139846A (zh) * 2017-01-05 2019-08-16 沙特基础全球技术有限公司 废塑料向丙烯和枯烯的转化
US10442997B2 (en) 2016-06-29 2019-10-15 Sabic Global Technologies B.V. Plastic pyrolysis
CN112063409A (zh) * 2020-09-08 2020-12-11 重庆科技学院 基于多相气固流态化反应的含氯塑料热解制油工艺及装置
WO2022144490A1 (fr) 2020-12-30 2022-07-07 Neste Oyj Procédé de traitement de déchets liquides liquéfiés
WO2022144491A1 (fr) 2020-12-30 2022-07-07 Neste Oyj Procédé de traitement de déchets plastiques liquéfiés
WO2023278264A1 (fr) * 2021-06-30 2023-01-05 Eastman Chemical Company Séparation et traitement de gaz de pyrolyse à contenu recyclé
WO2023278261A1 (fr) * 2021-06-30 2023-01-05 Eastman Chemical Company Installation et procédé de recyclage chimique à intégration améliorée
EP4133036B1 (fr) 2020-04-07 2024-06-12 TotalEnergies OneTech Belgium Purification d'huile à base de déchets plastiques par l'intermédiaire d'un hydrotraitement en deux étapes
WO2024132433A1 (fr) 2022-12-21 2024-06-27 IFP Energies Nouvelles Procede de traitement d'huiles de pyrolyse pour valorisation dans une unite de craquage catalytique ou des unites d'hydroraffinage
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FR3144154A1 (fr) 2022-12-21 2024-06-28 IFP Energies Nouvelles Pour valorisation dans une unite de craquage catalytique ou des unites d’hydroraffinage
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WO2024175220A1 (fr) 2023-02-23 2024-08-29 Axens Procede de production d'olefines par vapocraquage par valorisation d'un gaz de pyrolyse
FR3146141A1 (fr) 2023-02-23 2024-08-30 Axens Procede de production d’olefines par vapocraquage par valorisation d’un gaz de pyrolyse
FR3149017A1 (fr) 2023-05-26 2024-11-29 IFP Energies Nouvelles Procede de production de distillats moyens et de naphta d’une charge comportant une fraction d’huile de pyrolyse aromatique
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WO2024245770A1 (fr) 2023-05-26 2024-12-05 IFP Energies Nouvelles Procede de production de distillats moyens et de naphta d'une charge comportant une fraction d'huile de pyrolyse aromatique
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WO2025045487A1 (fr) * 2023-08-29 2025-03-06 Linde Gmbh Procédé et installation pour générer des produits oléfiniques

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