EP4048759A1 - Élimination du mercure et du silicium d'une huile de pyrolyse dérivée de plastique - Google Patents

Élimination du mercure et du silicium d'une huile de pyrolyse dérivée de plastique

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Publication number
EP4048759A1
EP4048759A1 EP20804725.8A EP20804725A EP4048759A1 EP 4048759 A1 EP4048759 A1 EP 4048759A1 EP 20804725 A EP20804725 A EP 20804725A EP 4048759 A1 EP4048759 A1 EP 4048759A1
Authority
EP
European Patent Office
Prior art keywords
plastic
pyrolysis oil
derived pyrolysis
mercury
steam
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP20804725.8A
Other languages
German (de)
English (en)
Inventor
Rohan RAMAN
Beshoy G. ABDELMALEK
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Chemical Patents Inc
Original Assignee
ExxonMobil Chemical Patents Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ExxonMobil Chemical Patents Inc filed Critical ExxonMobil Chemical Patents Inc
Publication of EP4048759A1 publication Critical patent/EP4048759A1/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/08—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one sorption step
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • 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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • 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
    • C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
    • C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
    • C10G55/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one thermal cracking step
    • 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
    • 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
    • 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
    • C10G2300/201—Impurities
    • C10G2300/205—Metal content

Definitions

  • the present disclosure relates to methods and systems for removing contaminants from plastic-derived pyrolysis oil.
  • One proposed method of reusing plastics is pyrolyzing plastic waste to reduce the carbon number.
  • the resultant product can be distilled where a pyrolyzed oil fraction can be used as feedstock for stream cracking, which further reduces the carbon number.
  • the final result is a low carbon number product that can be used as a feedstock in various syntheses including polymers synthesis.
  • Reprocessed Plastic v.79, pp. 595-606.
  • silicon and mercury can deactivate catalysts in the downstream synthesis processes. This can result in unreliable process operation and/or off-specification products.
  • mercury in addition to environmental emission issues, can weaken aluminum welds in downstream recovery and separation units, which poses process safety concerns.
  • the present disclosure relates to methods and systems for removing silicon and/or mercury contaminants from plastic-derived pyrolysis oil.
  • a first nonlimiting example method of the present disclosure comprises: removing silicon from a plastic-derived pyrolysis oil to yield a purified plastic-derived pyrolysis oil comprising 5 wppm or less of silicon; and steam cracking the plastic-derived pyrolysis oil in the presence of steam to produce a product.
  • a second nonlimiting example method of the present disclosure comprises: removing mercury from a plastic-derived pyrolysis oil to yield a purified plastic-derived pyrolysis oil comprising 1 wppb or less of mercury; and steam cracking the plastic-derived pyrolysis oil in the presence of a steam to produce a product.
  • a third nonlimiting example method of the present disclosure comprises: removing silicon and mercury from a plastic-derived pyrolysis oil to yield a purified plastic-derived pyrolysis oil comprising 5 wppm or less of silicon and 1 wppb or less of mercury; and steam cracking the plastic-derived pyrolysis oil in the presence of a steam to produce a product.
  • FIG. 1 is a diagram illustrating a process for reducing/removing silicon from a plastic-derived pyrolysis oil upstream of a steam cracking unit.
  • FIG. 2 is a diagram illustrating a process for reducing/removing mercury from a plastic-derived pyrolysis oil upstream of a steam cracking unit.
  • FIG. 3 is a diagram illustrating a process for reducing/removing silicon and mercury from a plastic-derived pyrolysis oil upstream of a steam cracking unit.
  • the present disclosure relates to methods and systems for removing silicon and/or mercury contaminants from plastic-derived pyrolysis oil. More specifically, in the methods and systems described herein, the plastic-derived pyrolysis oil is produced from plastic waste material in a plastic pyrolyzer where the plastic material is chemically broken down and then distilled. A plastic-derived pyrolysis oil cut is the primary product of the distillation. The plastic-derived pyrolysis oil is treated to reduce/remove silicon and/or mercury contaminants and then further processed by steam cracking to further reduce the carbon number. The resultant product is further processed to produce cuts suitable for use in various syntheses including polymers synthesis.
  • the product (or a fraction thereof) from the steam cracker may be treated to reduce/remove silicon and/or mercury contaminants ⁇
  • a reference to a “C x ” fraction, stream, portion, feed, or other quantity is defined as a fraction (or other quantity) where 50 wt% or more of the fraction corresponds to hydrocarbons having “x” number of carbons.
  • a range is specified, such as “C x -Cy”
  • 50 wt% or more of the fraction corresponds to hydrocarbons having a number of carbons from “x” to “y”.
  • a specification of “C x+ ” corresponds to a fraction where 50 wt% or more of the fraction corresponds to hydrocarbons having the specified number of carbons or more (or the specified number of carbons or less).
  • plastic-derived pyrolysis oil refers to pyrolysis oil where at least 50 wt% of the pyrolysis oil is derived from a plastic source. That is, the feedstock (also referred to as plastic feedstock) that is pyrolyzed comprises at least 50 wt% plastic.
  • plastic sources include, but are not limited to, plastic waste (e.g., plastic straws, plastic utensils, plastic bags, food containers, and the like), composite materials (e.g., composite packaging), and the like, and any combination thereof.
  • plastic waste e.g., plastic straws, plastic utensils, plastic bags, food containers, and the like
  • composite materials e.g., composite packaging
  • Said plastic sources may comprise one or more polymers that include, but are not limited to, polyolefins (e.g., homopolymer or copolymers of ethylene, propylene, butene, hexene, butadiene, isoprene, isobutylene, and other olefins), polystyrene, polyvinylchloride, polyamide (e.g., nylon), polyethylene terephthalate, polyurethane, ethylene vinyl acetate, and the like.
  • polyolefins e.g., homopolymer or copolymers of ethylene, propylene, butene, hexene, butadiene, isoprene, isobutylene, and other olefins
  • polystyrene polyvinylchloride
  • polyamide e.g., nylon
  • polyethylene terephthalate polyurethane
  • ethylene vinyl acetate ethylene vinyl acetate
  • the plastic portion of the plastic feedstock for pyrolysis may comprise polyolefin at 65 wt% to 100 wt% (or 65 wt% to 80 wt%, or 75 wt% to 90 wt%, or 80 wt% to 100 wt%) with a balance of one or more other polymers.
  • Pyrolysis of the plastic feedstock may be performed by known methods and in known systems (e.g., at temperatures of 400°C to 850°C, or 400°C to 600°C, or 500°C to 850°C).
  • the pyrolysis product is then distilled (or separated) into one or more cuts including a plastic-derived pyrolysis oil cut.
  • the plastic-derived pyrolysis oil may be a C5 + stream (or a C5-C30 stream, or a C5-C20 stream, or a C5-C25 stream, or a C5-C20 stream).
  • the plastic-derived pyrolysis oil may comprise 50 wt% or more (or 50 wt% to 100 wt%, or 50 wt% to 75 wt%, or 70 wt % to 90 wt%, or 80 wt% to 100 wt%) of C5 + hydrocarbons and less than 50 wt% (or 0 wt% to less than 50 wt%, or 25 wt% to 50 wt%, or 10 wt % to 30 wt%, or 0 wt% to 20 wt%, or 0 wt% to 5 wt%, or 0 wt% to 2 wt%) of C4. hydrocarbons.
  • the plastic-derived pyrolysis oil may have a specific gravity of 0.5 to 1.0 (or 0.5 to 0.7, or 0.6 to 0.9, or 0.7 to 1.0).
  • the plastic-derived pyrolysis oil may comprise 0 wt% to 60 wt% olefin content, 0 wt% to 25 wt% diolefin content, and balance other species like aromatics and paraffins for example.
  • the plastic -derived pyrolysis oil may have an initial boiling point of 30°C or greater (or 30°C to 200°C, or 30°C to 70°C, or 50°C to 150°C, or 100°C to 200°C).
  • the plastic- derived pyrolysis oil may have a final boiling point of 600°C or less (or 150°C to 600°C, or 250°C to 400°C, or 300°C to 500°C, or 400°C to 600°C).
  • the plastic-derived pyrolysis oil may have properties similar to a naphtha, a distillate, a wax, an atmospheric resid, and the like.
  • the plastic-derived pyrolysis oil may comprise silicon at 1 wppm to 50 wppm (or 1 wppm to 15 wppm, or 10 wppm to 30 wppm, or 25 wppm to 50 wppm) and/or mercury at 1 wppb to 500 wppb (or 1 wppb to 50 wppb, or 25 wppb to 100 wppb, or 50 wppb to 250 wppb, or 200 wppb to 350 wppb, or 250 wppb to 500 wppb, or 400 wppb to 500 wppb).
  • FIGS. 1-3 provide nonlimiting example diagrams illustrating said process.
  • FIG. 1 is a diagram illustrating a process 100 for reducing/removing silicon from a plastic-derived pyrolysis oil 102 upstream of a steam cracking unit 116.
  • the process 100 includes treating the plastic -derived pyrolysis oil 102 in a silicon removal unit 104 to produce a purified plastic-derived pyrolysis oil 106 having a silicon concentration of 5 wppm or less
  • the silicon concentration in the purified plastic derived pyrolysis oil 106 is less than the silicon concentration in the plastic-derived pyrolysis oil 102.
  • the purified plastic-derived pyrolysis oil 106 is then mixed with a steam cracker feed 110 to produce a mixed feed 114.
  • the purified plastic-derived pyrolysis oil 106 is admixed with the steam cracker feed 110 using a valve 108.
  • the purified plastic-derived pyrolysis oil 106 and the steam cracker feed 110 may be mixed in a vessel (not shown) or by any other suitable method to produce the mixed feed 114.
  • the steam cracker feed 110 and the purified plastic-derived pyrolysis oil 106 can be fed separately (not shown) steam cracking unit 116.
  • the purified plastic- derived pyrolysis oil 106 can be steam cracked without use of steam cracker feed 110. That is, the purified plastic-derived pyrolysis oil 106 can be used neat as the feed for the steam cracking unit 116.
  • the mixed feed 114 (or the steam cracker feed 110 and the purified plastic-derived pyrolysis oil 106 separately (not shown), or the purified plastic-derived pyrolysis oil 106 neat (not shown)) and steam 112 are fed into the steam cracking unit 116 for steam cracking to produce a product 118.
  • the mixed feed 114 can comprise the purified plastic -derived pyrolysis oil 106 at 1 wt% to 80 wt% (or 1 wt% to 5 wt%, or 1 wt% to 15 wt%, or 10 wt% to 25 wt%, or 20 wt% to 50 wt%, or 25 wt% to 65 wt%, or 50 wt% to 80 wt%) based on the total weight of the mixed feed 114.
  • the product 118 from the steam cracking unit 116 can then be processed in a recovery facility/unit(s) 120 to produce one or more products 122 suitable for use in various syntheses including polymer synthesis.
  • the silicon removal unit 104 can include a regenerable adsorbent where a regeneration gas 124 can be passed over the regenerable adsorbent in the silicon removal unit 104 at elevated temperatures to produce a spent regeneration gas 126 comprising silicon.
  • a method of the present disclosure can include: removing silicon from a plastic-derived pyrolysis oil to yield a purified plastic-derived pyrolysis oil comprising 5 wppm or less of silicon; and steam cracking the plastic-derived pyrolysis oil in the presence of steam to produce a product.
  • a system of the present disclosure can include: a silicon removal unit 104 upstream of and fluidly coupled to a steam cracking unit 116 configured to receive purified plastic-derived pyrolysis oil 106 from the silicon removal unit 104.
  • FIG. 2 is a diagram illustrating a process 200 for reducing/removing mercury from a plastic-derived pyrolysis oil 202 upstream of a steam cracking unit 216.
  • the process 200 includes treating the plastic-derived pyrolysis oil 202 in a mercury removal unit 204 to produce a purified plastic-derived pyrolysis oil 206 having a mercury concentration of 1 wppb or less ( ⁇ ? .g., 0 wppb to 1 wppb, or 0.001 wppb to 1 wppb, or 0.001 wppb to 0.5 wppb, or 0.001 wppb to 0.1 wppb).
  • the purified plastic-derived pyrolysis oil 206 is then mixed with a steam cracker feed 210 (e.g., steam cracker feeds 110 described above) to produce a mixed feed 214.
  • a steam cracker feed 210 e.g., steam cracker feeds 110 described above
  • the purified plastic-derived pyrolysis oil 206 is admixed with the steam cracker feed 210 using a valve 208.
  • the purified plastic-derived pyrolysis oil 206 and the steam cracker feed 210 may be mixed in a vessel (not shown) or by any other suitable method to produce the mixed feed 214.
  • the steam cracker feed 210 and the purified plastic-derived pyrolysis oil 206 can be fed separately (not shown) steam cracking unit 216.
  • the purified plastic-derived pyrolysis oil 106 can be steam cracked without use of steam cracker feed 110. That is, the purified plastic-derived pyrolysis oil 206 can be used neat as the feed for the steam cracking unit 216.
  • the mixed feed 214 (or the steam cracker feed 210 and the purified plastic-derived pyrolysis oil 206 separately (not shown), or the purified plastic-derived pyrolysis oil 206 neat (not shown)) and steam 212 are fed into the steam cracking unit 216 for steam cracking to produce a product 218.
  • the mixed feed 214 can comprise the purified plastic -derived pyrolysis oil 206 at 1 wt% to 80 wt% (or 1 wt% to 5 wt%, or 1 wt% to 15 wt%, or 10 wt% to 25 wt%, or 20 wt% to 50 wt%, or 25 wt% to 65 wt%, or 50 wt% to 80 wt%) based on the total weight of the mixed feed 214.
  • the product 218 from the steam cracking unit 216 can then be processed in a recovery facility/unit(s) 220 to produce one or more products 222 suitable for use in various syntheses including polymer synthesis.
  • the mercury removal unit 204 can include a regenerable adsorbent where a regeneration gas 224 can be passed over the regenerable adsorbent in the mercury removal unit 204 at elevated temperatures to produce a spent regeneration gas 226 comprising mercury.
  • the spent regeneration gas 226 may be passed through a mercury trap bed 228 to produce a reduced- mercury gas 230 that can be vented or recycled as regeneration gas 224.
  • a method of the present disclosure can include: removing mercury from a plastic-derived pyrolysis oil to yield a purified plastic-derived pyrolysis oil comprising 1 wppb or less of mercury; and steam cracking the plastic-derived pyrolysis oil in the presence of a steam to produce a product.
  • a system of the present disclosure can include: a mercury removal unit 204 upstream of and fluidly coupled to a steam cracking unit 216 configured to receive purified plastic-derived pyrolysis oil 206 from the mercury removal unit 204.
  • FIG. 3 is a diagram illustrating a process 300 for reducing/removing silicon and mercury from a plastic-derived pyrolysis oil 302 upstream of a steam cracking unit 320.
  • the process 300 includes treating the plastic-derived pyrolysis oil 302 in first in a silicon removal unit 304 to produce a partially purified plastic-derived pyrolysis oil 306 then in a mercury removal unit 308 to produce a purified plastic-derived pyrolysis oil 310 having a silicon concentration of 5 wppm or less (e.g.
  • the purified plastic-derived pyrolysis oil 310 is then mixed with a steam cracker feed 314 (e.g., steam cracker feeds 110 described above) to produce a mixed feed 318.
  • a steam cracker feed 314 e.g., steam cracker feeds 110 described above
  • the purified plastic -derived pyrolysis oil 310 is admixed with the steam cracker feed 314 using a valve 312.
  • the purified plastic-derived pyrolysis oil 310 and the steam cracker feed 314 may be mixed in a vessel (not shown) or by any other suitable method to produce the mixed feed 318.
  • the steam cracker feed 314 and the purified plastic-derived pyrolysis oil 310 can be fed separately (not shown) steam cracking unit 320.
  • the purified plastic-derived pyrolysis oil 106 can be steam cracked without use of steam cracker feed 110. That is, the purified plastic- derived pyrolysis oil 310 can be used neat as the feed for the steam cracking unit 320.
  • the mixed feed 318 (or the steam cracker feed 314 and the purified plastic-derived pyrolysis oil 310 separately (not shown), or the purified plastic-derived pyrolysis oil 310 neat (not shown)) and steam 316 are fed into the steam cracking unit 320 for steam cracking to produce a product 322.
  • the mixed feed 318 can comprise the purified plastic -derived pyrolysis oil 310 at 1 wt% to 80 wt% (or 1 wt% to 5 wt%, or 1 wt% to 15 wt%, or 10 wt% to 25 wt%, or 20 wt% to 50 wt%, or 25 wt% to 65 wt%, or 50 wt% to 80 wt%) based on the total weight of the mixed feed 318.
  • the product 322 from the steam cracking unit 320 can then be processed in a recovery facility/unit(s) 324 to produce one or more products 326 suitable for use in various syntheses including polymer synthesis.
  • the silicon removal unit 304 can include a regenerable adsorbent where a regeneration gas 328 can be passed over the regenerable adsorbent in the silicon removal unit 104 at elevated temperatures to produce a spent regeneration gas 330 comprising silicon.
  • the mercury removal unit 308 can include a regenerable adsorbent where a regeneration gas 332 can be passed over the regenerable adsorbent in the mercury removal unit 308 at elevated temperatures to produce a spent regeneration gas 334 comprising mercury.
  • the spent regeneration gas 334 may be passed through a mercury trap bed 336 to produce a reduced- mercury gas 338 that can be vented or recycled as regeneration gas 332.
  • a method of the present disclosure can include: removing silicon and mercury from a plastic-derived pyrolysis oil to yield a purified plastic -derived pyrolysis oil comprising 5 wppm or less of silicon and 1 wppb or less of mercury; and steam cracking the plastic-derived pyrolysis oil in the presence of a steam to produce a product.
  • a system of the present disclosure can include: a silicon removal unit 304 and a mercury removal unit 308 in series and each upstream of a steam cracking unit 320 configured to receive purified plastic-derived pyrolysis oil 310 from the silicon removal unit 304 or the mercury removal unit 308.
  • the product (or a fraction thereof) from the steam cracker may be treated to reduce/remove silicon and/or mercury contaminants.
  • Removal of silicon from the pyrolysis oil can be by any known method.
  • removal of the silicon can be achieved by passing the plastic-derived pyrolysis oil over an adsorbent (e.g. , a mixture of a lamellar double hydroxide like hydrotalcite and a hydrogenating metal like a group VI-B or group VIII metal, preferably Mo) in the presence of hydrogen at temperatures of 80°C to 360°C and a pressure of 70 psig to 750 psig, which is described in more detail in US Patent No. 8,106,250, which is incorporated herein by reference.
  • an adsorbent e.g. , a mixture of a lamellar double hydroxide like hydrotalcite and a hydrogenating metal like a group VI-B or group VIII metal, preferably Mo
  • Another method of removing silicon from the plastic -derived pyrolysis oil includes passing the plastic-derived pyrolysis oil over an adsorbent (e.g. , a mixture of copper oxide and a porous, inorganic refractory oxide containing at least 10 wt% alumina) in the presence of hydrogen at temperatures of 80°C to 500°C and a pressure of atmospheric pressure to 1000 psig, which is described in more detail in US Patent No. 4,645,587, which is incorporated herein by reference.
  • an adsorbent e.g. , a mixture of copper oxide and a porous, inorganic refractory oxide containing at least 10 wt% alumina
  • Removal of mercury from the pyrolysis oil can be by any known method.
  • Removal of mercury can be achieved by passing the plastic-derived pyrolysis oil over an adsorbent (e.g., metallic copper, gold, silver, nickel, thallium, platinum, palladium, gallium, and/or indium dispersed on an oxide support) in the presence of hydrogen at temperatures of 25°C to 100°C and a pressure of 0 psig to 300 psig, which is described in more detail in US Patent No. 5,463,167, which is incorporated herein by reference.
  • an adsorbent e.g., metallic copper, gold, silver, nickel, thallium, platinum, palladium, gallium, and/or indium dispersed on an oxide support
  • Another method of removing mercury from the plastic-derived pyrolysis oil includes contacting the plastic-derived pyrolysis oil with a sulfur compound (e.g., MM’S X where M is selected from a group consisting of alkali metal and ammonium radical, M’ is selected from a group consisting of alkali metal, ammonium radical, and hydrogen, and x is a number of at least 1) to produce a mercury sulfide.
  • a sulfur compound e.g., MM’S X where M is selected from a group consisting of alkali metal and ammonium radical, M’ is selected from a group consisting of alkali metal, ammonium radical, and hydrogen, and x is a number of at least
  • the mercury sulfide and other mercury compounds in the plastic-derived pyrolysis oil can be removed by passing the plastic- derived pyrolysis oil over an adsorbent (e.g., adsorbents described above) in the presence of hydrogen at temperatures of 25 °C to 100°C and a pressure of 0 psig to 300 psig.
  • an adsorbent e.g., adsorbents described above
  • Yet another method of removing mercury from the plastic-derived pyrolysis oil includes passing the plastic -derived pyrolysis oil over a sulfur-impregnated metal oxide filter or bed and/or a carbon-impregnated metal oxide filter or bed.
  • filters/beds trap the mercury by reacting with the mercury compound and maintaining the mercury in the filter/bed.
  • Such mechanisms are not regenerable and therefore, can be used in the mercury trap in FIGS. 2 and 3 or in the mercury removal unit of FIGS. 2 and 3 where the optional regeneration is not included.
  • steam cracking is a type of a pyrolysis process.
  • the feed for steam cracking can correspond to any type of liquid feed (i.e., feed that is liquid at 20°C and 100 kPa-a, as defined herein).
  • suitable steam cracking feeds can include hydrocarbon gases (e.g., ethane, propane, and the like), whole and partial crudes, naphtha boiling feeds, distillate boiling range feeds, resid boiling range feeds (atmospheric or vacuum), or combinations thereof.
  • a first nonlimiting example embodiment of the present disclosure is a method comprising: removing silicon from a plastic-derived pyrolysis oil to yield a purified plastic- derived pyrolysis oil comprising 5 wppm or less of silicon; and steam cracking the plastic- derived pyrolysis oil in the presence of steam to produce a product.
  • Said embodiment may also include one or more of the following: Element 1: wherein steam cracking the plastic-derived pyrolysis oil is further in the presence of a steam cracker feed; Element 2: Element 1 and admixing the purified plastic-derived pyrolysis oil with the steam cracker feed to yield a mixed feed; and steam cracking the mixed feed; Element 3 : Element 2 and wherein the mixed feed comprises the plastic-derived pyrolysis oil at 1 wt% to 80 wt% based on the weight of the mixed feed; Element 4: wherein removing the silicon from the plastic-derived pyrolysis oil comprises: contacting the plastic-derived pyrolysis oil with an adsorbent; and Element 5: Element 4 and wherein contacting the plastic -derived pyrolysis oil with the adsorbent is in the presence of hydrogen. Examples of combinations include, but are not limited to, Element 1 optionally in combination with Element 2 and Element 3 in combination with Element 4 and optionally Element 5; and Elements
  • a second nonlimiting example embodiment of the present disclosure is a method comprising: removing mercury from a plastic-derived pyrolysis oil to yield a purified plastic- derived pyrolysis oil comprising 1 wppb or less of mercury; and steam cracking the plastic- derived pyrolysis oil in the presence of a steam to produce a product.
  • Said embodiment may also include one or more of the following: Element 1; Element 2; Element 3; Element 6: wherein removing the mercury from the plastic-derived pyrolysis oil comprises: contacting the plastic-derived pyrolysis oil with an adsorbent in the presence of hydrogen; Element 7: Element 6 and the method further comprising; regenerating the adsorbent; and Element 8: wherein removing the mercury from the plastic-derived pyrolysis oil comprises: passing the plastic-derived pyrolysis oil through a mercury trap.
  • combinations include, but are not limited to, Element 1 optionally in combination with Element 2 and Element 3 in combination with Element 6 and optionally Element 7; Elements 1 and 2 in combination with Element 6 and optionally Element 7; Element 1 optionally in combination with Element 2 and Element 3 in combination with Element 8; Elements 1 and 2 in combination with 8; and Elements 6 and 8 an optionally Element 7 in combination and optionally in further combination with one or more of Elements 1-3.
  • a third nonlimiting example embodiment of the present disclosure is a method comprising: removing silicon and mercury from a plastic-derived pyrolysis oil to yield a purified plastic-derived pyrolysis oil comprising 5 wppm or less of silicon and 1 wppb or less of mercury; and steam cracking the plastic -derived pyrolysis oil in the presence of a steam to produce a product.
  • Said embodiment may also include one or more of the following: Element 1; Element 2; Element 3; Element 4; Element 5; Element 6; Element 7; and Element 8. Examples of combinations include, but are not limited to, two or more of Elements 1-3 in combination; two or more of Elements 4-8 in combination; and one or more of Elements 1-3 in combination with one or more of Elements 4-8.
  • compositions and methods are described herein in terms of “comprising” various components or steps, the compositions and methods can also “consist essentially of’ or “consist of’ the various components and steps.
  • compositions and methods are described in terms of “comprising,” “containing,” or “including” various components or steps, the compositions and methods can also “consist essentially of’ or “consist of’ the various components and steps. All numbers and ranges disclosed above may vary by some amount. Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range is specifically disclosed. In particular, every range of values (of the form, “from about a to about b,” or, equivalently, “from approximately a to b,” or, equivalently, “from approximately a-b”) disclosed herein is to be understood to set forth every number and range encompassed within the broader range of values.

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Abstract

Un procédé peut comprendre l'élimination du silicium et/ou du mercure d'une huile de pyrolyse dérivée de plastique pour obtenir une huile de pyrolyse dérivée de plastique purifié comprenant 5 ppm ou moins de silicium et/ou 1 ppm ou moins de mercure; et le craquage à la vapeur de l'huile de pyrolyse dérivée de plastique en présence d'une vapeur pour produire un produit.
EP20804725.8A 2019-10-24 2020-10-19 Élimination du mercure et du silicium d'une huile de pyrolyse dérivée de plastique Withdrawn EP4048759A1 (fr)

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US11479726B2 (en) 2020-09-28 2022-10-25 Chevron Phillips Chemical Company, Lp Circular chemicals or polymers from pyrolyzed plastic waste and the use of mass balance accounting to allow for crediting the resultant products as circular
GB2613166B (en) * 2021-11-25 2024-07-17 Plastic Energy Ltd A method for the removal of impurities from a pyrolysis oil
EP4306621A1 (fr) 2022-07-12 2024-01-17 Neste Oyj Élimination de silicium à partir d'huile dépolymérisée
WO2024013424A1 (fr) 2022-07-12 2024-01-18 Neste Oyj Élimination de silicium d'une huile dépolymérisée

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US4645587A (en) 1984-12-07 1987-02-24 Union Oil Company Of California Process for removing silicon compounds from hydrocarbon streams
WO1991015559A2 (fr) 1990-04-04 1991-10-17 Exxon Chemical Patents Inc. Procede d'elimination de mercure a l'aide d'adsorbants de metal disperse
US8038869B2 (en) * 2008-06-30 2011-10-18 Uop Llc Integrated process for upgrading a vapor feed
BRPI0802431B1 (pt) 2008-07-28 2017-02-07 Petróleo Brasileiro S/A - Petrobras processo de remoção de compostos de silício de correntes de hidrocarbonetos
CN104984743B (zh) * 2015-05-04 2017-10-13 华中科技大学 一种用于脱汞的废弃物衍生吸附剂制备方法及产品
JP7130632B2 (ja) * 2016-10-11 2022-09-05 サビック グローバル テクノロジーズ ベスローテン フェンノートシャップ 種々のスチームクラッカ構成を使用する、混合プラスチックからの高価値化学物質の最大化
RU2692082C1 (ru) * 2018-12-20 2019-06-21 Федеральное государственное бюджетное учреждение науки "Федеральный исследовательский центр "Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук" (ИК СО РАН, Институт катализа СО РАН) Катализатор защитного слоя для процесса гидроочистки кремнийсодержащего углеводородного сырья

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