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WO2025219653A1 - Hydrotraitement en phase liquide de déchets plastiques liquéfiés - Google Patents

Hydrotraitement en phase liquide de déchets plastiques liquéfiés

Info

Publication number
WO2025219653A1
WO2025219653A1 PCT/FI2025/050193 FI2025050193W WO2025219653A1 WO 2025219653 A1 WO2025219653 A1 WO 2025219653A1 FI 2025050193 W FI2025050193 W FI 2025050193W WO 2025219653 A1 WO2025219653 A1 WO 2025219653A1
Authority
WO
WIPO (PCT)
Prior art keywords
lwp
hydrotreatment
liquid phase
fraction
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/FI2025/050193
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English (en)
Inventor
Antti Kurkijarvi
Marjut Aho
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.)
Neste Oyj
Original Assignee
Neste Oyj
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Filing date
Publication date
Application filed by Neste Oyj filed Critical Neste Oyj
Publication of WO2025219653A1 publication Critical patent/WO2025219653A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • 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
    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
    • C10G1/065—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation in the presence of a solvent
    • 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
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/083—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts in the presence of a solvent
    • 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
    • C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
    • C10G19/02—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous alkaline solutions
    • 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
    • C10G45/22—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 with hydrogen dissolved or suspended in the oil
    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • 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
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
    • 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

Definitions

  • the present invention relates to a method for hydrotreatment of liquefied waste plastic by means of a liquid phase hydrotreatment process.
  • Liquefied waste plastics is a complex mixture of components. It has a wide boiling point range, and it contains problematic components like conjugated diolefins, metals, metalloids and halogens, which prevents its direct usage in most applications, like steam cracking. These problematic components are unique for LWP and these components cause problems in downstream processing through a variety of different (and not yet fully understood) mechanisms.
  • diolefins especially conjugated diolefins
  • metals and metalloids like silicon, may be adsorbed on a catalyst surface, thus blocking pores and active sites.
  • Halogens may cause corrosion through acid-based and chloride-based corrosion mechanisms, and may also lead to heat exchanger fouling through salt formation, especially after hydrotreatment.
  • the amount of these impurities should be minimised before the LWP is distributed into downstream processes, such as a conventional refinery process.
  • the hydrotreatment (such as diolefin removal) of LWP is carried out by hydrotreatment in a gaseous phase (in a so-called trickle bed reactor) in which at least hydrogen is present in gaseous phase, usually in large excess (very high hydrogen-to-oil ratio) in order to maintain a uniform reaction phase.
  • a gaseous phase in a so-called trickle bed reactor
  • at least hydrogen is present in gaseous phase, usually in large excess (very high hydrogen-to-oil ratio) in order to maintain a uniform reaction phase.
  • FI 2020 6383 Al discloses a process comprising hydrotreatment of a blend of LWP and a crude oil-derived feedstock in a FCC feed hydrotreater.
  • Finnish patent application No 2023 5610 discloses a method for LWP upgrading comprising a mild hydrotreatment step for e.g. diolefins removal and a subsequent hydrocracking step.
  • a large excess of hydrogen is employed, e.g. a H2 to oil ratio in the range of 200 to 450 Nm 3 /stdm 3 .
  • CN 111363580 A discloses a method for hydrotreating waste plastics comprising adding waste plastics into a liquid phase hydrogenation reactor and carrying out a hydrocracking reaction, feeding the cracking product into a second liquid phase hydrogenation reactor and carrying out a hydroisomerization reaction.
  • WO 2024/013430 Al relates to an improved method for processing liquefied waste plastics.
  • EP 4174150 Al discloses a method of processing liquefied waste plastic by hydrotreatment.
  • US 8008534 B2 discloses a multi-stage liquid phase hydroprocessing method, aiming at improved temperature management when treating high-boiling feedstocks.
  • US 2016/0264874 Al discloses a process for converting waste plastics to a high value product comprising, converting a waste plastics to a hydrocarbon stream in a liquid phase, hydroprocessing the hydrocarbon stream, recovering C5+ liquid hydrocarbons in a treated hydrocarbon stream, dechlorinating the treated hydrocarbons to provide a polished hydrocarbon stream, and steam cracking the treated or polished hydrocarbon stream. Dechlorination may occur in a hydroprocessing reactor.
  • the components of the hydrocarbon stream in the hydroprocessing reactor may be in the liquid phase, a liquid-vapour phase, or a vapour phase.
  • CN 115703976 A discloses a method for selective hydrogenation of oil to remove olefins from naphtha reforming.
  • CN 106479562 B discloses a method for hydrotreating petroleum products.
  • FIG. 1 shows a flow diagram of an embodiment of an integrated process of the present invention.
  • the present invention relates to one or more of the following items: 1.
  • step (iii) is carried out at a temperature in the range of 100-275 °C, preferably 170-250 °C.
  • step (iii) is carried out as a continuous process.
  • step (iii) is the first hydrotreatment to which the LWP is subjected.
  • liquid phase hydrotreatment (iii) includes a stage where a part of the liquid phase hydrotreated LWP is recycled back to the saturation step (ii).
  • the LWP is derived from liquefaction of polymer waste having an oxygen content of 15 wt.-% or less, preferably 10 wt.-% or less, more preferably 5 wt.-% or less, of the total weight of the polymer waste.
  • liquid phase hydrotreatment (iii) is carried out in a fixed bed reactor system.
  • the catalyst in the liquid phase hydrotreatment (iii) comprises at least one component selected from IUPAC group 6, 8 or 10 of the Periodic Table of Elements.
  • the catalyst in the liquid phase hydrotreatment (iii) is a supported catalyst and comprises at least Mo and at least one further transition metal on a support, such as a supported NiMo catalyst or a supported CoMo catalyst, wherein the support preferably comprises alumina and/or silica.
  • the catalyst in the liquid phase hydrotreatment (iii) is a supported CoMo catalyst and the support comprises alumina (CoMo/AhOa) and/or the catalyst is a supported NiMo catalyst and the support comprises alumina (NiMo/AhCh). 17.
  • the total fresh feed of the liquid phase hydrotreatment (iii) contains at least 50 wt.-% LWP, such as 50-100 wt.-%, or at least 60 wt.-%, at least 70 wt.-%, at least 80 wt.-%, at least 90 wt.-%, at least 95 wt.-%, or at least 99 wt.-% LWP.
  • the total fresh feed of the saturation step (ii) contains at least 50 wt.-% LWP, such as 50- 100 wt.-%, or at least 60 wt.-%, at least 70 wt.-%, at least 80 wt.-%, at least 90 wt.-%, at least 95 wt.-%, or at least 99 wt.-% LWP.
  • liquid phase hydrotreatment (iii) is performed under the following conditions:
  • LHSV liquid hourly space velocity
  • - a temperature in the range of 100-275 °C, preferably 170-250 °C.
  • the method further comprises a processing step providing at least an oil phase and an aqueous phase, wherein the saturation step (ii) and hydrotreating step (iii) is carried out before the processing step and the liquid phase hydrotreated LWP (10) is forwarded to the processing step; and/or the saturation step (ii) and hydrotreating step (iii) is carried out after the processing step and at least the oil phase is forwarded to the saturation step (ii).
  • processing step comprises at least aqueous alkaline heat treatment of the LWP followed by liquid-liquid separation (HT processing) to provide the oil phase and the aqueous phase.
  • HT processing liquid-liquid separation
  • the moving-catalyst type reactor system is a moving bed reactor system, a fluidised bed reactor system, an ebullated bed reactor system or a slurry reactor system.
  • the catalyst in the hydrocracking step is a supported catalyst and comprises at least Mo and at least one further transition metal on a support, such as a supported NiMo catalyst or a supported CoMo catalyst, wherein the support preferably comprises alumina and/or silica.
  • finishing step comprises subjecting at least a fraction of the hydrocracked product to at least one of an isomerisation step and/or a polishing hydrotreatment step.
  • finishing step comprises subjecting at least a fraction of the hydrocracked product to at least a polishing hydrotreatment step, and the polishing hydrotreatment step is carried out at a temperature in the range of from 300°C to 450°C.
  • finishing step comprises subjecting at least a fraction of the hydrocracked product to at least a polishing hydrotreatment step, and the polishing hydrotreatment step is carried out at a pressure in the range of from 20 bar to 80 bar, preferably 40-60 bar.
  • finishing step comprises subjecting at least a fraction of the hydrocracked product to at least a polishing hydrotreatment step, and the polishing hydrotreatment step is carried out in a fixed bed reactor.
  • An integrated process comprising at least one of the following diolefins removal (DOR) steps being carried out as a liquid phase hydrotreatment (c) preceded by a saturation step (b) in accordance with any one of items 1 to 58, the integrated process comprising at least one, preferably all of the following steps:
  • the present invention relates to a method for hydrotreatment of a liquefied waste plastic (LWP), the method comprising providing the LWP, saturating the LWP with hydrogen and subjecting the (hydrogen-saturated) LWP to liquid phase hydrotreatment in the presence of a solid hydrotreatment catalyst.
  • the method relates to removing diolefins from LWP by liquid phase hydrotreatment.
  • the hydrotreatment for diolefin removal (DOR) of LWP was carried out by hydrotreatment in a gaseous phase in which at least hydrogen is present in gaseous phase in order to achieve good result, in particular good diolefin (conjugated diolefin) removal efficiency.
  • liquid phase hydrotreatment In this operating mode the liquid reactor feed (LWP) is enriched (usually saturated) with hydrogen (molecular hydrogen; H2) and no gaseous hydrogen is present in the reactor.
  • LWP liquid reactor feed
  • H2 molecular hydrogen
  • liquid phase hydrotreatment does employ H2 and particularly does not refer to hydrogenation using only liquid hydrogen donors, such as hydrocarbon compounds.
  • liquid phase hydrotreatment is particularly favourable for LWP since LWP-based feeds contain unique impurities which can cause problems in downstream processing.
  • conventional feeds e.g. fossil feeds or hydrogenated-biomaterial-based feeds
  • the liquid phase hydrotreatment (with preceding saturation) of the present invention mainly aims at removing conjugated diolefins from the LWP, be it in treating crude LWP or in treating an already processed LWP.
  • the hydrotreatment for diolefins removal (DOR) by saturation and liquid phase hydrotreatment may also be referred to as selective hydrotreatment (for diolefins removal) or as mild hydrotreatment.
  • the present invention aims at removing at least 80% (by weight) of the conjugated diolefins which are present in the LWP (prior to saturation and liquid phase hydrotreatment).
  • liquefied waste plastics means a product (directly) obtained from liquefaction process comprising at least depolymerising waste plastics.
  • LWP is thus a material which is obtainable by depolymerizing waste plastics.
  • LWP may also be referred to as polymer wastebased oil, pyrolysis oil, depolymerized polymer waste or as liquefied polymer waste.
  • the waste plastics is typically in solid state and may be derived from any source, such as (collected) post-consumer plastics, (collected) industrial plastics or (collected) end-life-tires (ELT).
  • waste plastics refers to an organic polymer material which is no longer fit for its use or which has been disposed of for any other reason.
  • Waste plastics may more specifically refer to collected consumer plastics (also called “post-consumer waste plastics”; consumer plastics referring to any organic polymer material in consumer goods, even if not having "plastic” properties as such), collected industrial or commercial polymer (plastic) waste (also called to "post-industrial waste plastics”).
  • waste plastics or "polymer” in general does not encompass purely inorganic materials (which are otherwise sometimes referred to as inorganic polymers). Polymers in the waste plastics may be of natural and/or synthetic origin and may be based on renewable and/or fossil raw material.
  • the liquefaction process is typically carried out at elevated temperature, and preferably under non-oxidative conditions.
  • the liquefaction process may be carried out at elevated pressure.
  • Liquefaction processes comprise pyrolysis, hydrothermal liquefaction and others.
  • solid waste plastic is heated to a temperature of 400-600 °C under non-oxidative conditions.
  • the polymers thermally decompose and consequently release vapours and gases that exit the reactor in the gas phase.
  • This vapour/gas stream is subsequently cooled down to condense the (crude) LWP product and to separate the gases.
  • Crude LWP typically has a boiling range of about 40 °C - 550 °C, which corresponds approximately to carbon chain lengths of C5 to C55.
  • the final boiling point of the LWP can go up to 750°C.
  • the liquefaction process may be carried out in the presence of a catalyst.
  • the (liquid) effluent from the liquefaction process may be employed as the liquefied waste plastic (LWP) as such or may be subjected to fractionation (or separation) to provide a fraction (or separated liquid) of the effluent as the liquefied waste plastics.
  • the LWP may be a hydrothermal liquefaction oil or a fraction thereof.
  • multiple fractionations may be carried out.
  • two or more liquefaction process effluents and/or fractions thereof may be combined to give the LWP.
  • These effluents and/or fractions may have the same or similar boiling range or may have different boiling ranges.
  • fractionation comprises fractional distillation and/or fractional evaporation and/or fractional condensation.
  • typical product effluents from liquefaction processes comprise gaseous (NTP) hydrocarbons, and hydrocarbons that are waxy or solid at NTP but become liquids upon heating, for example upon heating to 80°C.
  • Crude LWP usually comprises the liquid (NTP) and (dissolved) waxy/solid components (i.e. the gaseous components are removed).
  • crude LWP is a mixture of hydrocarbonaceous organic components with a wide range of carbon chain lengths.
  • (crude) LWP is a complex mixture of mainly paraffins, olefins, naphthenes and aromatic hydrocarbons.
  • the total amount of olefins is typically high, which can be as high as 40 wt.% to 60 wt.%, whereas the amount of aromatic hydrocarbons is typically lower than 20 wt.%.
  • LWP also typically contains heteroatoms, including oxygen, nitrogen, chlorine and sulphur, in the form of organic compounds with heteroatom substituents.
  • heteroatoms including oxygen, nitrogen, chlorine and sulphur, in the form of organic compounds with heteroatom substituents.
  • the amounts of heteroatoms vary depending on the polymers used in production of LWP. Water is usually removed from the LWP product, but some dissolved water may still be present in the LWP.
  • depolymerizing waste plastic means decomposing or degrading the polymer backbones of the waste plastic, typically at least thermally, to the extent yielding polymer and/or oligomer species of smaller molecular weight compared to the starting waste plastic, but still comprising at least liquid (NTP) hydrocarbons.
  • NTP liquid
  • the liquefied waste plastic does not cover plastics in liquid form obtained merely by melting or by dissolving into a solvent, as these do not involve sufficient cleavage of the polymer backbones, nor waste plastics depolymerized completely to the monomer-level and thus being e.g. of gaseous (NTP) form.
  • Depolymerizing waste plastics may also involve cleavage of covalently bound heteroatoms such as O, S, and N from optionally present heteroatom-containing compounds.
  • the step of providing the LWP may comprise a liquefaction process (a process of depolymerizing waste plastics), preferably as described herein.
  • the waste plastics, or each waste plastics species in mixed waste plastics, to be subjected to liquefaction is usually in solid state, typically having a melting point in the range of 100°C or more as measured by DSC as described by Larsen et al. "Determining the PE fraction in recycled PP", Polymer testing, vol. 96, April 2021, 107058).
  • the waste plastics, or each waste plastics species may be at least partially melted before and/or during the depolymerisation.
  • Solid waste plastics may contain various further components, such as additives, reinforcing materials, etc., including fillers, pigments, printing inks, flame retardants, stabilizers, antioxidants, plasticizers, lubricants, labels, metals, paper, cardboard, cellulosic fibres, fibre-glass, even sand or other dirt. Some of the further components may be removed, if so desired, from the solid waste plastics, from melted waste plastic, and/or from liquefied waste plastic using commonly known methods.
  • the (solid) waste plastics (polymer waste) to be subjected to the liquefaction process (depolymerisation), and thus being the base material of the LWP has an oxygen content of 15 wt.-% or less, preferably 10 wt.-% or less, more preferably 5 wt.-% or less, of the total weight of the (solid) waste plastics.
  • the oxygen content may be 0 wt.-% and may preferably be in the range of 0 wt.-% to 15 wt.-% or 0 wt.-% to 10 wt.%.
  • Oxygen content in wt.-% can be determined by difference using the formula 100 wt.-% - (CHN content + ash content), wherein CHN content refers to combined content of carbon, hydrogen and nitrogen, as determined in accordance with ASTM D5291, and ash content refers to ash content as determined in accordance with ASTM D482/EN 15403.
  • the LWP of the present invention is derived from (crude) LWP and may, for example, be LWP (as defined above), crude LWP (i.e. the liquid fraction/product directly emerging from the liquefaction process), or a fraction of LWP being a fractionated crude LWP.
  • the LWP may comprise at least 90 wt.-% (crude) LWP, such as at least 95 wt.-% (crude) LWP or at least 99 wt.-% (crude) LWP.
  • the LWP feedstock may particularly be 100% LWP.
  • the LWP may be 100% crude LWP. This shall explicitly apply to all embodiments of the present invention.
  • LWP in particular crude LWP is a feed containing impurities which need to be removed, in particular Si and halogen (e.g. chlorine) impurities, and also conjugated diolefins.
  • the chlorine content of the crude LWP may be in the range of from 1 wt.-ppm to 4000 wt.-ppm, such as from 100 wt.-ppm to 4000 wt.-ppm, from 300 wt.-ppm to 4000 wt.-ppm, or from 400 to 4000 wt.-ppm.
  • the content of Cl (and similarly of F and Br) may be determined in accordance with ASTM-D7359-18.
  • crude LWP usually has a high acidity, such as expressed by a total acid number (determined e.g. according to method ASTM D664) of up to 100 mgKOH/g, such as 5.0 to 100.0 mg KOH/g, 7.0 to 100.0 mg KOH/g, 9.0 to 100.0 mg KOH/g, or 11.0 to 100.0 mg KOH/g.
  • the silicon content (Si content) of crude LWP may be high, such as in the range of from 15 to 3000 wt.-ppm, 50 to 3000 wt.-ppm, 100 to 3000 wt.-ppm, or 150 to 3000 wt.-ppm.
  • the content of silicon (Si) may be determined using X-ray fluorescence (XRF) spectroscopy or using ICP- AES based on ASTM D5185.
  • the content of conjugated diolefins in crude LWP may be particularly high, such as in the range of from 1.0 to 10.0 wt.-%, 2.0 to 10. wt.-%, or 3.0 to 10.0 wt.-%.
  • the content of diolefins can be determined by PIONA method as described by Pyl et al, Journal of Chromatography A, 1218 (2011) 3217-3223.
  • the LWP preferably comprises primarily hydrocarbons, typically more than 50 wt.- % based on the total weight of the LWP.
  • the LWP comprises two or more hydrocarbon species selected from paraffins, olefins, naphthenes and aromatics.
  • the composition of the LWP may vary depending e.g. on the composition of the waste plastics, liquefaction process type and condition. Further, the assortment of various species of waste plastics and impurities associated with collected waste may result in a presence of impurities including silicon, sulphur, nitrogen, halogens and oxygen related substances in various quantities in the LWP.
  • (Crude) LWP may specifically refer to an oil or an oil-like product obtainable from liquefaction using non-oxidative thermal or thermocatalytic depolymerisation of (solid) waste plastics (followed by optional subsequent fractionation).
  • (crude) LWP may also be referred to as "depolymerized polymer waste", “polymer waste-based oil”, “pyrolysis oil” or "liquefied polymer waste”.
  • the method of liquefaction is not particularly limited as long as it is a depolymerisation process and one may mention thermal depolymerisation processes, such as pyrolysis (e.g. fast pyrolysis) of waste plastics, or hydrothermal liquefaction of waste plastics.
  • thermal depolymerisation processes such as pyrolysis (e.g. fast pyrolysis) of waste plastics, or hydrothermal liquefaction of waste plastics.
  • a moving-catalyst type reactor system which may also be referred to as a "moving bed reactor system" is generally known as a reactor system in which the catalytic material flows alongside with the reactants (feed) and is then separated from the exit stream. The separated catalytic material may be recycled, after optional regeneration.
  • hydrotreatment generally refers to catalytic hydrotreatment, i.e. treatment in the presence of hydrogen and a hydrotreatment catalyst.
  • hydroprocessing which is carried out as catalytic hydroprocessing, i.e. in the presence of hydrogen and a hydroprocessing catalyst.
  • hydrotreatment is a treatment favouring (full or partial) olefin (or alkyne) saturation
  • hydroprocessing is a process favouring heteroatom (e.g. S, O) removal and/or aromates saturation in addition.
  • hydrocracking preferably refers to catalytic hydrocracking, i.e. cracking in the presence of hydrogen and a hydrocracking catalyst.
  • liquid phase hydrotreatment refers to a process in which a liquid phase-reactor feed is enriched (usually saturated) with hydrogen and no gaseous hydrogen is present in the reactor.
  • the liquid phase-reactor feed shall refer to the total (liquid) feed to the reactor, and may be referred to as the reactant / educt (excluding hydrogen and catalyst).
  • saturated shall encompass any condition in which hydrogen is present in the liquid-phase feed (at least the LWP), i.e. in an amount below saturation, in saturated amount and even in oversaturated condition (usually at most 150% of saturation) as long as the reaction mixture remains substantially liquid under the hydrotreatment conditions.
  • the catalyst may, for example, comprise at least one component selected from IUPAC group 6, 8 or 10 of the Periodic Table of Elements.
  • the catalyst preferably contains Mo and at least one further transition metal on a support. Examples of such a supported catalyst are a supported NiMo catalyst or a supported CoMo catalyst, or a mixture of both.
  • the support preferably comprises alumina and/or silica. These catalysts are usually employed as sulphided catalysts to ensure that the catalysts are in their active (sulphided) form.
  • Turning the catalysts into their active (sulphided) form may be achieved by sulphiding them in advance (i.e. before starting the hydrotreatment reaction) and/or by adding a sulphur-containing feed (containing sulphur e.g. as an organic or inorganic sulphide).
  • the feed may contain the sulphur from the start, or a sulphur additive may be admixed to the feed.
  • the hydrotreating employs a catalyst and the catalyst is a supported NiMo catalyst and the support comprises alumina (NiMo/AhCh) and/or the catalyst is a supported CoMo catalyst and the support comprises alumina (CoMo/AhOa).
  • a (content) percentage (%) mentioned in the present invention relates to % by weight.
  • this pressure value shall refer to an absolute pressure, unless specified to the contrary.
  • terms like "before” and “after” shall similarly apply to batch-like processes and to continuous processes.
  • the term “after” may also be referred to as “downstream” and the term “before” may be referred to as “upstream”.
  • the term "optional” when referring to a component or a method/process step or a unit/apparatus shall mean “with or without” that component (or “with or without” that step or “with or without” that unit/apparatus), or similar expression like "include or excluding."
  • a feed or (intermediate) product which is subjected to a certain treatment or step
  • a feed is split up (e.g. a feed line in a continuous process is split up) and one part of the feed is subjected to the specified treatment while another part of the feed is subjected to no treatment (or a different treatment).
  • step (b) it is possible that at least a part of the heavier fraction from step (b) is forwarded directly to hydrocracking while a further part of the heavier fraction is blended (co-processed) with the oil phase, suitably after the oil phase has been subjected to DOR.
  • the above-said shall refer to all feeds and (intermediate) products mentioned herein.
  • the method for hydrotreatment of LWP comprises saturating a liquid phase hydrotreatment feed (including the LWP) and subjecting the liquid phase hydrotreatment feed (including the hydrogen-saturated LWP) to liquid phase hydrotreatment in the presence of a hydrotreatment catalyst.
  • the thus produced liquid phase hydrotreated LWP may then be subjected to further workup and/or fed to a commonly known oil refinery upgrading process, in particular to an oil refinery upgrading process involving hydrocracking.
  • the liquid phase hydrotreatment removes diolefins from the LWP and makes it fit for further processing, e.g. in an oil refinery upgrading process.
  • the liquid phase hydrotreatment is preferably carried out at a temperature in the range of 100-275 °C, preferably 170-250 °C.
  • the liquid phase hydrotreatment may be carried out as a batch process or as a continuous process and is preferably carried out as a continuous process.
  • the liquid phase hydrotreatment is preferably the first hydrotreatment to which the LWP is subjected.
  • the inventors consider that diolefins in the LWP are harmful for many hydrotreatment catalysts and thus it is beneficial to carry out the liquid phase hydrotreatment (which may also be referred to as diolefins removal step) as the first hydrotreatment in the method of the present invention.
  • the "first hydrotreatment” means the first hydrotreatment after liquefaction.
  • the method comprises a step (ii) of saturating the liquefied waste plastic with hydrogen.
  • the thus hydrogen-saturated LWP is then ready to be subjected to the (actual) liquid phase hydrotreatment.
  • hydrogen may be mixed with the LWP before carrying out the liquid phase hydrotreatment.
  • mixing hydrogen with LWP means that the (usually gaseous) hydrogen is pressurized into the (liquid) LWP (or in general into the liquid phase hydrotreatment feed) until saturation is reached.
  • Mixing (pressurizing) hydrogen with/into LWP "before carrying out the liquid phase hydrotreatment” means that mixing is accomplished before the temperature exceeds the reaction temperature (e.g. as indicated above) and/or before the LWP reaches the hydrotreatment catalyst (catalyst bed). After saturating the LWP with hydrogen, excess hydrogen (gas) is suitably removed. Thus, it can be more easily ensured that an appropriate amount of hydrogen is present in the liquid LWP without (or substantially without) forming a gas phase in the hydrotreatment step.
  • a guard bed e.g. not containing hydrotreatment catalyst
  • the liquid phase hydrotreatment may include a stage in which a part (e.g. a fraction or a volumetric part) of the liquid phase hydrotreated LWP (formed in the liquid phase hydrotreatment) is recycled back to the saturation step. Recycling at least a part of the liquid phase hydrotreated LWP increases the total liquid volume using already-treated material (i.e. having lower or no reactivity to the hydrotreatment). Thus, the amount of hydrogen that can be mixed with/into the LWP (relative to fresh LWP) can be increased or adjusted.
  • a part e.g. a fraction or a volumetric part
  • liquid phase hydrotreated LWP contains lower amounts of impurities, contaminants and harmful components compared to the LWP, in particular much lower amounts of conjugated diolefins.
  • impurities, contaminants and harmful components is herein meant any substance, compound or composition which may have detrimental properties to any component, equipment or catalyst downstream of the hydrotreatment.
  • harmful components are compounds containing hetero atoms, metals and metalloids. Especially harmful hetero atoms include halogens such as chlorine.
  • Especially harmful metals include but are not limited to mercury, lead, sodium, arsenic, vanadium, iron, zinc and aluminium. Compounds containing silicon, phosphorous, oxygen, nitrogen and sulphur can also be problematic downstream the mild hydrotreatment, if not removed. Furthermore, especially conjugated diolefins (simply referred to as "diolefins" herein) and olefins are considered agents causing coking or fouling which the method of the present invention removes from the LWP in order for the treated LWP to be used downstream as a for an oil refinery upgrading process, such as a process including steam cracking or hydrocracking.
  • the liquid phase hydrotreatment (which is always preceded by a saturation step) of the present invention is specifically designed for diolefins removal (and may thus be referred to as selective or mild hydrotreatment). Even though other impurities (e.g. metal compounds, silicon compounds or halogens) may be removed as well, the majority thereof is suitably removed in a subsequent (main) hydrotreatment, or in a series of subsequent (main) hydrotreatments, in particular including hydrotreatment for hydrodemetallisation (HDM). In other words, the liquid phase hydrotreatment of the invention is mainly intended and suited for diolefins removal.
  • impurities e.g. metal compounds, silicon compounds or halogens
  • HDM hydrodemetallisation
  • diolefins removal is usually very effective in the liquid phase hydrotreatment step, even though some diolefins may remain in the liquid phase hydrotreated LWP.
  • the content of conjugated diolefins in the liquid phase hydrotreated LWP is 0.30 wt.-% or lower, more preferably 0.25 wt.-% or lower, 0.20 wt.-% or lower, 0.15 wt.-% or lower, or 0.10 wt.-% or lower.
  • the purpose of the liquid phase hydrotreatment according to the invention is to reduce the risk of harmful and/or detrimental properties of any of the impurities, contaminants and harmful components in the LWP.
  • the liquid phase hydrotreating step is suited to reduce the amount of these components and therefore reduces the risks and harms they would otherwise pose on any component, equipment or catalyst downstream of the liquid phase hydrotreatment.
  • the conjugated diolefin content in the LWP is preferably below 0.20 wt.%.
  • the liquid phase hydrotreatment is carried out in the presence of a solid catalyst (also referred to as a heterogeneous catalyst).
  • a solid catalyst also referred to as a heterogeneous catalyst.
  • the liquid phase hydrotreatment may carried out in a fixed bed reactor system.
  • the catalyst in the liquid phase hydrotreatment may be a supported catalyst, and the support preferably comprises alumina and/or silica.
  • the catalyst in the liquid phase hydrotreatment may comprise (as a catalytically active element) at least one component selected from IUPAC group 6, 8 or 10 of the Periodic Table of Elements.
  • the catalyst may comprises at least Mo and at least one further transition metal, preferably on a support, such as a supported NiMo catalyst or a supported CoMo catalyst, wherein the support preferably comprises alumina and/or silica.
  • the catalyst in the liquid phase hydrotreatment may for example be a supported CoMo catalyst and the support comprises alumina (CoMo/AhOs) and/or a supported NiMo catalyst and the support comprises alumina (NIMo/A ⁇ Os).
  • the above-mentioned catalysts are (each individually) preferably employed as sulphided catalysts to ensure that the catalysts are in their active (sulphided) form.
  • Turning the catalysts into their active (sulphided) form may be achieved by sulphiding them in advance (i.e. before starting the hydrotreatment reaction) and/or by adding a sulphur-containing feed (containing sulphur e.g. as an organic or inorganic sulphide).
  • the feed may contain the sulphur from the start, or a sulphur additive may be admixed to the feed.
  • the total fresh feed of the saturation step (ii) preferably contains at least 50 wt.-% LWP, such as 50-100 wt.-%, or at least 60 wt.-%, at least 70 wt.-%, at least 80 wt.-%, at least 90 wt.-%, at least 95 wt.-%, or at least 99 wt.-% LWP.
  • the same amounts apply to the total fresh feed of the hydrotreatment step (iii) considering that hydrogen and catalyst are not considered to be "feed”. It is preferred that all the hydrogen-saturated LWP (all the feed material having been subjected to saturation in step (ii)) be (directly) forwarded to the hydrotreatment step (iii).
  • the remainder of the total fresh feed may be a co-feed and/or a diluent, preferably a hydrocarbon (co)feed or diluent which is/are suitably added upstream and/or in the saturation step (ii). It is particularly preferably for the remainder of the total fresh feed, i.e. the feed other than the LWP, to have an impurities pattern which differs from that of the LWP.
  • the remainder of the total fresh feed may particularly be at least one of a crude oil-derived comprising at least one crude oil-fraction, e.g.
  • VGO vacuum gas oil
  • GO gas oil
  • HGO heavy gas oil
  • kerosene fraction light gas oil fraction
  • AR atmospheric residue
  • VR vacuum residue
  • DAO deasphalted oil
  • a bio-based hydrocarbon feed derived from fat(s) or oil(s) or fatty acid(s), or derivatives of fat(s), oil(s) or fatty acid(s), lignocellulose-based hydrocarbon(s), used lubricating oil(s), and Fischer Tropsch hydrocarbon(s).
  • the amount of LWP being subjected to saturation and liquid phase hydrotreatment be high because this step is specifically designed for an LWP feed.
  • a co-feed as mentioned above be added (blended) only (or mainly) with the liquid phase hydrotreated LWP (i.e. after liquid phase hydrotreatment and e.g. prior to a main hydrotreatment).
  • the total feed does not include catalyst, hydrogen or other gas, if any.
  • the fresh feed to the liquid phase hydrotreatment may particularly be (consist of) LWP, more specifically crude LWP.
  • the liquid phase hydrotreatment (iii) may be performed under the following conditions:
  • LHSV liquid hourly space velocity
  • - a temperature in the range of 100-275 °C, preferably 170-250 °C.
  • LHSV is the flow rate (in kg/h) of liquid phase hydrotreatment feed (oil) divided by weight (in kg) of the catalyst employed in the step.
  • oil means the feed of the liquid phase hydrotreatment (the “feed” excludes H 2 , catalyst and carrier gas, if any).
  • the method of present invention may comprise a further oil refinery upgrading process (employing the hydrotreated LWP) which provides an upgraded hydrocarbon fraction.
  • the upgraded hydrocarbon fraction may in particular be a distillate fraction (at least one distillate fraction) obtained from a distillation (fractionation) step in the oil refinery upgrading process.
  • the present invention provides an efficient method for producing valuable products from LWP depending on needs and thus contributes to sustainability.
  • the method of the present invention may comprise a processing step (processing the LWP) before the saturation step or after the hydrotreatment (or in-between two saturation-plus-hydrotreatment stages / sequences).
  • the processing step may comprise at least aqueous alkaline heat treatment of the LWP followed by liquidliquid separation (HT processing, also referred to as HTP) to produce an oil phase and a (waste) water phase.
  • HT processing also referred to as HTP
  • the oil phase may be forwarded to the saturation (and hydrotreatment) step (as the LWP).
  • the liquid phase hydrotreated LWP is forwarded to the processing step (and afterwards the oil phase may be forwarded to a further saturation and liquid phase hydrotreatment). That is, HT processing may be carried out before saturation and hydrotreatment or may alternatively or in addition be carried out after the liquid phase hydrotreatment (but prior to an oil refinery upgrading process mentioned herein).
  • the HT processing (and/or the oil refinery upgrading process) is (are) preferably carried out in accordance with the (preferred) embodiments of the respective step(s) of the integrated process mentioned herein.
  • the method may comprise fractionating the LWP (suitably crude LWP or liquid phase hydrotreated crude LWP) to produce at least one distillate fraction and a residue fraction.
  • the method may comprise purifying the LWP (e.g. by means of HT processing) to produce a purified LWP and then fractionating the purified LWP to produce at least one distillate fraction and a purified residue fraction.
  • the processing is preferably carried out after fractionation.
  • liquid phase hydrotreatment in accordance with the present invention may preferably be carried out both before the fractionation (suitably employing crude LWP) and after the HT processing (employing the oil phase).
  • the fractionation is preferably carried out in accordance with the (preferred) embodiments of the respective step(s) of the integrated process mentioned herein.
  • Employing at least one fractionation step is particularly useful. That is, the inventors surprisingly found that heavy (high molecular weight) material may cause catalyst fouling in downstream (oil refinery) processing.
  • the oil refinery upgrading process preferably comprises at least a (main) hydrotreatment step (or more than one hydrotreatment step).
  • This (subsequent) hydrotreatment process is preferably adapted to remove at least one of metal(s), metalloid(s) and halogen(s) (adapted to remove / under conditions for removing metal impurities, metalloid impurities and/or halogen impurities).
  • This step (or at least one of these steps, preferably at least the first one) may be referred to as a hydrodemetallisation (HDM).
  • the (subsequent) hydrotreatment thus makes the LWP material (liquid phase hydrotreated LWP) even more suitable for subsequent processing.
  • This hydrotreatment step may be performed in the presence of gaseous hydrogen.
  • the hydrotreatment step may be performed in a fixed bed reactor or a moving-catalyst type reactor.
  • the HDM is preferably carried out in accordance with the (preferred) embodiments of the respective step of the integrated process mentioned herein.
  • the oil refinery upgrading process may further comprise a hydrocracking step.
  • the hydrocracking step may be performed alternatively to the above-mentioned (oil refinery upgrading) hydrotreatment step or maybe performed in addition to the (oil refinery upgrading) hydrotreatment step.
  • the hydrocracking step is carried out after (downstream) the hydrotreatment step. In this manner, improved catalyst life can be expected.
  • the hydrocracking step is preferably carried out in accordance with the (preferred) embodiments of the respective step of the integrated process mentioned herein.
  • the present invention also relates to an upgraded hydrocarbon fraction obtainable (or obtained) by the method of the invention.
  • the product of the method of the present invention contains the usual LWP-based impurities (which cannot be fully removed), such as specific metal/metalloid impurities but contains lower than usual (as compared to other impurities) reaction products of diolefins.
  • the method of the present invention is preferably carried out as a part of (or independently as multiple parts of) an integrated process for treating crude LWP and involving hydrocracking.
  • the integrated process is a process comprising at least one, preferably all of the following steps:
  • At least one of the DOR steps is actually carried out and is carried out as a sequence of the saturation step (b) and the liquid phase hydrotreatment step (c) of the method of the present invention.
  • FIG. 1 is a flow diagram illustrating the overall concept (and embodiments) of an integrated process of the present invention.
  • diamond shapes on arrows designate feeds/products (intermediates).
  • solid arrows and rectangles refer to mandatory steps/stages/units (unless a solid arrow starts/ends in a dashed rectangle) whereas dashed arrows (and rectangles) refer to optional steps / units.
  • FIG. 1 shows that a crude LWP feed (1) is subjected to fractionation (either directly or after optional hydrotreatment for diolefins removal; DOR).
  • the fractionation results in a distillate fraction (2) and a heavier fraction (3).
  • the distillate fraction (2) is forwarded to HT processing (HTP) together with an (optional) LWP co-feed.
  • HTP HT processing
  • Liquid-liquid separation (in HTP) yields an oil phase (5) and an aqueous phase (6).
  • the oil phase (5) is suitably forwarded to hydrotreatment for diolefins removal (DOR) and subsequent optional hydrotreatment for hydrodemetallisation (HDM).
  • DOR diolefins removal
  • HDM hydrodemetallisation
  • a further/second (optional) fractionation may be carried out, yielding a second distillate fraction (8) and a second heavier fraction (7).
  • the second distillate fraction (8) may e.g. be forwarded to steam cracking (after optional further work-up, which is not shown).
  • At least one DOR step preferably each DOR step, is carried out as a liquid phase hydrotreatment (including the saturation step) in accordance with the method of the present invention.
  • at least the (first) fractionation, the HT processing and the hydrocracking is carried out in addition.
  • the hydrocracking employs at least one fraction (or product/intermediate) as a feed, preferably a heavy fraction (3; 7).
  • the heavier fraction (3) from the first fractionation may be used as such (illustrated by the lowermost arrow), in particular when the LWP has beforehand been subjected to DOR, or may be fed to any one of the optional DOR or HDM (and even to the second fractionation; not shown) for co-processing (with material, e.g. oil phase (5), after HTP).
  • the heavier fraction (3) may be directly forwarded to hydrocracking.
  • hydrocracking is carried out, and is carried out using at least one material (5; 7; 9; 11) emerging from the oil phase (simply referred to as “oil phase” (5) as the case may be) and/or at least one material (3; 7; 9; 11) emerging from the heavier fraction (3) (simply referred to as "heavier fraction” (3) as the case may be).
  • at least one material (5; 7; 9; 11) emerging from the oil phase (simply referred to as "oil phase” (5) as the case may be) and/or at least one material (3; 7; 9; 11) emerging from the heavier fraction (3) (simply referred to as “heavier fraction” (3) as the case may be).
  • the integrated process of an embodiment of the present invention comprises subjecting the crude LWP feed (1) to fractionation to provide at least one distillate fraction (2) and a heavier fraction (3), subjecting the distillate fraction (2), together with an LWP co-feed (4), to aqueous alkaline heat treatment followed by liquid-liquid separation (HT processing; HTP) to provide at least an oil phase (5) and an aqueous phase (6), and subjecting the oil phase (5) and/or the heavier fraction (3) to hydrocracking to obtain a hydrocracked product (12).
  • HT processing liquid-liquid separation
  • HTP liquid-liquid separation
  • the oil phase (5) and/or the heavier fraction (3) may be subjected (each individually or together, i.e.
  • HT processing HT processing
  • the integrated process preferably further comprises subjecting the oil phase (5) (obtained from HTP) to hydrotreatment for diolefins removal (DOR) and optionally for hydrodemetallisation (HDM). That is, the oil phase (5) is preferably subjected to hydrotreatment under conditions adapted for diolefins removal (DOR), suitably as a liquid phase hydrotreatment of the invention.
  • the integrated process may comprise a further hydrotreatment under conditions adapted for hydrodemetallisation (HDM). Even though such a sequential processing is beneficial in view of catalyst life, it is also possible to employ a single hydrotreatment step under conditions adapted for both diolefins removal and hydrodemetallisation.
  • oil phase (5) may still be designated as “oil phase” (5) in the following, even though it is also more accurately referred to as “DOR hydrotreated material (9)” (or “DOR hydrotreated oil phase (9)") and as “HDM hydrotreated material (11)".
  • DOR hydrotreated material (9) or “DOR hydrotreated oil phase (9)”
  • HDM hydrotreated material (11) This similarly applies to the "heavier fraction", the “second distillate fraction” and the "second heavier fraction”.
  • a HDM (step) is carried out on at least the oil phase (5), more preferably after DOR on DOR hydrotreated material (9).
  • all the LWP-based material (3; 5; 9) which is fed to the HDM (step) has undergone at least one DOR (step).
  • each material which is derived from LWP i.e. which emerges from the crude LWP feed and/or from the LWP co-feed
  • has undergone (at least one) DOR at least the oil phase (5) has undergone DOR if only the oil phase (5) is fed as LWP based material, or at least both the oil phase (5) and the heavy fraction (3) have undergone DOR, or at least both the oil phase (5) and the crude LWP feed (1) (before fraction and yielding the heavy fraction (3)) have undergone DOR.
  • the integrated process may comprise subjecting at least a fraction of the oil phase (5) to hydrocracking (of step (c)), optionally together with the heavier fraction (3).
  • at least a heavier fraction (7) of the oil phase (5) (more preferably a fraction of the oil phase from which a naphtha range fraction has been removed by fractionation) is subjected to hydrocracking (of step (c)).
  • the oil phase (5) may be treated prior to such second fractionation, suitably by at least DOR, i.e. it may be a DOR and/or HDM hydrotreated oil phase (9; 11), and thus at least a fraction (7) thereof (preferably a heavier fraction as stated above) may be subjected to hydrocracking (of step (c)).
  • the integrated process comprises subjecting a blend of the heavier fraction (3) of step (b) and the oil phase (5) of step (c) to hydrodemetallisation (HDM), followed by a second fractionation and subsequent hydrocracking of a thus- obtained fraction (preferably a second heavier fraction (7)).
  • the oil phase (5) is suitably subjected to hydrotreatment for diolefins removal (DOR) prior to subjecting the blend to HDM.
  • Subjecting (or feeding) a "blend" to a process/reaction/unit in the present invention shall (generally) include any kind of co-processing. In particular, it shall not be limited to pre-blending in the sense of blending outside the reactor or unit, even though such pre-blending is an option.
  • the integrated process may comprise subjecting crude LWP feed (1) to hydrotreatment for diolefins removal (DOR) (i.e. under conditions adapted for diolefins removal; suitably as a liquid phase hydrotreatment of the invention) prior to fractionation in step (b).
  • DOR diolefins removal
  • the crude LWP feed (1) having been subjected to DOR is employed as (and may still be referred to as) crude LWP feed (1) in step (b).
  • DOR hydrotreated crude LWP 10
  • liquid phase hydrotreated LWP liquid phase hydrotreated LWP
  • DOR hydrotreated material this shall refer to both the DOR hydrotreated oil phase (which may also comprise heavy fraction (3) being co-fed to DOR) and to the DOR hydrotreated crude LWP feed (10).
  • the crude LWP feed (1) is subjected to hydrotreatment for diolefins removal (DOR) prior to fractionation in step (b).
  • DOR diolefins removal
  • any LWP-based material be subjected to at least one DOR prior to being subjected to a HDM step and/or to a hydrocracking step.
  • at least one DOR step (more preferably each DOR) is carried out as a liquid phase hydrotreatment of the method of the present invention.
  • the heavier fraction (3) (from step (b)) is not subjected to HT processing (prior to hydrocracking). Furthermore, the heavier fraction (3) may be forwarded to hydrocracking without intermediate hydrotreatment. In particular, the heavier fraction (3) may be forwarded directly to subsequent processes, such as hydrocracking (preferably without any intermediate step; note, however, that steps/stages which are necessary/usual for hydrocracking, such as temperature and pressure changes, shall not be considered as "intermediate step” even if not carried out exclusively in a hydrocracking unit).
  • the heavier fraction (3) (or a part thereof, in particular a volumetric part thereof) may be unified (blended/co-processed) with the (suitably DOR hydrotreated) oil phase (5) and treated together (co-process) with the oil phase (5), e.g. by (optional) HDM and (optional) second fractionation, and eventually at least a part of the material (7; 9; 11) resulting from the unified/co-processed material (blend) may then be subjected to the hydrocracking.
  • the "hydrocracking" shall refer to the hydrocracking reaction and/or the hydrocracking stage (whatever fits best in the respective context), even when carried out in multiple reactors.
  • the distillate fraction (2) from step (b) is preferably a naphtha range fraction (this similarly applies to the second distillate fraction, if present).
  • a naphtha range fraction in the present invention is preferably a fraction having a final boiling point in the range of 150°C to 210°C, more preferably in the range of 160 to 200°C, such as in the range of 170 to 190°C 170 to 190°C or in the range of 175 to 185°C.
  • the initial boiling point of a naphtha range fraction is preferably in the range of from 20°C to 60°C, more preferably in the range of from 25°C to 50°C, in the range of from 30°C to 45°C, or in the range of from 30°C to 40°C. Unless stated to the contrary, boiling points (and ranges) in the present invention are determined in accordance with ASTM-D2887.
  • the heavier fraction (3) is generally heavier (higher-boiling) than the distillate fraction (2) (lighter fraction).
  • the heavier fraction (3) has a 10 vol% boiling point which is higher than the 90 vol% boiling point of the distillate fraction (2).
  • the heavier fraction (3) may be a bottoms (residue) fraction.
  • the distillate fraction (2) is subjected to HT processing together with an LWP cofeed (4) (i.e. the distillate fraction is co-processed with the LWP co-feed).
  • the distillate fraction (4) may be pre-blended with the LWP co-feed (4) before being subjected to HT processing or it may be blended at the time of being subjected to HT processing (e.g. as a co-feed via a separate feed inlet to that step).
  • the LWP co-feed may in particular comprise or be crude LWP (LWP directly after depolymerisation, of course with water and gases removed; the liquid product).
  • the oil phase (5) from HTP may in particular be subjected to hydrotreatment for diolefins removal (DOR), subsequently subjected to hydrotreatment for hydrodemetallisation (HDM), thereafter subjected to a second fractionation to provide at least a second distillate fraction (8) and a second heavier fraction (7), and the second heavier fraction (7) is then forwarded to hydrocracking.
  • the second distillation may of course similarly be carried out in the absence of one or both of the DOR and the HDM.
  • the second distillate fraction (8) is preferably a naphtha range fraction as well.
  • DOR and HDM are not performed (i.e. these steps may be optional).
  • the second heavier fraction (7) is generally heavier (higher-boiling) than the second distillate (lighter) fraction (8).
  • the second heavier fraction (7) has a 10 vol% boiling point which is higher than the 90 vol% boiling point of the second distillate fraction (8).
  • the second heavier fraction (7) may in particular be a bottoms (residue) fraction.
  • At least a part (e.g. volumetric part) of the heavy fraction (3) of step (b) may be blended with the oil phase (5), e.g. after DOR but prior to HDM, or after HDM (but prior to second fractionation, if present).
  • "blending" prior to a certain step shall include the case in which the blending components are admixed in the reactor (e.g. co-fed) rather than being actually blended before being fed (pre-blending).
  • this expression shall refer to coprocessing in general, while pre-blending is an option.
  • at least the second heavier fraction (7) is subjected to hydrocracking.
  • At least one of the second distillate fraction (8) and the oil phase (5) is subjected to steam cracking, preferably after further work-up such as a polishing treatment. That is, since each of these fractions (preferably naphtha fractions) has undergone HT processing, the silicon content thereof is usually low enough for processing under steam cracking conditions, at least after having been subjected to e.g. polishing.
  • a co-feed such as a fossil co-feed, may be employed in steam cracking.
  • a steam cracking co-feed may be or comprise a renewable (bio-based) feed and/or a fossil feed (a crude oil fraction) which have commentary impurities profiles (as compared to LWP-based feeds / LWP-based material).
  • the distillate fraction (2) is subjected to HT processing while the amount of LWP co-feed is in the range of at least 50 wt.-% (such as in the range of 50 to 95 wt.-%, in the range of 50 to 90 wt.-%, or in the range of 60 to 80 wt.-%) of the total feed, the rest being the distillate fraction.
  • a lighter fraction (2) (preferably naphtha fraction) is subjected to HT processing and the resulting (light/naphtha) oil phase (5) is ready to be fed to steam cracking.
  • a naphtha fraction has been found to be particularly suitable for steam cracking, at least after having been subjected to further work-up e.g. polishing. As a matter of course, this similarly applies to the second distillate fraction (8).
  • the hydrotreatment for hydrodemetallisation is usually carried out under conditions which are harsher than the conditions under which the hydrotreatment for diolefins removal (DOR) is carried out.
  • the HDM may in particular be carried out at a higher temperature than the DOR.
  • the temperature (for HDM) may be in the range of from 300 to 500°C, such as 355 to 450°C, 355 to 500°C, or 360°C to 400°C.
  • the HDM may be carried out under a higher hydrogen partial pressure than the DOR.
  • the oil phase (5) is subjected at least to DOR.
  • the oil phase (5) is further subjected at least to HDM.
  • the oil phase (5) may be subjected to DOR and to HDM in this order.
  • the integrated process of the present invention is preferably carried out as a continuous process as a whole. Individual steps may be carried out as a batch process or as a continuous process. Preferably, at least the hydrotreatment(s) (DOR, HDM) and/or the hydroprocessing(s) (hydrocracking) are carried out as a continuous process (step).
  • DOR, HDM hydrotreatment(s)
  • hydroprocessing(s) hydrocracking
  • DOR (if more than one DOR is present, at least one thereof) is carried out as a liquid phase hydrotreatment in the presence of a solid hydrotreatment catalyst.
  • step (b) it is particularly preferable that at least DOR before fractionation of step (b), if present, be carried out as a liquid phase hydrotreatment because such a treatment has to process a lot of material (e.g. all the crude LWP feed) in which case liquid phase hydrotreatment is particularly efficient. Nevertheless, it is also preferable that DOR after HT processing, if present, be carried out as a liquid phase hydrotreatment because this DOR step similarly benefits from the high efficiency of the method of the present invention.
  • DOR removes diolefins from the crude LWP feed (1) and/or from the oil phase (5) and/or from the heavier fraction (3) and/or from the LWP co-feed (4) and makes it fit for processing in an oil refinery upgrading process, including but not limited to the downstream hydrocracking mentioned herein.
  • the DOR may be carried out as a batch process or as a continuous process and is preferably carried out as a continuous process.
  • the DOR before fractionation (b) is preferably the first hydrotreatment to which the crude LWP feed (1) is subjected.
  • the DOR after HT processing is preferably the first hydrotreatment to which the distillate fraction (2) (or the oil phase (5) emerging from the distillate fraction after HT processing) is subjected after the fractionation of step (b); and it is preferably the first hydrotreatment in the overall integrated process when no DOR (of the crude LWP feed (1)) is present before the fractionation step.
  • the "first hydrotreatment” means the first hydrotreatment after liquefaction.
  • the integrated process comprises the step of saturating the feed(s) (1; 3; 5) to liquid phase hydrotreatment (referred to as "liquid phase-reactor feed” or simply as "LWP” in the more general context of the method of the invention) with hydrogen for carrying out the liquid phase hydrotreatment.
  • liquid phase-reactor feed referred to as "liquid phase-reactor feed” or simply as "LWP” in the more general context of the method of the invention.
  • hydrogen- saturated feed e.g.
  • liquid phase hydrotreatment is then ready to be subjected to the liquid phase hydrotreatment, as set forth in detail above with respect to the method of the present invention. It is to be understood that all embodiments and preferred conditions of the liquid phase hydrotreatment (including saturation step) of the method of the present invention similarly apply to the DOR step(s) of the integrated process. Unless resulting in a contradiction, this even applies if one or more of the DOR step(s) is not carried out as a liquid phase hydrotreatment, while according to the integrated process at least one DOR step is carried out as a liquid phase hydrotreatment.
  • the integrated process of the present invention provides an upgraded hydrocarbon fraction.
  • the upgraded hydrocarbon fraction may in particular be a distillate fraction (at least one distillate fraction) obtained from fractionation of the hydrocracking product (12), after optional post-treatment.
  • the present invention provides an efficient integrated process for producing valuable products from LWP depending on needs and thus contributes to sustainability.
  • the integrated process of the present invention comprises an aqueous alkaline heat treatment of at least the distillate fraction (2) obtained in step (b), followed by liquid-liquid separation (HT processing).
  • the HT processing provides at least an oil phase (5) (product phase) and an aqueous phase (6) (usually for later work-up I product recovery, as it may still contain product).
  • the aqueous alkaline heat treatment and subsequent separation are collectively referred to as "HT processing" or "HT processing stage” or"HT processing step” (HTP).
  • the aqueous alkaline heat treatment is a heat treatment of (at least) the distillate fraction (2) with an aqueous medium under alkaline (basic) conditions.
  • the alkaline conditions mean a pH of the aqueous solution of more than 7.0, preferably at least 8.0, at least 9.0 or at least 10.0.
  • the alkaline conditions are preferably adjusted by employing an alkaline substance dissolved in the aqueous medium.
  • the content of the alkaline substance is preferably in the range of from 0.2 to 10.0 wt.-%, preferably at least 0.5 wt.-% or at least 1.0 wt.-%.
  • the aqueous medium is preferably water and may contain further components (in addition to water and alkaline substance) as long as they do not interfere with the HT processing.
  • the aqueous alkaline heat treatment is preferably carried out at a temperature in the range of 150°C to 450°C, more preferably 200°C to 450°C.
  • a temperature of 150°C or above, in particular 200°C or above is particularly preferable because such a temperature results not only in washing/acid removal but actually results in reactive treatment of the distillate fraction (reactive extraction), thus even reducing/removing impurities such as organic halogen compounds.
  • a high temperature results in reaction of impurity compounds which are otherwise insoluble in water and allows removing the impurities (such as organic-bound halogen).
  • reactive extraction using an aqueous solution of a alkali metal/alkaline earth metal hydroxide at 150°C or more, preferably 200°C or more removes not only chlorine contaminants and to some degree nitrogen contaminants (both of which are undesired in steam cracker feeds) but most importantly can remove silicon- containing contaminants (such as organic silicon compounds and/or colloidal inorganic silicon material).
  • the aqueous alkaline heat treatment (in HTP) may be carried out at a temperature of 150°C or more, preferably 190°C or more, 200°C or more, 210°C or more, 220°C or more, 240°C or more, or 260°C or more.
  • the aqueous alkaline heat treatment may be carried out at a temperature of 450°C or less, preferably 400°C or less, 350°C or less, 320°C or less, or 300°C or less.
  • the aqueous alkaline heat treatment may be carried out at a temperature in the range of 200°C to 350°C, preferably 220°C to 330°C, 240°C to 320°C, or 260°C to 300°C.
  • the aqueous alkaline heat treatment (and HTP in general) may be carried out as a reactive extraction, as specified in FU28848B.
  • fractionation (independently any fractionation step/stage mentioned herein) may be done by any known means of providing at least two fractions based on different boiling properties and shall encompass distillation, evaporation and stripping.
  • the fractionation of step (b) is preferably carried out using a fractionation method with low thermal impact, more preferably hot hydrogen stripping.
  • the hydrotreatment for hydrodemetallisation is a process adapted to remove at least one of metal(s), metalloid(s) and halogen(s).
  • HDM adapted to remove / carried out under conditions for removing metal impurities, metalloid impurities and/or halogen impurities.
  • the catalyst employed in the HDM step may be (independently) selected from those listed for the DOR step.
  • the HDM makes the hydrotreated material (HDM hydrotreated material (11)) even more suitable for subsequent processing.
  • the HDM may be performed in the presence of gaseous hydrogen.
  • the HDM may be performed in a fixed bed reactor or a moving-catalyst type reactor.
  • the total feed of the hydrocracking step (the total feed to the hydrocracker) preferably contains at least 0.5 wt.-%, more preferably at least 1.0 wt.-% or at least 2.0 wt.-% of LWP-based material.
  • the LWP-based material shall refer to material which results from / is based on (crude) LWP, such as material resulting from the crude LWP feed (1) of step (a) and from the LWP co-feed (4) in the HT processing stage.
  • the (hydrotreated) "oil phase” (5) and the "heavier fraction” (3) as well as the "distillate fraction” (2) each are a "LWP-based material" (as far as originating from LWP).
  • the total feed of the hydrocracking step (the total feed to the hydrocracker) further preferably contains at least 0.5 wt.-%, more preferably at least 1.0 wt.-% or at least 2.0 wt.-% of the heavier fraction (3).
  • the heaver fraction (3) which may have undergone additional treatment such as DOR and/or HDM before hydrocracking, and may therefore be referred to as a material resulting from the heavier fraction (3).
  • the total feed (to the hydrocracking step) shall encompass all feeds for conversion (which are mainly hydrocarbons) and shall not encompass catalyst (or carrier) or diluents, such as carrier gas, if present.
  • the content (upper limit) of LWP-based material e.g.
  • optionally treated heavier fraction (3) and/or treated oil phase (5)) in the total feed to the hydrocracker is not particularly limited, but is preferably independently selected from 95 wt.-% or less, 70 wt.-% or less, or 50 wt.-% or less.
  • the content of the LWP-based material cannot exceed 100 wt.-%.
  • Hydrocracking may be carried out in a fixed catalyst bed type reactor system or in a moving-catalyst type reactor system, and is preferably carried out in a movingcatalyst type reactor system to obtain a hydrocracked product.
  • the movingcatalyst type reactor system is preferably selected from the group consisting of a moving bed reactor system, a fluidised bed reactor system, an ebullated bed reactor system and a slurry reactor system.
  • the above reactor system types shall independently refer to both hydrocracking reactor systems in case hydrocracking of (optionally treated) oil phase is carried out in parallel (in a different reactor system) to hydrocracking of (optionally treated) heavier fraction and shall refer to the (only) reactor system when (optionally treated) oil phase and (optionally treated) heavier fraction are processed together in the same system.
  • the optional treatment refers to DOR, HDM and/or fraction, e.g. forming a hydrotreated material (9; 10; 11), such as DOR hydrotreated material (9; 10) and/or HDM hydrotreated material (11) or a fraction thereof (7).
  • the temperature in the hydrocracking step (or in at least one hydrocracking step in the case of a multi-stage hydrocracking step) is preferably in the range of from 300°C to 500°C, preferably from 300°C to 450°C.
  • the pressure in hydrocracking step is preferably in the range of from 125 bar to 200 bar.
  • the hydrocracking step may be carried out in a fixed bed reactor.
  • the hydrocracking step is preferably carried out in the presence of a heterogeneous catalyst.
  • the catalyst is preferably a supported catalyst.
  • the support preferably comprises alumina and/or silica.
  • the catalyst in the hydrocracking step preferably comprises at least one component selected from IUPAC group 6, 8 or 10 of the Periodic Table of Elements.
  • the catalyst is preferably a supported catalyst and comprises at least Mo and at least one further transition metal on a support, such as a supported NiMo catalyst or a supported CoMo catalyst, wherein the support preferably comprises alumina and/or silica.
  • the catalyst in the hydrocracking step is a supported CoMo catalyst and the support comprises alumina (COMO/AI2O3) and/or the catalyst is a supported NiMo catalyst and the support comprises alumina (NiMo/AhCh).
  • the catalyst in the hydrocracking step may be a supported NiMo catalyst and the support comprises alumina (NiMo/AhCh).
  • These catalysts are preferably employed as sulphided catalysts to ensure that the catalysts are in their active (sulphided) form.
  • Turning the catalysts into their active (sulphided) form may be achieved by sulphiding them in advance (i.e. before starting the hydrotreatment reaction) and/or by adding a sulphur-containing feed (containing sulphur e.g. as an organic or inorganic sulphide).
  • the feed may contain the sulphur from the start, or a sulphur additive may be admixed to the feed.
  • the hydrocracked product (12) may be subjected to fractionation to obtain at least a (third) distillate fraction and a (third) residue fraction.
  • a naphtha fraction and a diesel fraction is obtained from fractionating the hydrocracked product (12).
  • at least both a naphtha fraction and a diesel fraction are obtained from fractionating the hydrocracked product (12).
  • At least one of a gasoline fraction, a heavy fuel oil fraction, and a jet fuel fraction may further be obtained from fractionating the hydrocracked product (12).
  • the integrated process of the present invention may further comprise a finishing step as a part of an oil refinery upgrading process, particularly preferably after/downstream a hydrocracking step.
  • the finishing step may comprise subjecting at least a fraction of the hydrocracked product (12) to at least one of an isomerisation step and/or a polishing hydrotreatment step.
  • the finishing step may specifically comprise subjecting at least a fraction of the hydrocracked product (12) to at least a polishing hydrotreatment step.
  • the polishing hydrotreatment step preferably is carried out at a temperature in the range of from 300°C to 450°C.
  • the polishing hydrotreatment step may be carried out at a pressure in the range of from 20 bar to 80 bar, preferably 40-60 bar.
  • the polishing hydrotreatment step may be carried out in a fixed bed reactor.
  • the integrated process of the present invention may be carried out in an apparatus (or integrated system) adapted to carry out the integrated process.
  • an apparatus may be comprise at least a fractionation unit configured to process at least a crude LWP feed (1), a HT processing unit (HTP; also referred to a pretreatment unit "PTU") including an aqueous alkaline heat treatment stage and a liquid-liquid separator and configured to co-process at least a distillate fraction (2) from the fractionation unit and a LWP co-feed, and a hydrocracking unit configured to process (hydrocrack) at least one of an oil phase (5) from the PTU and a heavier fraction (3) from the fractionation unit.
  • HTP HT processing unit
  • PTU pretreatment unit
  • hydrocracking unit configured to process (hydrocrack) at least one of an oil phase (5) from the PTU and a heavier fraction (3) from the fractionation unit.
  • Oil phase (5) and/or heavier fraction (5) may individually go through additional unit(s) (stages) before entering the hydrocracking unit, as set forth in detail with respect to the integrated process.
  • a DOR unit may be provided after (downstream) the PTU and adapted to process the oil phase from the PTU.
  • a HDM unit may be provided after the PTU, preferably after a DOR unit downstream the PTU (and adapted to process the respective material).
  • a second fractionation unit may be provided after the PTU, preferably after the (optional) HDM unit (and adapted to process the respective material).
  • a DOR unit preferably a liquid-phase DOR unit, may be provided before (upstream) the fractionation unit and configured to process (by DOR) the crude LWP feed (1).
  • units corresponding to the process I method steps mentioned above may be provided and transfer means between these units may be provided so that the integrated process of the present invention (optionally including its optional steps/stages) can be carried out.
  • the integrated process of the present invention is preferably a continuous process (and the apparatus/system is thus preferably configured for continuous operation).
  • the integrated process (and apparatus) may comprise non-continuous storage and/or transportation means.
  • the oil phase (5) is continuously forwarded to further operation, it is also possible that the oil phase (5) (or a part thereof) be forwarded to a storage tank (or transportation tank) and is subjected to further processing at a later time.
  • the present invention also relates to an upgraded hydrocarbon fraction obtainable (or obtained) by the integrated process of the invention.
  • a crude LWP feed having a bromine number of 67 g/lOOg (according to ISO 3839) and a density of 810 kg/m 3 was subjected to diolefin removal by liquid phase hydrogenation under continuous flow conditions over a sulphided alumina- supported NiMo catalyst extrudate.
  • the feed flow rate ratio H2/HC (of individual components, i.e. before saturation) between hydrogen (H 2 ) and crude LWP (HC) was about 16 Nl/I and the pressure in the reactor was set to 5 bar(a).
  • the reaction temperature was 200°C.
  • Example 1 The procedure of Example 1 was repeated except for feeding the hydrogen under gas phase conditions, more specifically a feed flow rate ratio H 2 /HC of about 300 Nl/I while keeping the pressure at 5 bar(a).
  • the bromine number and density of the resulting product was analysed. The results are shown in Table 1. It can be seen that product bromine number is higher than for Example 1. It is assumed that the reaction is less efficient because the contact time of catalyst and (liquid) product is shorter due to the presence of considerable amounts of gaseous hydrogen and thus worse wetting of the catalyst.
  • Comparative Example 1 was repeated under gas phase conditions, while increasing the pressure within the reactor to 50 bar(a).
  • the conditions are in accordance with a LWP hydrotreatment employing gas-phase hydrogen as disclosed in EP 4174150 Al.

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Abstract

L'invention concerne un procédé d'hydrotraitement de déchets plastiques liquéfiés (LWP), le procédé consistant à fournir des LWP, à saturer les LWP avec de l'hydrogène et à soumettre les LWP saturés en hydrogène à un hydrotraitement en phase liquide en présence d'un catalyseur d'hydrotraitement solide pour fournir des LWP hydrotraités en phase liquide.
PCT/FI2025/050193 2024-04-19 2025-04-17 Hydrotraitement en phase liquide de déchets plastiques liquéfiés Pending WO2025219653A1 (fr)

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