Next generation liquefied waste plastic upgrading

Abstract

The present invention relates to a method for upgrading a crude liquefied waste plastic (LWP) feed. The method comprises providing the crude LWP feed, subjecting the crude LWP feed to fractionation to provide at least one distillate fraction and a heavier fraction, and subjecting the distillate fraction and a LWP co-feed to aqueous alkaline heat treatment followed by liquid-liquid separation (HT processing) to provide at least an oil phase and an aqueous phase. The oil phase and / or the heavier fraction may be subjected to further hydrotreatment and to hydrocracking.

Description

[0001] NEXT GENERATION LIQUEFIED WASTE PLASTIC UPGRADING

[0002] Technical field

[0003] The present invention relates to a method for upgrading crude liquefied waste plastics, in particular a method comprising a sequence of fraction, pre-treatment and hydroprocessing.

[0004] Technical field

[0005] Liquefied waste plastics (LWP) 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.

[0006] In this respect, diolefins, especially conjugated diolefins, have a tendency to foul equipment at elevated temperatures and deactivate catalysts through coking. 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.

[0007] Due to these adverse effects, the amount of these impurities should be minimised before the LWP is distributed into downstream processes, such as a conventional refinery process.

[0008] Several approaches have been tried to take care of all impurities present in LWP and to thus provide a feed which can be used as a drop-in replacement or supplement for fossil feeds without deterioration of the product properties and without harming the processing equipment. To date, however, no effective though efficient process has been found.

[0009] 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 (not published at the time of filing this application), discloses a method for LWP upgrading comprising a mild hydrotreatment step for e.g. diolefins removal and a subsequent fractionation and hydrocracking step.

[0010] Further, US 11692139 Bl discloses a method of feeding LWP to fractionation to produce a distillate boiling in the range of from 36-370°C and a vacuum gas oil (VGO) fraction boiling above 370°C, followed by feeding the distillate fraction to a two-step oligomerisation process including a diolefins removal step and an oligomerisation step.

[0011] Brief description of drawing

[0012] FIG. 1 shows a flow diagram of an embodiment of the method of the present invention.

[0013] Summary of the invention

[0014] In brief, the present invention relates to one or more of the following items:

[0015] 1. A method for upgrading crude liquefied waste plastic (LWP), the method comprising

[0016] (a) providing a crude LWP feed (1),

[0017] (b) subjecting the crude LWP feed (1) to fractionation to provide at least one distillate fraction (2) and a heavier fraction (3), characterized by

[0018] (c) subjecting the distillate fraction (2), together with an LWP co-feed (4), to aqueous alkaline heat treatment (HT processing; HTP), followed by liquid-liquid separation 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 optional hydrotreatment(s) for olefins removal (DOR) and / or for hydrodemetallisation (HDM) and / or to optional further fractionation.

[0019] 2. The method according to item 1, comprising subjecting the oil phase (5) to hydrotreatment for diolefins removal (DOR) and / or hydrotreatment for hydrodemetallisation (HDM), more preferably both diolefins removal (DOR) and hydrodemetallisation (HDM). 3. The method according to any one of the preceding items, comprising subjecting the heavier fraction (3) of step (b) to hydrodemetallisation (HDM).

[0020] 4. The method according to any one of the preceding items, further comprising subjecting the crude LWP feed (1) to hydrotreatment for diolefins removal (DOR) prior to fractionation in step (b) .

[0021] 5. The method according to any one of the preceding items, wherein the hydrotreatment for hydrodemetallisation (HDM) is performed in the presence of gaseous hydrogen.

[0022] 6. The method according to any one of the preceding items, wherein the hydrotreatment for hydrodemetallisation (HDM) is performed with a fixed bed reactor or a moving-catalyst type reactor.

[0023] 7. The method according to any one of the preceding items, wherein the hydrotreatment for hydrodemetallisation (HDM) is performed under conditions for removing metal impurities, metalloid impurities and / or halogen impurities.

[0024] 8. The method according to any one of the preceding items, wherein the step of providing the crude LWP feed (1) comprises depolymerizing waste plastics.

[0025] 9. The method according to any one of the preceding items, further comprising a step of providing the LWP co-feed (4) by depolymerizing waste plastics.

[0026] 10. The method according to any one of the preceding items, wherein the oil phase (5) is subjected to steam cracking, after optional further treatment, such as purification and / or polishing treatment.

[0027] 11. The method according to any one of the preceding items, wherein the heavier fraction (3) of step (b) has a 5 vol% boiling point (ASTM-D2887) in the range of from 160°C to 240°C, such as in the range of from 165°C to 220°C, or in the range of from 175°C to 195°C. 12. The method according to any one of the preceding items, wherein the heavier fraction (3) is a bottoms (residue) fraction.

[0028] 13. The method according to any one of the preceding items, wherein the distillate fraction (2) is a naphtha range fraction, preferably having a final boiling point (ASTM-D2887) 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 or in the range of 175 to 185°C.

[0029] 14. The method according to any one of the preceding items, wherein the heavier fraction (3) has a 10 vol% boiling point (ASTM-D2887) which is higher than the 90 vol% boiling point (ASTM-D2887) of the distillate fraction.

[0030] 15. The method according to any one of the preceding items, wherein the LWP cofeed (4) is crude LWP.

[0031] 16. The method according to any one of the preceding items, wherein the oil phase (5) is subjected to a second fractionation to provide at least a second distillate fraction (8) and a second heavier fraction (7).

[0032] 17. The method according to item 16, wherein the oil phase (5) is subjected to hydrotreatment for diolefins removal (DOR) (thus providing a DOR hydrotreated material (9)), subsequently subjected to hydrotreatment for hydrodemetallisation (HDM) (thus providing a HDM hydrotreated material (11)), thereafter subjected to the second fractionation to provide at least the second distillate fraction (8) and the second heavier fraction (7).

[0033] 18. The method according to item 16 or 17, wherein the second heavier fraction (7) is subjected to hydrocracking.

[0034] 19. The method according to any one of items 16 to 18, wherein the second distillate fraction (8) is a naphtha range fraction, preferably having a final boiling point (ASTM-D2887) 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, or in the range of 175 to 185°C.

[0035] 20. The method according to any one of items 16 to 19, wherein the second heavier fraction (7) has a 10 vol% boiling point (ASTM-D2887) which is higher than the 90 vol% boiling point (ASTM-D2887) of the second distillate fraction (8).

[0036] 21. The method according to any one of items 16 to 20, wherein the second heavier fraction (7) is a bottoms (residue) fraction.

[0037] 22. The method according to any one of items 16 to 21, wherein the second distillate fraction (8) is subjected to steam cracking, after optional further treatment, such as purification and / or polishing treatment.

[0038] 23. The method according to any one of items 16 to 22, wherein at least a part of the heavier fraction (3) of step (b) is blended with the oil phase (5) prior to the second fractionation, such as after DOR but prior to HDM.

[0039] 24. The method according to any one of items 16 to 23, wherein the second heavier fraction (7) is subjected to hydrocracking.

[0040] 25. The method according to any one of the preceding items, wherein the hydrotreatment for hydrodemetallisation (HDM) is carried out under conditions which are harsher than the conditions under which the hydrotreatment for diolefins removal (DOR) is carried out.

[0041] 26. The method according to any one of the preceding items, wherein the hydrotreatment for hydrodemetallisation (HDM) is carried out at a higher temperature than the hydrotreatment for diolefins removal (DOR).

[0042] 27. The method according to any one of the preceding items, wherein the hydrotreatment for hydrodemetallisation (HDM) is carried out at a higher hydrogen partial pressure than the hydrotreatment for diolefins removal (DOR). 28. The method according to any one of the preceding items, wherein the oil phase (5) is subjected at least to hydrotreatment for diolefins removal (DOR).

[0043] 29. The method according to any one of the preceding items, wherein the oil phase (5) is subjected to hydrotreatment for hydrodemetallisation (HDM) and the method comprises subjecting the oil phase (5) to hydrotreatment for diolefins removal (DOR) prior to HDM.

[0044] 30. The method according to any one of the preceding items, wherein the oil phase (5) is subjected to hydrotreatment for hydrodemetallisation (HDM) and the method comprises subjecting the crude LWP feed (1) and / or the LWP co-feed (4), preferably both the crude LWP feed (1) and the LWP co-feed (4), to hydrotreatment for diolefins removal (DOR).

[0045] 31. The method according to any one of the preceding items, wherein at least the fractionation of step (b) and the HT processing of step (c) is carried out as a continuous process, preferably the whole method being carried out as a continuous process.

[0046] 32. The method according to any one of the preceding items, wherein hydrotreatment for diolefins removal (DOR) is carried out in the presence of a hydrogenation catalyst.

[0047] 33. The method according to any one of the preceding items, wherein hydrotreatment for diolefins removal (DOR) is carried out as a liquid phase hydrotreatment.

[0048] 34. The method according to any one of the preceding items, comprising hydrotreatment for diolefins removal (DOR) prior to the fractionation in step (b), and at least the hydrotreatment for diolefins removal (DOR) prior to fractionation in step (b) is carried out as a liquid phase hydrotreatment.

[0049] 35. The method according to any one of the preceding items, wherein hydrotreatment for diolefins removal (DOR) is carried out at a temperature in the range of 100°C to 350°C, preferably 100°C to 275°C, 130°C to 275°C, 160°C to 275°C, 170°C to 250°C, or 200°C to 250°C.

[0050] 36. The method according to any one of the preceding items, wherein hydrotreatment for diolefins removal (DOR) is carried out as a continuous process and / or the HDM is carried out as a continuous process.

[0051] 37. The method according to any one of the preceding items, wherein hydrotreatment for diolefins removal (DOR) is the first hydrotreatment to which the crude LWP feed (1), the LWP co-feed (4) and / or the material (1; 2; 4; 5) emerging from the crude LWP feed (1) and / or from the LWP co-feed (4) (LWP- based material) is subjected.

[0052] 38. The method according to any one of the preceding items, further comprising a step of saturating the crude LWP feed (1) with hydrogen and subjecting the hydrogen-saturated material to liquid phase hydrotreatment, preferably to liquid phase hydrotreatment for diolefins removal (DOR), and / or saturating the oil phase (5) with hydrogen and subjecting the hydrogen-saturated material to liquid phase hydrotreatment for diolefins removal (DOR).

[0053] 39. The method according to any one of the preceding items, wherein hydrotreatment for diolefins removal (DOR) includes a stage where a part of the material having been subjected to hydrotreatment for diolefins removal (DOR hydrotreated material (9; 10)) is recycled back to the hydrotreatment for diolefins removal (DOR).

[0054] 40. The method according to any one of the preceding items, wherein the content of conjugated diolefins in the DOR hydrotreated material (9; 10) is 0.30 wt.-% or lower, preferably 0.25 wt.-% or lower, 0.20 wt.-% or lower, 0.15 wt.-% or lower, or 0.10 wt.-% or lower.

[0055] 41. The method according to any one of the preceding items, wherein hydrogen is being mixed with the crude LWP feed (1) and / or the oil phase (5) before carrying out the hydrotreatment for diolefins removal (DOR). 42. The method according to any one of the preceding items, wherein the crude LWP feed (1) is derived from thermal liquefaction of polymer waste.

[0056] 43. The method according to any one of the preceding items, wherein the (crude) LWP forming the LWP co-feed (4) is derived from thermal liquefaction of polymer waste.

[0057] 44. The method according to any one of the preceding items, wherein the crude LWP feed (1) 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.

[0058] 45. The method according to any one of the preceding items, wherein the (crude) LWP forming the LWP co-feed (4) 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.

[0059] 46. The method according to any one of the preceding items, wherein the hydrotreatment for diolefins removal (DOR) is carried out in the presence of a heterogeneous catalyst.

[0060] 47. The method according to any one of the preceding items, wherein the hydrotreatment for diolefins removal (DOR) is carried out in a fixed bed reactor system.

[0061] 48. The method according to any one of the preceding items, wherein the hydrotreatment for diolefins removal (DOR) is carried out in the presence of a supported catalyst.

[0062] 49. The method according to any one of the preceding items, wherein the hydrotreatment for diolefins removal (DOR) is carried out in the presence of a supported catalyst, and the support comprises alumina and / or silica. 50. The method according to any one of the preceding items, wherein the hydrotreatment for diolefins removal (DOR) is carried out in the presence of a catalyst and the catalyst comprises at least one component selected from IllPAC group 6, 8 or 10 of the Periodic Table of Elements.

[0063] 51. The method according to any one of the preceding items, wherein the hydrotreatment for diolefins removal (DOR) is carried out in the presence of a catalyst and the catalyst 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.

[0064] 52. The method according to any one of the preceding items, wherein the hydrotreatment for diolefins removal (DOR) is carried out in the presence of a catalyst and the catalyst is a supported CoMo catalyst and the support comprises alumina (C0M0 / AI2O3) and / or the catalyst is a supported NiMo catalyst and the support comprises alumina (NiMo / A Os).

[0065] 53. The method according to any one of the preceding items, wherein the total fresh feed (3; 5) of the hydrotreatment for diolefins removal (DOR) after HT processing contains at least 50 wt.-% LWP-based material, 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-based material.

[0066] 54. The method according to any one of the preceding items, wherein hydrotreatment for diolefins removal (DOR) is performed as a liquid phase hydrotreatment under the following conditions:

[0067] - a LHSV (liquid hourly space velocity) in the range of 0.10 to 10.00 h’1, preferably

[0068] 0.25 to 6.00 h’1, more preferably 0.50 to 4.00 h’1;

[0069] - a temperature in the range of 100-275 °C, preferably 170-250 °C.

[0070] 55. The method according to any one of the preceding items, wherein the aqueous alkaline heat treatment of step (c) is carried out at a temperature in the range of 150°C to 450°C, preferably in the range of 200°C to 450°C. 56. The method according to any one of the preceding items, wherein the aqueous alkaline heat treatment of step (c) is 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.

[0071] 57. The method according to any one of the preceding items, wherein aqueous alkaline heat treatment of step (c) is 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.

[0072] 58. The method according to any one of the preceding items, wherein aqueous alkaline heat treatment of step (c) is carried out at a temperature in the range of 200°C to 350°C, preferably in the range of 220°C to 330°C, in the range of 240°C to 320°C, or in the range of 260°C to 300°C.

[0073] 59. The method according to any one of the preceding items, wherein fractionating in step (b) is carried out by at least hot hydrogen stripping and / or vacuum distillation.

[0074] 60. The method according to any one of the preceding items, comprising subjecting at least a fraction (7) of the oil phase (5) to hydrocracking.

[0075] 61. The method according to any one of the preceding items, wherein the heavier fraction (3) of step (b) is subjected to hydrocracking.

[0076] 62. The method according to any one of items 60 or 61, comprising subjecting a blend of the heavier fraction (3) of step (b) and the oil phase (5) to hydrodemetallisation (HDM), followed by a second fractionation and subsequent hydrocracking of a thus-obtained fraction, preferably a second heavier fraction (7).

[0077] 63. The method according to item 62, wherein the oil phase (5) is subjected to hydrotreatment for diolefins removal (DOR) prior to subjecting the blend to HDM. 64. The method according to any one of items 60 to 63, wherein the feed material (3; 7; 9; 11) subjected to hydrocracking has a 5 vol% boiling point of 170°C or more, preferably 180°C or more.

[0078] 65. The method according to any one of items 60 to 64, wherein the heavier fraction (3) of step (b) is not subjected to HT processing of step (c) before hydrocracking.

[0079] 66. The method according to any one of items 60 to 65 wherein the heavier fraction (3) of step (b) is forwarded to hydrocracking without intermediate hydrotreatment, and is preferably forwarded directly to hydrocracking.

[0080] 67. The method according to any one of items 60 to 66, wherein the hydrocracking is a single stage or a multi-stage (two or three or more stages) process.

[0081] 68. The method according to any one of items 60 to 67, wherein the total feed (3; 5; 7; 9; 11) to the hydrocracking contains at least 0.5 wt.-%, preferably at least 1.0 wt.-% or at least 2.0 wt.-% of the heavier fraction (3).

[0082] 69. The method according to any one of items 60 to 68, wherein hydrocracking is carried out in a moving-catalyst type reactor system or a moving-catalyst type reactor system to obtain a hydrocracked product (12), preferably a movingcatalyst type reactor system.

[0083] 70. The method according to any one of items 60 to 69, wherein hydrocracking is carried out in a moving-catalyst type reactor system in the presence of hydrogen and a hydrogenation catalyst to obtain a hydrocracked product (12).

[0084] 71. The method according to item 69 or 70, wherein 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. 72. The method according to any one of items 60 to 71, wherein the temperature in hydrocracking is in the range of from 300°C to 500°C, preferably from 300°C to 450°C.

[0085] 73. The method according to any one of items 60 to 72, wherein the pressure in hydrocracking is in the range of from 125 bar to 200 bar.

[0086] 74. The method according to any one of items 60 to 73, wherein the hydrocracking is carried out in the presence of a heterogeneous catalyst.

[0087] 75. The method according to any one of items 60 to 74, wherein the hydrocracking is carried out in the presence of a supported catalyst.

[0088] 76. The method according to any one of items 60 to 75, wherein the hydrocracking is carried out in the presence of a supported catalyst, and the support comprises alumina and / or silica.

[0089] 77. The method according to any one of items 60 to 76, wherein the hydrocracking is carried out in the presence of a catalyst and the catalyst comprises at least one component selected from IllPAC group 6, 8 or 10 of the Periodic Table of Elements.

[0090] 78. The method according to any one of items 60 to 77, wherein the hydrocracking is carried out in the presence of a supported catalyst and the catalyst 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.

[0091] 79. The method according to any one of items 60 to 78, wherein the hydrocracking is carried out in the presence of a supported CoMo catalyst and the support comprises alumina (C0M0 / AI2O3) and / or the catalyst is a supported NiMo catalyst and the support comprises alumina (NiMo / A Ch). 80. The method according to any one of items 60 to 79, wherein the hydrocracking is carried out in the presence of a supported NiMo catalyst and the support comprises alumina (NiMo / AhOs).

[0092] 81. The method according to any one of items 60 to 80, further comprising fractionating the hydrocracked product (12) to obtain at least a distillate fraction and a residue fraction.

[0093] 82. The method according to item 81, wherein at least a naphtha fraction and a diesel fraction are obtained from fractionating the hydrocracked product (12).

[0094] 83. The method according to item 81 or 82 wherein at least one of a gasoline fraction, a heavy fuel oil fraction, and a jet fuel fraction is further obtained from fractionating the hydrocracked product (12).

[0095] 84. An upgraded hydrocarbon fraction being obtainable by the method according to any one of the preceding items.

[0096] 85. An integrated system configured to carry out the method of any one of items 1 to 83.

[0097] Detailed description of the present invention

[0098] The present invention relates to a method for upgrading a crude liquefied waste plastic (LWP) feed, the method comprising providing the crude LWP feed, subjecting the crude LWP feed to fractionation to obtain at least a (lighter) distillate fraction and a heavier fraction, and subjecting the distillate fraction to aqueous alkaline heat treatment followed by liquid-liquid separation (HT processing) to provide at least an oil phase, and subjecting at least one of the oil phase and the heavier fraction (each, individually or collectively) to optional further hydrotreatment for diolefins removal and / or optional further hydrotreatment for hydrodemetallisation and / or optional further fractionation.

[0099] Silicon is a severe problem in LWP upgrading, as it deactivates catalysts relatively quickly. The inventors surprising found that most silicon species in LWP tend to be present in a lighter LWP fraction (such as a naphtha fraction) and light fractions may furthermore be problematic in downstream processes, e.g. in a hydrocracking unit. However, removing silicon-based impurities by fractionation alone would lead to a new problem, because the silicon rich (naphtha) fraction needs to be processed to a quality suitable for further processing. This high silicon content, however, makes the catalyst lifetime in e.g. a fixed bed limited, and therefore the reactor would have very short catalyst lifetime.

[0100] By feeding (only) the distillate fraction (and not the heavier fraction) to HT processing, the majority of the silicon impurities can be removed in the HT processing without the need to process all the crude LWP feed by HT processing, thus solving a multitude of problems. As a consequence, less waste (e.g. contaminated water from HT processing) will be produced.

[0101] The method of the present invention preferably further comprises a hydrocracking step. Specifically, the heavier fraction (or a part thereof or a fraction thereof) may be subjected to hydrocracking. The heavier fraction may be subjected to hydrocracking as-is, or it may be subjected to DOR and / or HDM and / or further (second) fractionation. The oil phase may also be subjected to hydrocracking, while the oil phase is subjected to DOR (and preferably further to HDM and / or fractionation) prior to hydrocracking.

[0102] The hydrocracking step (hydrocracking stage I unit) will preferably be provided for a heavier feed having reduced catalyst deactivating impurities profile such as silicon, metals, halogens, etc, thereby reducing the demand and load on the hydrocracking catalysts. This embodiment of the method of the present invention can reduce the load (volume flow) of light feeds in the hydrocracking step, which can also reduce the catalyst consumption in hydrocracking as less silicon is fed to the unit. In addition, it has been found that silicon-contaminated hydrocracking catalyst is more difficult to work-up (e.g. regeneration or reclaiming valuable metal compounds, such a vanadium), so that the method of the present invention adds further value in an integrated process (including hydrocracking as well as regenerating a used hydrocracking catalyst or reclaiming metal compounds from a used hydrocracking catalyst). The lighter feed fractions will also have reduced contact with the hydrocracking catalyst and thus reduced conversion resulting in slip through of the impurities.

[0103] In the present invention, (crude) liquefied waste plastics, also referred to as (crude) LWP, 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 waste-based oil, pyrolysis oil, depolymerized polymer waste or as liquefied polymer waste.

[0104] 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). In particular, the term 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"). In the sense of the present invention, the term 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.

[0105] 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. In a typical pyrolysis process, 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. The crude LWP typically has a boiling range of about 40 °C - 550 °C, which corresponds approximately to carbon chain lengths of C5 to C55. Depending on the conversion technology, the final boiling point of the crude LWP can go up to 750°C.

[0106] The liquefaction process may be carried out in the presence of a catalyst.

[0107] In addition to liquid (NTP) hydrocarbons, i.e. hydrocarbons being liquid at normal temperature and pressure (NTP; 20°C, 101.325 kPa, as said above, pressure is absolute pressure), 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). In other words, crude LWP is typically a mixture of hydrocarbonaceous organic components with a wide range of carbon chain lengths. Provided the large variations of carbon chain lengths and chemical structures and the properties of the crude LWP vary depending on the types of plastics (polymers) used in the production of crude LWP, the type of liquefaction process and conditions of the liquefaction process. Specifically, (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.%. (Crude) LWP also typically contains 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.

[0108] In the context of the present disclosure, 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. In other words, as used herein, 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.

[0109] The step of providing the crude LWP feed may comprise a liquefaction process (a process of depolymerizing waste plastics), preferably as described herein.

[0110] Initially, 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). However, the waste plastics, or each waste plastics species, may be at least partially melted before and / or during the depolymerisation.

[0111] 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.

[0112] Preferably, the (solid) waste plastics (polymer waste) to be subjected to the liquefaction process (depolymerisation), and thus being the base material of the (crude) 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 / EN15403. The crude LWP feed 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 obtained from the liquefaction process), or a fraction of LWP being a fractionated crude LWP. In particular the crude LWP feed may comprise at least 90 wt.-% crude LWP, such as at least 95 wt.-% crude LWP or at least 99 wt.-% crude LWP. Specifically, the LWP feed is 100% crude LWP meaning that no treatment step has been performed on the liquefaction product. This shall explicitly apply to all embodiments of the present invention.

[0113] The crude LWP feed of the present invention is a feed containing impurities which need to be removed, in particular Si and halogen (e.g. chlorine) impurities. More specifically, depending on the source (waste plastic) of the crude LWP feed, the chlorine content of the crude LWP feed 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. Moreover, crude LWP feed 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. Similarly, the silicon content (Si content) of the crude LWP feed 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 feed 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.

[0114] The LWP co-feed 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 obtained from the liquefaction process), or a fraction of LWP being a fractionated (crude) LWP. In particular the LWP co-feed preferably comprises at least 90 wt.-% crude LWP, such as at least 95 wt.-% crude LWP or at least 99 wt.- % crude LWP. Specifically, the LWP feed may be 100% crude LWP meaning that no treatment step has been performed on the liquefaction product. This shall explicitly apply to all embodiments of the present invention.

[0115] The crude LWP feed (and similarly crude LWP in general) preferably comprises primarily hydrocarbons, typically more than 50 wt.-% based on the total weight of the crude LWP feed. Typically the crude LWP feed comprises two or more hydrocarbon species selected from paraffins, olefins, naphthenes and aromatics. The composition of the crude LWP feed 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 crude LWP feed.

[0116] 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). In other words, (crude) LWP may also be referred to as "depolymerized polymer waste", "polymer waste-based oil", "pyrolysis oil" or "liquefied polymer waste".

[0117] 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.

[0118] 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. In the present disclosure, when reference is made to a standard, the latest revision available on January 1, 2023 shall be meant, unless stated to the contrary.

[0119] In the present invention, hydrotreatment generally refers to catalytic hydrotreatment, i.e. treatment in the presence of hydrogen and a hydrotreatment catalyst. The same applies to hydroprocessing, which is carried out as catalytic hydroprocessing, i.e. in the presence of hydrogen and a hydroprocessing catalyst. In this respect, as commonly known in the present technical field, hydrotreatment is a treatment favouring (full or partial) olefin (or alkyne) saturation whereas hydroprocessing is a process favouring heteroatom (e.g. S, O) removal and / or aromates saturation in addition. Similarly, hydrocracking preferably refers to catalytic hydrocracking, i.e. cracking in the presence of hydrogen and a hydrocracking catalyst.

[0120] In the present invention, 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 (e.g. crude LWP feed (1), oil phase (5), or heavy fraction (3)), and may be referred to as the reactant I educt (excluding hydrogen and catalyst). In this respect, "saturated" shall encompass any condition in which hydrogen is present in the liquid-phase feed (e.g. crude LWP feed), 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.

[0121] All of the hydrotreatments (and hydroprocessing, including hydrocracking) stated herein are performed in the presence of at least one catalyst. The catalyst may, for example, comprise at least one component selected from IllPAC group 6, 8 or 10 of the Periodic Table of Elements. When employing a supported catalyst, 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. In a supported catalyst, 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. In a preferable embodiment, the hydrotreating employs a catalyst and the catalyst is a supported NiMo catalyst and the support comprises alumina (NiMo / AhOs) and / or the catalyst is a supported CoMo catalyst and the support comprises alumina (C0M0 / AI2O3).

[0122] Moreover, unless specified to the contrary, a (content) percentage (%) mentioned in the present invention relates to % by weight. When reference is made to a pressure value, this pressure value shall refer to an absolute pressure, unless specified to the contrary.

[0123] In the present invention, terms like "before" and "after" shall similarly apply to batch-like processes and to continuous processes. In the latter, the term "after" may also be referred to as "downstream" and the term "before" may be referred to as "upstream". The same applies to corresponding expressions, as will be understood by the skilled person.

[0124] In the present invention, 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...".

[0125] When referring to a feed or (intermediate) product which is subjected to a certain treatment or step, it is to be understood that this shall similarly mean that "at least part" of that feed or product is subjected to that step. In other words, it is possible that e.g. 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). For example, 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 (coprocessed) 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, in particular to the crude LWP feed (1) of step (a), the LWP co-feed (4), the heavier fraction (3), the distillate fraction (2), the oil phase (5), the DOR hydrotreatment material (9), the HDM hydrotreated material (11), the second distillate fraction (8), and the second heavier fraction (7).

[0126] All embodiments (such as all preferred values and / or ranges within the embodiments, even from Examples) of the present invention may be combined with each other to give (preferred) embodiments, unless explicitly specified otherwise or unless such a combination would result in a contradiction. Specifically, it is to be understood that the embodiments of the respective process / method steps recited herein may be combined with each other and with embodiments of other process / method steps. For example, any embodiment of the fractionation step may be combined with any embodiment of the hydrocracking step and any embodiment of both of these may individually or commonly (together) combined with any embodiment of the HT processing, unless indicated to the contrary.

[0127] In the following, reference will be made to the enclosed FIG for illustration purposes. It is, however, to be understood that the invention is not limited to the embodiments shown in the FIG but is only limited by the appended claims. Specifically, FIG. 1 is a flow diagram illustrating the overall concept (and embodiments) of the present invention. In Fig. 1, 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 I units. Diamond shapes (on arrows) designate feeds / products (intermediates).

[0128] In brief, FIG. 1 shows that 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 LWP cofeed. Liquid-liquid separation (in HTP) yields an oil phase (5) and an aqueous phase (6). The oil phase (5) may be forwarded to an (optional) hydrotreatment for diolefins removal (DOR) and subsequent optional hydrotreatment for hydrodemetallisation (HDM). After HDM (or if no HDM is carried out after DOR, or if neither DOR nor HDM is carried out after HTP), 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).

[0129] The heavier fraction (3) from the first fractionation may be used as such (illustrated by the lowermost dashed arrow) or may be fed to any one of the optional DOR or HDM (and even to the second fractionation; not shown) for coprocessing (with material, e.g. oil phase (5), after HTP). Alternatively or in addition (in addition means that only part of the heavier fraction (3), such as a volumetric part is forwarded / co-processed in each route) the heavier fraction (3) may be directly forwarded to hydrocracking.

[0130] As shown by the solid rectangle, hydrocracking is carried out in any case 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).

[0131] A more general description of the present invention is given in the following, still referring to the FIG for illustration.

[0132] The method 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). Prior to hydrocracking, the oil phase (5) and / or the heavier fraction (3) may be subjected (each individually or together, i.e. co-processed) to hydrotreatment(s) for olefins removal (DOR) and / or hydrodemetallisation (HDM) and / or to further fractionation. The aqueous alkaline heat treatment and subsequent liquid-liquid separation may be referred to as "HT processing" (HTP) in the present invention. The method of the present invention preferably further comprises subjecting the oil phase (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). After the diolefins removal (DOR), the method 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. Note that even after having undergone further work-up, in particular DOR and / or HDM and / or (second) fractionation, the oil phase (5) may still be designated as "oil phase" (5) in the present invention, 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)". This similarly applies to the "heavier fraction", the "second distillate fraction" and the "second heavier fraction".

[0133] Preferably, a HDM (step) is carried out on at least the oil phase (5), more preferably after DOR on DOR hydrotreated material (9). In case a HDM step is carried out, all the LWP-based material (3; 5; 9) which is fed to the HDM (step) should have undergone at least one DOR (step). This shall mean that each material which is derived from LWP (i.e. which emerges from the crude LWP feed and / or from the LWP co-feed) should have undergone (at least one) DOR. For example, 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) have undergone DOR.

[0134] The method may comprise subjecting at least a fraction of the oil phase (5) to hydrocracking, optionally together with the heavier fraction (3). Preferably, at least a heavier fraction (7) (more preferably a fraction of the oil phase from which a naphtha range fraction has been removed by fractionation) of the oil phase (5) is subjected to hydrocracking. The oil phase (5) is suitably treated prior to such second fractionation 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.

[0135] The method may comprise subjecting a blend of the heavier fraction (3) of step (b) and the oil phase (5) (the oil phase suitably after DOR) to hydrodemetallisation (HDM), followed by a second fractionation and subsequent hydrocracking of a thus- obtained fraction (preferably a second heavier fraction (7)).

[0136] 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.

[0137] As already indicated above, the method may comprise subjecting the crude LWP feed (1) to hydrotreatment for diolefins removal (DOR) (i.e. under conditions adapted for diolefins removal) prior to fractionation in step (b). In this case, 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). However, the present specification also more accurately refers to this material as DOR hydrotreated crude LWP (10). Moreover, when reference is made to "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).

[0138] Preferably, the crude LWP feed (1) is subjected to hydrotreatment for diolefins removal (DOR) prior to fractionation in step (b). In addition, it is preferred that 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.

[0139] Preferably, 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). Alternatively, or in addition, 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. In this respect, 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.

[0140] 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.

[0141] The heavier fraction (3) is generally heavier (higher-boiling) than the distillate fraction (2) (lighter fraction). Preferably, 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.

[0142] 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). For example, 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).

[0143] 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). The second heavier fraction (7) may then be 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. The skilled person will understand that the same applies if one or both of DOR and HDM are not performed (i.e. these steps may be optional).

[0144] The second heavier fraction (7) is generally heavier (higher-boiling) than the second distillate (lighter) fraction (8). Preferably, 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.

[0145] At least a part (e.g. volumetric part) of the heavy fraction (3) of step (b) may be blended with the oil phase (5), suitably after DOR but prior to (optional) HDM, or after HDM (but prior to second fractionation, if present). In this respect, "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). In other words, this expression (and similar expressions of preparing a "blend" which are subjected to a certain processing) shall refer to co-processing in general, while pre-blending is an option. Preferably, at least the second heavier fraction (7) is subjected to hydrocracking.

[0146] Preferably, at least one of the second distillate fraction (8) and the oil phase (5) (from HT processing, after optional DOR and / or HDM) 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. As a matter of course, a co-feed, such as a fossil co-feed, may be employed in steam cracking. Preferably, 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 I LWP-based material).

[0147] When the oil phase (5) is (e.g. without further fractionation, but after optional DOR and / or HDM and / or optional further work-up) subjected to stream cracking, it is preferable that 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. That is, in that case, mainly 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. In particular, a naphtha fraction has been found to be particularly suitable for steam cracking, at least after having been subjected to further workup e.g. polishing. As a matter of course, this similarly applies to the second distillate fraction (8).

[0148] The hydrotreatment for hydrodemetallisation (HDM) 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. For example, the temperature (for HDM) may be in the range of from 355 to 500°C, such as 355 to 450°C or 360°C to 400°C. The HDM may be carried out under a higher hydrogen partial pressure than the DOR.

[0149] Preferably, the oil phase (5) is subjected at least to DOR. Preferably, the oil phase (5) is subjected at least to HDM. The oil phase (5) may be subjected to DOR and to HDM in this order. The method 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).

[0150] DOR (if more than one DOR is present, at least one thereof) may be carried out as a liquid phase hydrotreatment in the presence of a hydrogenation catalyst. In this respect, DOR may specifically referred to as a selective hydrotreatment for diolefins removal.

[0151] In the present invention, when making reference to hydrotreatment for diolefins removal (DOR), this generally applies to both the (optional) DOR after HT processing and to an optional DOR before fractionation (before step (b)), unless explicitly stated to the contrary.

[0152] 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.

[0153] 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.

[0154] 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 process when no DOR (of the crude LWP feed (1)) is present before the fractionation step. In this respect, the "first hydrotreatment" means the first hydrotreatment after liquefaction.

[0155] In particular, the inventors consider that diolefins in crude LWP (forming the basis of the crude LWP feed and the LWP co-feed) are harmful for many hydrogenation catalysts and thus it is beneficial to carry out a DOR (which may also be referred to as diolefins removal step) as the first hydrotreatment in the method of the present invention.

[0156] The method may further comprise a step of saturating the feed(s) to liquid phase hydrotreatment (referred to as "liquid phase-reactor feed") with hydrogen for carrying out the liquid phase hydrotreatment. The thus hydrogen-saturated feed (e.g. crude LWP feed and / or oil phase) is then ready to be subjected to the liquid phase hydrotreatment. In particular, it is favourable to carry out saturation in a dedicated apparatus before forwarding the liquid phase-reactor feed (1; 3; 5) to a liquid phase hydrotreatment reactor. For example, hydrogen may be mixed with the liquid phase-reactor feed before carrying out the liquid phase hydrotreatment. This means that mixing is accomplished before the temperature exceeds the reaction temperature (e.g. as indicated above) and / or before the liquid phasereactor feed reaches the hydrotreatment catalyst (catalyst bed). Thus, it can be more easily ensured that an appropriate amount of hydrogen is present in the liquid phase-reactor feed without (or substantially without) forming a gas phase in the hydrotreatment step. A guard bed (e.g. not containing hydrotreatment catalyst) may be provided as well (and may be provided before / upstream or after / downstream mixing hydrogen, when employed).

[0157] Even though not necessary, DOR may include a stage in which a part (e.g. a fraction or a volumetric part) of the material having been subjected to DOR (the material formed in the DOR, also referred to "DOR hydrotreated material" (9; 10)) is recycled back to the DOR. Recycling at least a part of the DOR hydrotreated material may facilitate temperature control in the DOR. The diolefins removal, in particular when employing liquid phase hydrotreatment step, is very effective, even though some diolefins may remain in the DOR hydrotreated material (9; 10). Preferably, the content of conjugated diolefins in the DOR hydrotreated material (e.g. DOR hydrotreated crude LWP (10) and / or DOR hydrotreated oil phase (9)) 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.

[0158] As a result of the DOR, a DOR hydrotreated material (9; 10) is formed. The formed DOR hydrotreated material (9; 10) contains lower amounts of impurities, contaminants and harmful components compared to the feed material of the diolefins removal (DOR step), i.e. the crude LWP feed (1) and / or the oil phase (5) (and / or heavy fraction (3)). With 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. Especially 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 material in order for the treated material to be used downstream as a feedstock for an oil refinery upgrading process, such as a process including steam cracking and / or hydrocracking.

[0159] The purpose of the hydrotreatment for diolefins removal (DOR) is to reduce the risk of harmful and / or detrimental properties of any of the impurities, contaminants and harmful components in the crude LWP feed (and / or oil phase). The DOR 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 DOR. After the DOR, the conjugated diolefin content in the DOR hydrotreated material is preferably below 0.20 wt.%. The DOR may carried out in the presence of a heterogeneous catalyst. The DOR may carried out in a fixed bed reactor system. The catalyst in the DOR may be a supported catalyst, and the support preferably comprises alumina and / or silica.

[0160] The catalyst in the DOR may comprise (as a catalytically active element) at least one component selected from IllPAC group 6, 8 or 10 of the Periodic Table of Elements. In particular, the catalyst may comprise 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.

[0161] The catalyst in the DOR may for example be a supported CoMo catalyst and the support comprises alumina (C0M0 / AI2O3) and / or a supported NiMo catalyst and the support comprises alumina (NiMo / A Os).

[0162] 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 (to the DOR step) may contain the sulphur from the start, or a sulphur additive may be admixed to the feed.

[0163] In the present invention, the total fresh feed of the DOR preferably contains at least 50 wt.-% LWP-based material, 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-based material, or 100% LWP-based material. In this respect, LWP-based material refers to a material originating from LWP, e.g. the crude LWP feed (1) in the case of a hydrotreatment prior to fractionation in step (b) and the oil phase (3) (and / or heavy fraction (3)) originating from the summed amount of crude LWP feed (1) (distillate fraction (2)) and LWP co-feed (4) in the case of DOR after the HT processing. The remainder of the total fresh feed may be a (non-LWP- based) co-feed and / or a (non-LWP-based) diluent, preferably a (non-LWP-based) hydrocarbon (co)feed or diluent. It is particularly preferably for the remainder of the total fresh feed to have an impurities pattern which differs from that of LWP. The remainder of the total fresh feed may particularly be at least one of a crude oil-derived feed comprising at least one crude oil-fraction, e.g. selected from vacuum gas oil (VGO) fraction, gas oil (GO) fraction, heavy gas oil (HGO) fraction, kerosene fraction, light gas oil fraction, atmospheric residue (AR) fraction, vacuum residue (VR) fraction and deasphalted oil (DAO) fraction, 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 total feed (fresh feed and optional recycle feed) does not include catalyst, hydrogen or other gas, if any. The fresh feed to the (optional) DOR before fractionation may particularly be (consist of) LWP, more specifically crude LWP.

[0164] In the present invention, it is preferred that at least one DOR (also referred to as DOR stage) be carried out as a liquid phase hydrotreatment. In particular, at least the DOR stage prior to fractionation in step (b) may preferably carried out as a liquid phase hydrotreatment.

[0165] The liquid phase hydrotreatment may be performed under the following conditions:

[0166] - a LHSV (liquid hourly space velocity) in the range of 0.10 to 10.00 h’1, preferably

[0167] 0.25 to 6.00 h’1, more preferably 0.50 to 4.00 h’1;

[0168] - a temperature in the range of 100-275 °C, preferably 170-250 °C.

[0169] 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. In this respect, "oil" means the feed of the liquid phase hydrotreatment (the "feed" excludes H2, catalyst and carrier gas, if any).

[0170] The content of conjugated diolefins in a liquid phase hydrotreated LWP (10) (and in DOR hydrotreated material (9; 10) in general) is preferably 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. An embodiment of the method 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.

[0171] The present invention provides an efficient method for producing valuable products from LWP depending on needs and thus contributes to sustainability.

[0172] The method 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).

[0173] The aqueous alkaline heat treatment (in HT processing) 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.-%.

[0174] 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.

[0175] The aqueous alkaline heat treatment (in HTP) is preferably carried out at a temperature in the range of 150°C to 450°C, more preferably 200°C to 450°C. Employing 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. In other words, such 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). Specifically, 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. For example, 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. Specifically, the aqueous alkaline heat treatment (and HTP in general) may be carried out as a reactive extraction, as specified in FI128848B.

[0176] In the present invention, 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. In particular, the fractionation of step (b) is preferably carried out using a fractionation method with low thermal impact, more preferably hot hydrogen stripping.

[0177] The hydrotreatment for hydrodemetallisation (HDM) is a process adapted to remove at least one of metal(s), metalloid(s) and halogen(s). In other words, HDM adapted to remove I 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. As said above, the LWP-based material shall refer to material which results from I is based on (crude) LWP, such as material resulting from the crude LWP feed (1) of step (a) and from the LWP cofeed (4) in the HT processing stage. For example, 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. As a matter of course, the content of the LWP-based material cannot exceed 100 wt.-%.

[0178] 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. When referring the conditions or equipment (e.g. reactor system) of the respective steps of the invention, such description shall refer independently to each individual equipment or condition in case multiple such steps are carried out. For example, 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).

[0179] 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.

[0180] 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 IllPAC group 6, 8 or 10 of the Periodic Table of Elements. Specifically, 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. Preferably, the catalyst in the hydrocracking step is a supported CoMo catalyst and the support comprises alumina (C0M0 / AI2O3) and / or the catalyst is a supported NiMo catalyst and the support comprises alumina (NiMo / A Os). In particular, the catalyst in the hydrocracking step may be a supported NiMo catalyst and the support comprises alumina (NiMo / AbOs).

[0181] 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. Preferably, at least one of a naphtha fraction and a diesel fraction is obtained from fractionating the hydrocracked product (12). In a preferred embodiment, 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).

[0182] The method 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.

[0183] Furthermore, the method of the present invention may be carried out in an apparatus (or integrated system) adapted to carry out the method. Such 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. 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 method. Specifically, 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). Similarly, 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). In general, units corresponding to the method steps mentioned above may be provided and transfer means between these units may be provided so that the method of the present invention (optionally including its optional steps / stages) can be carried out.

[0184] In this respect, the method of the present invention is preferably a continuous process (and the apparatus / system is thus preferably configured for continuous operation). However, individual steps / stages may be carried out in batch mode and / or even if all steps / stages are carried out in continuous operation, the method (and apparatus) may comprise non-continuous storage and / or transportation means. For example, even though it is preferred that 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.

[0185] The present invention also relates to an upgraded hydrocarbon fraction obtainable (or obtained) by the method of the invention.

Claims

CLAIMS1. A method for upgrading crude liquefied waste plastic (LWP), the method comprising(a) providing a crude LWP feed (1),(b) subjecting the crude LWP feed (1) to fractionation to provide at least one distillate fraction (2) and a heavier fraction (3), characterized by(c) subjecting the distillate fraction (2), together with an LWP co-feed (4), to aqueous alkaline heat treatment (HT processing; HTP), followed by liquid-liquid separation 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 optional hydrotreatment(s) for olefins removal (DOR) and / or for hydrodemetallisation (HDM) and / or to optional further fractionation.

2. The method according to claim 1, comprising subjecting the oil phase (5) to hydrotreatment for diolefins removal (DOR) and / or for hydrodemetallisation (HDM), more preferably both diolefins removal (DOR) and hydrodemetallisation (HDM).

3. The method according to any one of the preceding claims, comprising subjecting at least a part of the heavier fraction (3), after optional DOR and / or HDM and / or optional further fractionation, to hydrocracking to obtain hydrocracked product (12).

4. The method according to any one of the preceding claims, comprising subjecting the DOR hydrotreated oil phase (7; 9; 11), after optional HDM and / or optional further fractionation, to hydrocracking to obtain hydrocracked product (12).

5. The method according to any one of claims 3 to 4, wherein the feed material (3; 7; 9; 11) subjected to hydrocracking has a 5 vol% boiling point of 170°C or more, preferably 180°C or more.

6. The method according to any one of claims 3 to 5, further comprising fractionating the hydrocracked product (12) to obtain at least a distillate fraction and a residue fraction, and at least one of a naphtha fraction, a diesel fraction, a gasoline fraction, a heavy fuel oil fraction, and a jet fuel fraction is obtained from fractionating the hydrocracked product (12).

7. The method according to any one of claims 3 to 6, wherein the heavier fraction (3) of step (b) is not subjected to HT processing before hydrocracking.

8. The method according to any one of claims 3 to 7, comprising subjecting a blend of the heavier fraction (3) of step (b) and the oil phase (5) to hydrotreatment for diolefins removal (DOR), followed by a second fractionation and subsequent hydrocracking of a thus-obtained fraction, preferably a second heavier fraction (7).

9. The method according to any one of claims 3 to 8, comprising subjecting the oil phase (5) to hydrotreatment for diolefins removal (DOR) to obtain DOR hydrotreated oil phase (9), and subjecting a blend of the heavier fraction (3) of step (b) and DOR hydrotreated oil phase (9) to hydrodemetallisation (HDM), followed by a second fractionation and subsequent hydrocracking of a thus- obtained fraction, preferably a second heavier fraction (7).

10. The method according to any one of the preceding claims, wherein the oil phase (5) is 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).

11. The method according to any one of claims 8 to 10, wherein the second heavier fraction (7) is forwarded to hydrocracking.

12. The method according to claim 10 or 11, wherein the second distillate fraction (8) is subjected to steam cracking, after optional further treatment, such as purification and / or polishing treatment.

13. The method according to any one of the preceding claims, wherein the distillate fraction (2) is a naphtha range fraction.

14. The method according to any one of the preceding claims, wherein the heavier fraction (3) is a bottoms (residue) fraction.

15. The method according to any one of the preceding claims, further comprising subjecting the crude LWP feed (1) to a hydrotreatment for diolefins removal (DOR) prior to the fractionation in step (b).

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