A process for producing hydrocarbon fractions having waste polymer originating hydrocarbon content

Abstract

A process for producing hydrocarbon fractions is provided. In the process, a liquefied waste polymer feed and a petroleum feed containing at least 10 wt.-% of hydrocarbons boiling above 480°C are provided. The petroleum feed is subjected to hydroconversion in the presence of a hydrotreatment catalyst in a first hydroconversion stage. After an optional interstage separation flashing off a volatiles fraction, at least a non-volatiles fraction of the first hydroconversion stage effluent and the liquefied waste polymer feed are subjected to hydroconversion in the presence of a hydrotreatment catalyst in a second hydroconversion stage. The second hydroconversion stage effluent, and optionally the volatiles fraction from the interstage separation, is / are fed to a separation stage, and at least one or more heavy fraction(s) usable in marine fuels and one or more lighter fraction(s) are recovered.

Description

[0001] A PROCESS FOR PRODUCING HYDROCARBON FRACTIONS HAVING WASTE POLYMER ORIGINATING HYDROCARBON CONTENT

[0002] TECHNICAL FIELD

[0003] The present disclosure generally relates to a process for producing hydrocarbon fractions having waste polymer originating hydrocarbon content. The disclosure relates particularly, though not exclusively, to a process for producing at least one or more heavy fraction(s) usable in marine fuels, especially in residual marine fuels according to ISO 8217:2024 Table 2, and one or more lighter fraction(s) usable as feedstock(s) for downstream further conversion step(s).

[0004] BACKGROUND

[0005] This section illustrates useful background information without admission of any technique described herein representative of the state of the art.

[0006] There is an ongoing need to reduce greenhouse gas (GHG) emissions and / or carbon footprint in the transportation and petrochemical industry. Accordingly, interest towards sustainable materials usable in these fields is growing.

[0007] Liquefied waste polymers (LWP), such as plastic or rubbers, is one of the studied sustainable materials, as driven by the circular economy. Depending on the source of the waste polymers, LWP has variable levels of impurities, such as chlorine-, nitrogen-, sulphur- and oxygen-containing compounds as well as metals. These impurities are common for example in post-consumer packaging waste which is a large-scale source for plastics waste. The impurity levels and species, and also the presence and levels of certain hydrocarbons in LWP, such as diolefins, olefins and cyclic hydrocarbons, pose a challenge to the desired end-uses, and to upgrading of the LWP, e.g. involving increased risk of fouling, coking, catalyst deactivation etc. Several approaches have been developed to manage these challenges, such as the those described in WO2022144490A1 , WO2022144491 A1 , WO2022144495A1 , WO2021105327A1 , WO2021105326A1 in the name of Neste Oyj.

[0008] In addition to the concepts dedicated for processing sustainable materials, for tackling global warming and vanishing crude oil reserves, as well as for meeting the above- mentioned needs, further solutions for industrial processes and products are urgently needed. In this regard, co-feeding of sustainable feed streams into existing petroleum refineries has a growing interest not least because of the existing infrastructure, allowing almost instant implementation.

[0009] SUMMARY

[0010] There is a need for novel processes capable of co-processing sustainable materials, including circular such as waste based materials. Typically, the sustainable carbon content, “credits”, provided by a waste polymer-based material is considered non-detectable. However, the sustainable credits remain in the mass balance of the refinery unit and can be further allocated to one or more of the output streams. The credits may hence be allocated e.g. to output streams intended to be fed to steam cracking or other processes providing monomers to produce polymers having sustainable content and also acting as long-term carbon storage. At the same time, the share of virgin feeds in the refinery unit’s feed pool may be reduced substantially.

[0011] It is an aim to solve or alleviate at least some of the problems related to prior art, including reducing GHG emissions and dependence from petroleum sources, especially in the petrochemicals and transportation sectors. An aim is to provide a process having an improved overall economy and / or producing a product slate having higher overall value. A further aim is to improve the yield of liquid hydrocarbons boiling within diesel range, or lighter, and having circular hydrocarbon content. Yet a further aim is to provide one or more heavy fraction(s) usable in marine fuels.

[0012] The appended claims define the scope of protection. Any examples and technical descriptions of products, processes, and / or uses in the description and / or drawings not covered by the claims are presented as examples useful for understanding the invention.

[0013] According to a first example aspect there is provided a process for producing hydrocarbon fractions, the process comprising: a) providing a liquefied waste polymer (LWP) feed; b) providing a petroleum feed containing at least 10 wt.-%, preferably at least 30 wt.-%, more preferably at least 50 wt.-%, of hydrocarbons boiling above 480°C (EN 15199-2:2020), based on the total petroleum feed weight; c) subjecting the petroleum feed to hydroconversion in the presence of a hydrotreatment catalyst in a first hydroconversion stage comprising one or more hydroconversion zone(s) to obtain a first hydroconversion stage effluent; d) subjecting at least a portion of the first hydroconversion stage effluent and the liquefied waste polymer feed to hydroconversion in the presence of a hydrotreatment catalyst in a second hydroconversion stage comprising one or more hydroconversion zone(s) to obtain a second hydroconversion stage effluent; and e) feeding the second hydroconversion stage effluent to a separation stage and recovering from the separation stage at least one or more heavy fraction(s) having T10 temperature (10 wt.-% recovered, EN 15199-2:2020) of at least 350°C, preferably at least 380°C, more preferably at least 420°C, and one or more lighter fraction(s).

[0014] The inventors have found the present process and embodiments thereof to provide certain advantages compared to prior art processes. The advantages are related e.g to reducing GHG emissions and dependence from petroleum sources, improved overall economy and / or product slate having higher overall value. In the conducted experiments it was observed that when co-feeding the liquefied waste polymer (LWP) feed only to the second hydroconversion stage, over-cracking of the LWP-originating molecules into lower value gases may be reduced, and yield of naphtha boiling range and middle distillates increased. This may be due to LWP feeds generally containing chemical species that are less complex compared to the compounds e.g. in heavy crude oil feeds. At the same time, the impurity levels of the petroleum and LWP feeds were effectively reduced. The co-fed LWP feed resulted also in certain improvements in the obtained product fractions, as discussed in the following.

[0015] The heavy fraction(s) obtainable by the present process may, even as such, meet several or essentially all specification requirements for at least one residual marine fuel category as laid down in ISO 8217:2024 Table 2. In the present Examples it was surprisingly observed that the sulphur levels of the obtained heavy fractions were reduced to an extent that cannot be explained by mere dilution effect caused by the co-fed LWP. The reduced S levels are highly beneficial for the profitability of using the heavy fractions as blend components in marine fuels: heavy fractions with lower S content can help to reduce the S content of the final marine fuel, allowing higher sales margins, or be blended with blend components having higher S content, the blend still meeting specifications. A further profitability benefit comes from the reduced density of the obtained heavy fractions, that allows higher shares of low-quality heavy components, even asphaltenes e.g. as recovered from conventional solvent deasphalting (SDA) of heavy crude oil feed, to be added to the final marine fuels before reaching the maximum density limits specified e.g. in ISO 8217:2024 Table 2 for residual marine fuels. Accordingly, in certain preferred embodiments, at least one heavy fraction recovered in step e) is incorporated into a marine fuel pool, preferably into a residual marine fuel pool.

[0016] In the present Examples it was also observed that co-processing LWP feed led to an increase in total liquid yields, and especially yields of naphtha boiling range and middle distillates. In other words, with the present process more material can be produced for downstream upgrading to higher value products. The recovered lighter fractions had also elevated paraffins content, which is especially beneficial for use as steam cracker feeds, when plastics are converted back to plastics. Furthermore, the co-fed LWP appeared to dilute the impurities especially in the middle distillates range. Thanks to the higher paraffins content and lower impurity levels in the lighter fraction(s) recovered in step e), catalytic upgrading thereof is foreseen easier e.g. in terms of less severe process conditions, slower catalyst deactivation, reduced coking and plugging, compared to upgrading streams with lower paraffins and e.g. higher cyclic hydrocarbon contents. Consequently, fixed bed reactors may be utilised in catalytic hydroprocessing such as hydrotreatment, hydrocracking, hydroisomerisation, and / or hydrodearomatisation. Also the risk of impurity slippage to the converted products is foreseen lower.

[0017] Hence, in certain preferred embodiments, the process further comprises f) subjecting at least a portion of the lighter fraction(s) recovered in step e) to one or more further conversion step(s), preferably to one or more catalytic conversion step(s), more preferably to one or more catalytic hydroprocessing step(s), even more preferably to one or more catalytic fixed- bed hydroprocessing step(s) selected from hydrotreatment, hydrocracking, hydroisomerisation, and / or hydrodearomatisation. In view of circular economy, for example steam cracking and fluid catalytic cracking steps may be particularly desired for further conversion of naphtha boiling range hydrocarbons and heavier hydrocarbons, respectively, as providing polymerizable light olefins. On the other hand, hydroprocessing step(s), such as hydrotreatment, hydrocracking, hydroisomerisation, and / or hydrodearomatisation, may be especially advantageous for obtaining high-quality aviation fuel components, diesel components and / or solvents with good cold properties and / or reduced aromatics contents. Moving catalyst bed systems are particularly beneficial when co-feeding LWP feed, as for example waste polymer pyrolysis oils have typically significant content of olefins, hydrogenation of which is highly exothermic, and elevated content of diolefins that may polymerise easily, which may be troublesome for fixed bed systems. Consequently, use of moving catalyst beds ensures more constant conditions, reduced side reactions, and hence more constant product properties as well as constant, elevated yields of the lighter fraction(s), especially of naphtha and middle distillates boiling range. Ebullated beds are particularly preferred as in these reactors the catalyst is typically continuously or intermittently renewed i.e. withdrawn and replaced with fresh catalyst, instead of regenerating i.e. continuously or intermittently withdrawing, regenerating, and replacing with the regenerated catalyst that may not have as high activity and / or same selectivity as the catalyst had when fresh. Hence, in certain preferred embodiments, in step d) the second hydroconversion stage comprises at least one hydroconversion zone containing the hydrotreatment catalyst arranged in a moving catalyst bed, wherein the moving catalyst bed is preferably an ebullated bed.

[0018] According to the second example aspect, there is provided use of a heavy fraction selected from an atmospheric distillate, a vacuum distillate, an atmospheric bottom and a vacuum tower bottom, preferably a vacuum distillate or a vacuum tower bottom, obtainable by the process according to the first example aspect, as a blend component in a marine fuel, especially in a residual marine fuel meeting one or more characteristics laid down in ISO 8217:2024 Table 2, preferably in an amount of 1 vol-% to 90 vol-%, more preferably 1 vol- % to 80 vol-%, based on the marine fuel volume.

[0019] Different non-binding example aspects and embodiments have been illustrated in the foregoing. The embodiments in the foregoing are used merely to explain selected aspects or steps that may be utilised in different implementations. Some embodiments may be presented only with reference to certain example aspects. It should be appreciated that corresponding embodiments may apply to other example aspects as well.

[0020] BRIEF DESCRIPTION OF THE FIGURES

[0021] Some example embodiments will be described with reference to the accompanying Figure 1 , which illustrates schematically an example embodiment of the present process.

[0022] DETAILED DESCRIPTION In the following description, like reference signs denote like elements or steps. All standards referred to herein are the latest revisions available at the filing date, unless otherwise mentioned.

[0023] Unless otherwise stated, regarding distillation characteristics, such as T10 temperature (10 wt.-% recovered), T90 temperature (90 wt.-% recovered), and boiling point ranges (from IBP to FBP, unless otherwise specified), reference is made to GC-based methods (simulated distillation) ASTM D7096-2019 for naphtha or gasoline range fractions i.e. having final boiling point max. 280 °C, to ASTM D2887-2023 for feeds or fractions predominantly in middle distillates or vacuum gas oil distillates range typically having final boiling point max 538 °C, and to EN 15199-2:2020 for heavy feeds, fractions or residues having initial boiling points (IBP) above 100 °C and high final boiling points (FBP), even above 750 °C.

[0024] As used in the context of this disclosure, marine fuel range fraction or component refers to hydrocarbon compositions suitable for use, at least as blend components, in fuels meeting standard specifications for marine fuels, such as specifications laid down in ISO 8217:2024. Typically, such marine fuel range fractions or components boil, i.e. have IBP and FBP, within a range starting from about 180 °C or more, such as from about 180 °C to about 600 °C, as determined according to EN 15199-2:2020. Marine fuel range components suitable for use in residual marine fuels (herein referred to as residual marine fuel components) may contain even very high boiling compounds, so instead of FBP, such marine fuel range components may be characterised by their kinematic viscosity (KV) at 50°C. Marine fuel range components suitable for use in residual marine fuels, i.e. residual marine fuel components, may have kinematic viscosity (KV) at 50°C for example at most 750 mm2 / s, or at most 700 mm2 / s, as determined according to EN ISO 3104-2020. Hence, hydrocarbons having IBP and KV at 50°C within these ranges may be regarded as suitable for use in marine fuels.

[0025] Regarding various separation and / or fractionation methods and systems, involving e.g. distillation, it is to be understood that the separation and / or fractionation precision may vary, and that in practice even consecutive liquid fractions recovered from a separation stage may boil, i.e. have IBP and FBP, within partly overlapping ranges. Generally, any consecutive liquid fractions have different T50 temperatures. More specifically, a liquid fraction recovered from a separation stage may have a T60 temperature that is lower than the T40 temperature of the consecutive higher boiling fraction. Preferably a liquid fraction recovered from a separation stage may have a T70 temperature that is lower than the T30 temperature of the consecutive higher boiling fraction. As used herein, hydrocarbons refer to compounds consisting of carbon and hydrogen, including paraffins, n-paraffins, i-paraffins, olefins, naphthenes, and aromatics. Heteroatomcontaining hydrocarbons, such as oxygenated hydrocarbons, refer herein to hydrocarbons comprising covalently bound heteroatom such as oxygen.

[0026] As used herein, paraffins refer to non-cyclic alkanes, i.e. non-cyclic, open chain saturated hydrocarbons that are linear (normal paraffins, n-paraffins), or branched (isoparaffins, i- paraffins) having one or more alkyl side chains. In other words, paraffins refer herein to n- paraffins and / or i-paraffins. Correspondingly, the term “paraffins” refers to sum amount of any n-paraffins, and any i-paraffins, if present.

[0027] In the context of the present disclosure, olefins refer to unsaturated, linear, branched, or cyclic hydrocarbons, excluding aromatic compounds. In other words, olefins refer to hydrocarbons having at least one unsaturated bond, excluding unsaturated bonds in aromatic rings. Correspondingly, the term “diolefins” is used for hydrocarbons having at least two unsaturated bonds.

[0028] As used herein, cyclic hydrocarbons refer to all hydrocarbons containing cyclic structure(s), including cyclic olefins, naphthenes, and aromatics. Naphthenes refer herein to cycloalkanes i.e. saturated hydrocarbons containing at least one cyclic structure, with or without side chains. As naphthenes are saturated compounds, they are compounds without aromatic ring structure(s) present. Aromatics refer herein to hydrocarbons containing at least one aromatic ring structure, i.e. cyclic structure having delocalized, alternating TT bonds all the way around said cyclic structure.

[0029] Unless otherwise stated, in the context of the present disclosure, for fractions or compositions boiling at <250°C at standard atmospheric pressure, contents of n-paraffins, i-paraffins, olefins, naphthenes, and aromatics are expressed as weight-% (wt-%) relative to the weight of the fraction / composition in question, or, when so defined, as weight-% (wt- %) relative to the (total) weight of paraffins, or (total) weight of i-paraffins of the feed, stream, effluent, product, component, or sample in question. Said contents may be determined by GC-FID / GC-MS method, preferably conducted as follows: GC-FID as disclosed in ASTM D6839 was run using parameters: column ZB-1 60m, ID 0.25mm, df 1.0 microns, or similar; oven 0°C (2 min) - 1.5 °C / min 300 °C (5 min); injector and detector 300 °C; carrier gas helium 1.0 ml / min; detector gases H2 35 ml / min and air 350 ml / min; make up flow helium 30ml / min; split flow 165:1 (165 ml / min). Individual compounds were identified using GC-MS (run parameters: ion source 230°C; interface 280 °C; scan 25 - 280 m / z; scan speed 303; scan event time 0.88). Commercial tools (Shimadzu LabSolutions / GCMSSolutions and Agilent OpenLab) were used for identification of the detected compounds or hydrocarbon groups, and for determining their mass concentrations by application of response factors relative to n-heptane to the areas of detected peaks followed by normalization to 100 wt-% (for the liquid volume concentrations: by application of density factors to the calculated mass concentration of the detected peaks followed by normalization to 100 vol-%). Cyclic olefins are lumped with naphthenes, unless separately reported. The limit of quantitation for individual compounds of this method is 0.1 wt-%.

[0030] Unless otherwise stated, in the context of the present disclosure, for fractions or compositions boiling at 36°C or higher at standard atmospheric pressure, contents of n- paraffins, i-paraffins, naphthenes, and aromatics are expressed as weight % (wt.-%) relative to the degassed weight of the fraction / composition in question. Said contents may be determined by GCxGC-FID / GCxGC-MS method, preferably conducted as follows: GCxGC (2D GC) method was run as generally disclosed in UOP 990-2011 and by Nousiainen M. in the experimental section of his Master's Thesis Comprehensive two-dimensional gas chromatography with mass spectrometric and flame ionization detectors in petroleum chemistry, University of Helsinki, August 2017, with the following modifications. The GCxGC was run in reverse mode, using a semipolar column (Rxi 17Sil) first and a non-polar column (Rxi5Sil) thereafter, followed by FID detector, using run parameters: carrier gas helium 31.7 cm / s (column flow at 40 °C 1.60 ml / min); split ratio 1 :350; injector280 °C; Column T program 40 °C (0 min) - 5 °C / min - 250 °C (0 min) - 10 °C / min - 300 30 °C (5 min), run time 52 min; modulation period 10 s; detector 300 °C with H2 40 ml / min and air 400 ml / min; makeup flow helium 30 ml / min; sampling rate 250 Hz and injection size 0.2 microliters. Individual compounds were identified using GCxGC-MS, with MS-parameters: ion source 230 °C; interface 300 °C; scan range 25 - 500 amu; event time (sec) 0.05; scan speed 20000. Commercial tools (Shimadzu's LabSolutions, Zoex's GC Image) were used for data processing including identification of the detected compounds or hydrocarbon groups, and for determining their mass concentrations by application of response factors relative to n- heptane to the volumes of detected peaks followed by normalization to 100 wt.-%. Olefins are lumped with naphthenes and heteroatomic species with aromatics, unless separately reported. The limit of quantitation for individual compounds of this method is 0.1 wt.-%.

[0031] As used herein, the term circular in connection with content or materials such as (co-)feeds, fractions, or compositions refers to content or material that is based on or contains discarded, rejected, reused and / or recycled non-biogenic carbon, but that may additionally contain biogenic carbon. Typical exemplary sources for such discarded, rejected, reused and / or recycled materials, possibly also containing at least some biogenic carbon, include reclaimed organic polymer commodities, especially waste plastics and / or end of life tires. As used in the present disclosure, the term “waste polymers” as e.g. in “liquefied waste polymers” or “LWP”, covers discarded, rejected, reused and / or recycled polymers, whether thermoplastic, thermoset or elastomeric, i.e. including both plastics and rubbers such as end of life tires (ELT). The term “liquefied waste polymers” or “LWP” refers to the liquid and / or waxy product of a waste polymer liquefaction process, i.e. not including char or noncondensable gases.

[0032] Renewable, circular, and petroleum content, materials, (co-)feeds, fractions, or compositions are considered differing from one another based on their origin and impact on environmental issues. Therefore, they may be treated differently under legislation and regulatory framework. Typically, renewable, circular, and petroleum materials etc. are differentiated based on their origin and information thereof provided by the producer.

[0033] The renewable (i.e. biological) or non-renewable (such as petroleum) origin of carbon- containing compounds, including hydrocarbons, can be determined by suitable method for analysing the content of carbon from renewable sources e.g. DIN 51637:2014-02, ASTM D6866-2022, or EN 16640:2017. Said methods are based on the fact that carbon atoms of renewable or biological origin comprise a higher number of unstable radiocarbon (14C) atoms compared to carbon atoms of fossil origin. Therefore, it is possible to distinguish between carbon compounds derived from renewable sources and carbon compounds derived from non-renewable sources by analysing the ratio of 12C and 14C isotopes. Thus, a particular ratio of said isotopes can be used as a “tag” to identify a renewable carbon compound and differentiate it from non-renewable carbon compounds. Numerically, the biogenic carbon content can be expressed as the amount of biogenic carbon in the material as a weight percent of the total carbon (TC) in the material (in accordance with ASTM D6866-2022 or EN 16640:2017).

[0034] By hydroconversion in the presence of a hydrotreatment catalyst is meant herein a process of treating organic material by means of molecular hydrogen at an elevated temperature. The hydrotreatment catalyst may be any conventionally used hydrotreatment catalyst or combination thereof, e.g. those well known in the field of petroleum refining. The reactions occurring in the hydroconversion may include thermal and catalytic reactions, especially thermal cracking, but also catalytic cracking, ring-opening, heteroatom cleavage, metal removal, etc, the catalytic reactions including particularly hydrotreatment reactions. The hydrotreatment reactions may include removal of oxygen from oxygenated hydrocarbons as water i.e. hydrodeoxygenation (HDO), sulphur from organic sulphur compounds as dihydrogen sulphide (H2S), i.e. hydrodesulphurisation, (HDS), nitrogen from organic nitrogen compounds as ammonia (NH3), i.e. hydrodenitrogenation (HDN), halogens, for example chlorine from organic chloride compounds as hydrochloric acid (HCI), i.e. hydrodechlorination (HDCI), and / or metals by hydrodemetallization; and / or hydrogenation of olefinic bonds to saturated bonds and / or of aromatics to naphthenes. Depending e.g. on the composition of the feed to the hydroconversion, particularly the composition of the feed fed to the hydroconversion stage or zone in question, different thermal and catalytic reactions may occur and / or prevail. Generally, the hydroconversion is capable of converting feeds of varying compositions to lower-boiling compounds e.g. by cracking, and to more pure materials, e.g. by reducing content of heteroatoms, metals, olefins, aromatics, or the like.

[0035] Hydroprocessing is used in the present disclosure as a general expression including various different catalytic processes conducted in the presence of added hydrogen, such as hydrotreatment, hydrocracking, hydroisomerisation and / or hydrodearomatisation, these processes, as well as reactors and catalysts usable therein being well known e.g. in the field of petroleum refining.

[0036] In the present disclosure, the term “effluent" as in “hydroconversion stage effluent” refers to the effluent from a step of hydroconversion in the presence of a hydrotreatment catalyst, or to the effluent that may be obtained from any further conversion step(s), such as from further catalytic conversion step(s), excluding the catalyst and possibly formed coke. This applies to all process configurations, whether using fixed bed or moving catalyst bed configurations, such as ebullated beds.

[0037] The present disclosure provides a process for producing hydrocarbon fractions, the process comprising: a) providing a liquefied waste polymer (LWP) feed; b) providing a petroleum feed containing at least 10 wt.-%, preferably at least 30 wt.-%, more preferably at least 50 wt.-%, of hydrocarbons boiling above 480°C (EN 15199-2:2020), based on the total petroleum feed weight; c) subjecting the petroleum feed to hydroconversion in the presence of a hydrotreatment catalyst in a first hydroconversion stage comprising one or more hydroconversion zone(s) to obtain a first hydroconversion stage effluent; d) subjecting at least a portion of the first hydroconversion stage effluent and the liquefied waste polymer feed to hydroconversion in the presence of a hydrotreatment catalyst in a second hydroconversion stage comprising one or more hydroconversion zone(s) to obtain a second hydroconversion stage effluent; and e) feeding the second hydroconversion stage effluent to a separation stage and recovering from the separation stage at least one or more heavy fraction(s) having T10 temperature (10 wt.-% recovered, EN 15199-2:2020) of at least 350°C, preferably at least 380°C, more preferably at least 420°C, and one or more lighter fraction(s).

[0038] In conventional petroleum refineries, crude oil distillation may yield atmospheric residue as much as about half of the crude oil feed. Also the yield of vacuum distillation residue is high, for example about 25% of the crude oil feed. The amount of these heavy fractions varies depending on the crude oil origin, heavier crude oil types yielding 2-3 times more vacuum residue compared to a medium or light crude oil type. Various technologies have been developed for converting such crude oil residues or heavy vacuum distillates to lighter fractions, in order to get value out of them. Such conversions may involve extensive processing, such as reducing the boiling point, increasing the hydrogen-to-carbon ratio, and removing impurities such as metals, sulfur, nitrogen and coke precursors. Exemplary conversions include hydrocracking processes using conventional heterogeneous catalysts to upgrade the heavy crude oil feeds for example by fixed-bed hydroprocessing, or by ebullated or other moving catalyst type hydroprocessings. Exemplary noncatalytic upgrading processes include thermal cracking, such as delayed coking, flexicoking, visbreaking, and solvent extraction. Despite an extensive processing of the heavy crude oil feeds, the bottom product remains as the lowest quality and highest impurities containing fraction among the recovered conversion products. Use thereof in marine fuels has been suggested, but quality improvements would help to relieve blending ratio limitations and to improve profitability. The present process allows co-processing even such crude oil distillation residues with LWP feeds to heavy fraction(s) usable in marine fuels and having reduced S content and density, compared to heavy fractions obtained with an otherwise similar process but without using LWP feed. Furthermore, in the conducted experiments it was observed that when co-feeding the LWP feed only to the second hydroconversion stage, over-cracking of the LWP-originating molecules into lower value gases may be reduced, and yield of naphtha range and middle distillates increased. This may be due to LWP feeds generally containing chemical species that are less complex compared to the compounds e.g. in heavy crude oil feeds. The cofed LWP resulted also in certain improvements in the recovered fractions, as discussed hereinafter.

[0039] Shipping is the backbone of international trade, accounting for approximately 80 percent of global transportation measured by volume. But shipping is also responsible for 2-3 percent of global GHG emissions. Bringing it to zero is a huge challenge. The heavy fraction(s) obtainable by the present process will help to reduce GHG emissions and to meet the International Maritime Organization's (IMO's) target of net-zero GHG emissions by 2050. The heavy fraction(s) obtainable by the present process may, even as such, meet several or essentially all specification requirements for at least one residual marine fuel category as laid down in ISO 8217:2024 Table 2. The heavy fraction(s) obtainable with the present process have negligent residual heteroatom content and are essentially fully olefins-free and hence stable even upon prolonged exposure to varying temperature and / or pressure conditions, especially to elevated temperatures, in fuel tanks and feeding systems of vessels. As the obtained heavy fraction(s) have significant petroleum-originating content, their physicochemical properties, especially viscosity and density, are not too different from those of fully fossil heavy fraction(s) produced by an otherwise similar process, so that forming homogeneous blends with further fossil marine fuel components is straight-forward. Additionally, as the present process is based on co-processing, the required equipment is simpler compared to processing the LWP feed in a dedicated unit, thereby reducing both investment and operating costs.

[0040] Furthermore, in the present Examples it was surprisingly observed that the sulphur levels of the obtained heavy fractions were reduced to an extent that cannot be explained by mere dilution effect caused by the co-fed LWP. The reduced S levels are highly beneficial for the profitability of using the heavy fractions as blend components in marine fuels: heavy fractions with lower S content can help to reduce the S content of the final marine fuel, allowing higher sales margins, or be blended with blend components having higher S content, the blend still meeting specifications. At the same time, no impairment of the sediment levels in the heavy fractions was observed, which is also beneficial for use in marine fuels. A further profitability benefit comes from the reduced density of the obtained heavy fractions, that allows higher shares of low-quality heavy components, even asphaltenes e.g. as recovered from conventional solvent deasphalting (SDA) of heavy crude oil feed, to be added to the final marine fuels before reaching the maximum density limits specified e.g. in ISO 8217:2024 Table 2 for residual marine fuels.

[0041] Accordingly, in certain preferred embodiments, at least one heavy fraction recovered in step e) is incorporated into a marine fuel pool, preferably into a residual marine fuel pool.

[0042] In the present process, in step c) the petroleum feed is subjected to hydroconversion in the presence of a hydrotreatment catalyst in a first hydroconversion stage comprising one or more hydroconversion zone(s) to obtain a first hydroconversion stage effluent, and in step d) at least a portion of the first hydroconversion stage effluent and the liquefied waste polymer feed are subjected to hydroconversion in the presence of a hydrotreatment catalyst in a second hydroconversion stage comprising one or more hydroconversion zone(s) to obtain a second hydroconversion stage effluent. Even though fixed bed systems have been developed and are being used for converting even heavy crude oil feeds, for example as swing mode fixed bed systems, preferably at least the second hydroconversion stage, more preferably both the first and the second hydroconversion stage, comprises at least one hydroconversion zone containing the hydrotreatment catalyst arranged in a moving catalyst bed, more preferably in an ebullated bed. Use of moving catalyst beds allows continuous catalyst renewing (addition and withdrawal) and / or regeneration during operation, allowing essentially constant catalyst activity, longer turnaround intervals and less down-time. Using moving catalyst beds is especially beneficial when processing heavy crude oil feeds, as well as LWP feeds that typically also have elevated metal contents. Moving catalyst bed systems are devoid of issues common in fixed bed systems like catalyst bed plugging or channelling and allow maximal contact between the catalyst particles and the gaseous and liquid molecules of the feeds and formed intermediates. Additionally moving catalyst bed systems have essentially the same temperature throughout the reaction space (catalyst bed), so that formation of e.g. hot spots due to the exothermic reactions is not foreseen, and also the desired, high operating temperature can be ensured throughout the bed, which is important as significant part of the conversion to lower boiling components is advantageously due to thermal cracking. Moving catalyst bed systems are particularly beneficial when co-feeding LWP feed, as for example waste polymer pyrolysis oils have typically significant content of olefins, hydrogenation of which is highly exothermic, and even elevated content of diolefins that may polymerise easily, which may be troublesome for fixed bed systems. Consequently, use of moving catalyst beds ensures more constant conditions, reduced side reactions, and hence more constant product properties as well as constant, elevated yields of the lighter fraction(s), especially of naphtha and middle distillates boiling range. Ebullated beds are particularly preferred as in these reactors the catalyst is typically continuously or intermittently renewed i.e. withdrawn and replaced with fresh catalyst, instead of regenerating i.e. continuously or intermittently withdrawing, regenerating, and replacing with the regenerated catalyst that may not have as high activity and / or same selectivity as the catalyst had when fresh.

[0043] Hence, in certain preferred embodiments, in step d) the second hydroconversion stage comprises at least one hydroconversion zone containing the hydrotreatment catalyst arranged in a moving catalyst bed, wherein the moving catalyst bed is preferably an ebullated bed.

[0044] In certain further preferred embodiments, in step c) the first hydroconversion stage comprises at least one hydroconversion zone containing the hydrotreatment catalyst arranged in a moving catalyst bed, preferably at least two hydroconversion zones in series each containing the hydrotreatment catalyst arranged in a moving catalyst bed, wherein the moving catalyst bed is preferably an ebullated bed.

[0045] In certain preferred embodiments, the hydrotreatment catalyst in step c) and / or step d) includes one or more hydrotreatment catalysts selected independently for each hydroconversion zone from sulfided hydrotreatment catalysts comprising at least one or more metals from Group VIII of the Periodic Table and / or from Group VI B of the Periodic Table, preferably at least one or more of Ni, Mo, W, and / or Co, even more preferably at least one or more of Ni and / or Co and Mo and / or W, such as NiMo, CoMo, NiCoMo, NiW, and / or NiMoW, preferably on a support such as alumina and / or silica. This kind of solid heterogeneous hydrotreatment catalysts are commercially available for use in ebullated bed and fixed bed hydroconversion systems, including catalysts designed primarily for certain hydrotreatment reactions such as hydrodemetallization, and / or even for hydrocracking. In addition to the hydrotreatment catalyst(s), also co-catalysts may be utilised in step c) and / or step d) to achieve additional reactions and / or to boost any of the hydrotreatment reactions, as known in the art. The heterogeneous hydrotreatment catalyst typically comprises a support structure having a large surface area and interconnected channels or pores and the active metal(s), such as sulfides of cobalt, nickel, tungsten, and / or molybdenum, e.g. dispersed within the channels or pores. The pores of the support may be of limited size to maintain mechanical integrity of the heterogeneous catalyst and prevent breakdown and formation of excessive fines in the reactor. Heterogeneous catalysts usable in the present process may have a shape of cylindrical pellets, cylindrical extrudates, trilobes, rings, saddles, spherical solids, or the like. Also dispersed metal sulfide catalysts may be used in the present process. These catalysts have typically a submicron particle size (below 1 pm), such as less than about 500 nm, or even less than about 50 nm. These catalysts may also include molecular or molecularly-dispersed catalyst compounds.

[0046] In certain preferred embodiments, each hydroconversion zone in step c) and step d) is operated at a temperature (as determined at the zone inlet), selected independently from each other, within a range from 350 °C to 480 °C, preferably from 370 °C to 460 °C. Within these temperature ranges thermal cracking is abundant, and catalytic heteroatom removal and hydrogenation of any present or formed olefins are enhanced. In certain preferred embodiments, each hydroconversion zone in step c) and step d) is operated at a pressure (as determined at the zone outlet), selected independently from each other, within a range from 8 MPa to 20 MPa, preferably from 10 MPa to 20 MPa. Within the specified elevated pressure ranges, sufficient hydrogen partial pressure may be ensured and residual olefins and heteroatoms minimised in the hydroconversion products despite the significant hydrogen consumption and the formed gaseous cracking products reducing the H2 partial pressure towards the end of the stage or zone, whether after the last hydrogen injection point or between injection points. In certain embodiments, each hydroconversion zone in step c) and step d) is operated using a space velocity, selected independently from each other, within a range from 0.05 to 5, preferably from 0.1 to 2 m3 feed entering said zone per m3 reaction space per hour, and / or a ratio of H2 to the feed entering said zone, selected independently from each other, within a range from 50 to 2000, preferably from 100 to 1500 normal liters H2 per liter feed. Regarding the space velocity, for fixed beds this may be expressed as volume of the liquid feed entering the zone per volume of the catalyst per hour, however the above-mentioned numerical ranges for the space velocity still apply. Regarding hydroconversion zones wherein the hydrotreatment catalyst is arranged in a moving catalyst bed, such as an ebullated bed, the catalyst loading and fresh catalyst addition rate shall be selected so that the catalyst activity may be maintained essentially constant. Adjusting these process conditions as specified herein further enhances reaching the desired conversion level, yields and / or product fraction properties.

[0047] In the present process, a petroleum feed containing at least 10 wt.-%, preferably at least 30 wt.-%, more preferably at least 50 wt.-%, of hydrocarbons boiling above 480°C (EN15199- 2:2020), based on the total petroleum feed weight, is provided. Such feeds have substantial content of heavy compounds, that need to be cracked to produce lower-boiling compounds having higher value, and that typically have significant content of impurities, such as heteroatoms, especially S and N, and metals. Typically such petroleum feeds, particularly crude oil distillation residues, also contain heavier molecules compared to the LWP feeds, and these heavier molecules may also be thermodynamically easier to crack. This is believed to contribute to the lower than expected cracking level of the LWP feed molecules, which helps to enrich the waste polymer originating hydrocarbon content in the middle distillates and lighter boiling liquids, without excessive over-cracking to gases.

[0048] In certain preferred embodiments, the petroleum feed comprises a heavy petroleum feed component in an amount of at least 25 wt.-%, preferably at least 50 wt.-%, more preferably at least 75 wt.-%, wherein the heavy petroleum feed component preferably comprises at least 50 wt.-%, preferably at least 60 wt.-%, more preferably at least 70 wt.-% of compounds boiling above 565°C (EN 15199-2:2020), based on the heavy petroleum feed component weight, and / or has a density at 15°C within a range from 900 kg / m3 to 1150 kg / m3 (EN ISO 12185-1996), preferably within a range from 920 kg / m3 to 1100 kg / m3, more preferably within a range from 950 kg / m3 to 1050 kg / m3, and / or has a viscosity at 135°C within a range from 20 mm2 / s to 200 mm2 / s (EN 12595-2023), preferably within a range from 40 mm2 / s to 180 mm2 / s, more preferably within a range from 50 mm2 / s to 160 mm2 / s. Even more preferably, the petroleum feed consists essentially of a heavy petroleum feed component, further preferably a crude oil distillation residue, as specified herein.

[0049] The present process allows using low quality crude oil materials, such as crude oil distillation residue(s), for example crude oil atmospheric residue or even crude oil vacuum residue, and / or crude oil heavy vacuum distillate(s), which is beneficial for the process economy. In certain preferred embodiments, the heavy petroleum feed component comprises distillation residue(s) and / or crude oil heavy vacuum distillate(s), preferably as solvent deasphalted (SDA). By subjecting at least a portion of the crude oil distillation residue(s), particularly the crude oil vacuum residue, to solvent deasphalting (SDA) reducing content of asphaltenes, sulphur and other impurities, lower quality crude oils may be utilised, or heavy fraction(s), even heavy separation stage bottom, of higher quality, e.g. with lower sulphur contents, may be obtained. Hence, in certain further preferred embodiments, step b) comprises subjecting at least a portion of a crude oil distillation residue to solvent deasphalting to obtain a deasphalted oil (DAO) and an asphaltenes fraction, and in step c) the deasphalted oil (DAO) and optionally a portion of the crude oil distillation residue are fed as the petroleum feed to the hydroconversion, preferably the weight ratio of the DAO to the portion of the crude oil distillation residue ranging from 90:10 to 20:80, more preferably from 80:20 to 30:70. Embodiments using solvent deasphalted oil as the petroleum feed or component thereof provide the additional benefit that the separated asphaltenes fraction may be blended in marine fuels, especially in residual marine fuels, with the heavy fraction(s) recovered in step e). This has been observed to enhance stability of the final marine fuels, reduce the need for high value aromatic blending components in such marine fuels to achieve the desired aged sediment levels, and to improve compatibility of such marine fuels with other marine fuels especially of lower quality, e.g. when refuelling the vessel.

[0050] In certain further preferred embodiments, the petroleum feed has a sulphur content of more than 1.0 wt.-%, preferably at least 1.2 wt.-%, such as within a range from 1.2 wt.-% to 6.0 wt.-%, more preferably at least 1 .5 wt.-%, such as within a range from 1 .5 wt.-% to 4.0 wt.- % (EN ISO 8754-2003), based on the total petroleum feed weight. The present process and use of the LWP feed provide a significant reduction in the S content. Especially in the recovered heavy fraction(s) the observed S reduction was greater than the dilution effect provided by the co-fed LWP.

[0051] The liquefied waste polymer (LWP) feed for use in the present process may be provided by any well-known method in the art of liquefaction of waste plastics and rubbers. For example, the LWP feed may comprise thermally such as hydrothermally or by pyrolysis, or catalytically such as thermo-catalytically liquefied waste polymers including plastics and rubbers such as end of life tires (ELT). Due to its mixed waste nature, the LWP has typically non-biogenic carbon content, but it may also have some biogenic carbon content. For example, the biogenic carbon content of ELT may vary, but is typically significant, such as from 15 to 40 wt.-%, based on the total weight of carbon (TC) in the ELT, due to e.g. natural rubber present in ELT. Also the biogenic carbon content of waste plastics may vary, but is currently foreseen much lower than the share of non-biogenic carbon content, due to the low share of bio-based plastics in the plastic waste, however this may change over time when the production of bio-based plastics increases.

[0052] In certain preferred embodiments, the liquefied waste polymer feed comprises at least waste polymer pyrolysis oil and / or waste polymer hydrothermal liquefaction oil. Preferably, in step a) providing the liquefied waste polymer feed in step a) includes depolymerizing waste polymer by pyrolysis to provide waste polymer pyrolysis oil and / or by hydrothermal liquefaction to provide waste polymer hydrothermal liquefaction oil, wherein the waste polymer preferably comprises at least mixed waste plastics and / or end of life tires (ELT). Typical LWP materials wherefrom the LWP feed may be recovered, or serving as the LWP feed, comprise impurities including metals such as iron, metalloids such as silicon, and / or halogenated compounds such as chlorinated compounds. These impurities may be present in the LWP materials even in high contents, for example 500 w-ppm or more, 1000 w-ppm or more, or even 5000 w-ppm or more of halogen elements provided by halogenated compounds, and / or 2500 w-ppm or more, or even 10 000 w-ppm or more of metals and metalloids in total, including alkali, alkaline-earth, transition and post transition metals. Other impurities typically present in LWP materials include sulphur-, nitrogen- and / or oxygencontaining compounds, in total contents generally less than 20 000 w-ppm of these heteroelements provided by respective heteroatom compounds.

[0053] The LWP materials exemplified in the foregoing are readily available, and various established pre-treatment techniques exist. Exemplary pre-treatment methods suitable for the present disclosure comprise alkaline heat-treatment, selective diolefin hydrogenation, demetallation e.g. by mild hydrotreatment, washing with aqueous solution, distillation, removal of solids, and any combinations thereof. However, due to the efficiency of the present process, such pretreatment may not be needed or may be minimised or optimised to recover an LWP fraction of highest impurities as the LWP feed in step a). In the context of the present process, the LWP feed provided in step a) refers to these materials in their as-is or pretreated forms, as the case may be.

[0054] Since the present process is able to convert even heavy crude oil feeds having high impurity contents, it is not limited to co-processing only less complicated LWP grades, such as LWP from predominantly polyethylene and polypropylene based sorted waste plastic (such as plastics recycle classification types 2, 4, and 5), but the co-fed LWP feed may also comprise LWP from polystyrene (such as plastics recycle classification type 6), and even some LWP from polyvinyl chloride based sorted waste plastic (such as plastics recycle classification type 3) and LWP from other polymers (such as plastics recycle classification type 7). In other words, the present process allows utilising higher share of other than polyolefin-based LWP in the feed. The present process may also handle LWP from mixed plastic waste as well as rejects from mechanical recycling. The present process is also suited for processing LWP from waste rubber, such as end of life tires (ELT), including natural rubber and / or synthetic rubber such as styrene-butadiene rubber. For using complicated LWP grades, a moving catalyst bed and especially an ebullated bed in the second hydroconversion stage may be advantageous, providing the benefits discussed in the foregoing. Similarly, the present process is not limited to co-processing only distillate fractions of LWP. Preferably, the LWP feed is a full-range LWP oil or a naphtha-removed LWP fraction, i.e. having substantial content of heavy compounds. Hence, in certain preferred embodiments, the liquefied waste polymer feed comprises at least 5 wt.-%, preferably at least 10 wt.-%, more preferably at least 20 wt.-% of compounds boiling above 360°C (ASTM D2887-2023), based on the total LWP feed weight. In certain further preferred embodiments, the liquefied waste polymer feed comprises at least 1 wt.-%, preferably at least 3 wt.-%, more preferably at least 5 wt.-% of compounds boiling above 480°C (ASTM D2887-2023), based on the total LWP feed weight. In certain embodiments, fractionation of the LWP may be omitted, reducing investment and operating costs as well as complexity of the process.

[0055] In certain further preferred embodiments, the liquefied waste polymer feed has a T10 temperature (10 wt-% recovered, ASTM D2887-2023) at least 150°C, preferably at least 180°C, more preferably at least 200°C. These embodiments are foreseen to contribute beneficially to the heavy fraction yields and / or properties. These LWP feeds may be prepared e.g. by subjecting a full-range LWP material to distillation to remove a naphtha boiling range fraction, that may be fed to steam cracking, optionally as hydrotreated, for producing light olefinic monomers for polymer manufacture.

[0056] Since the present process is suitable for converting even heavy crude oils as the petroleum feed, it is not limited to co-processing only fully hydrotreated LWP or diolefin-depleted LWP (selectively hydrogenated LWP to remove diolefins), unlike many other conversion processes. In certain preferred embodiments, the liquefied waste polymer feed has a Bromine number more than 1 g Br / 100g of the LWP feed, preferably more than 5 g Br / 100g, more preferably more than 30 g Br / 100g (ISO 3839-1996). Bromine numbers more than 1 g Br / 100g of the LWP feed are typical e.g. for crude LWP feeds, or non-hydrotreated or at most partially hydrotreated LWP feeds, while Bromine numbers more than 5 or more than 30 g Br / 100g of the LWP feed are typical for crude LWP feeds or non-hydrotreated LWP feeds or to LWP feeds subjected to selective diolefin hydrogenation, only. In certain preferred embodiments, the liquefied waste polymer feed has not been subjected to any catalytic hydrotreatment. In these embodiments even Bromine numbers more than 100 g Br / 100g of the LWP feed are possible. All these embodiments are preferred, as corresponding to less than fully hydrotreated or even not at all hydrotreated LWP feeds. In this way expensive catalytic treatment steps may be reduced, again reducing investment and operating costs as well as complexity of the process. Hence, in certain particularly preferred embodiments, the liquefied waste polymer feed comprises at least 5 wt.-%, preferably at least 10 wt.-%, more preferably at least 20 wt.-% of compounds boiling above 360°C (ASTM D2887-2023), based on the total LWP feed weight, and has a Bromine number more than 1 g Br / 100g of the LWP feed, preferably more than 5 g Br / 100g, more preferably more than 30 g Br / 100g (ISO 3839-1996). In certain further preferred embodiments, the liquefied waste polymer feed has a T10 temperature (10 wt-% recovered, ASTM D2887-2023) at least 150°C, preferably at least 180°C, more preferably at least 200°C and has a Bromine number more than 1 g Br / 100g of the LWP feed, preferably more than 5 g Br / 100g, more preferably more than 30 g Br / 100g (ISO 3839- 1996). In this way combined benefits of the embodiments discussed in the foregoing may be reached.

[0057] Generally, the higher the content of compounds boiling above 360°C or above 480°C and / or the higher the T10 temperature, and especially concerning non-hydrotreated LWP feeds, the higher the expected viscosity and / or density of the LWP feed. If needed or desired, a lower viscosity feed stream, e.g. comprising fossil atmospheric and / or vacuum disti llate(s) , may be blended as a minority component with the LWP feed, to ease handling, such as pumping, of the LWP feed. When not originating from waste polymers, such additional feed stream is to be regarded as a further co-feed to the second hydroconversion stage, and not part of the LWP feed.

[0058] In certain embodiments, in step d) the liquefied waste polymer feed and the at least a portion of the first hydroconversion stage effluent are fed to the second hydroconversion stage within a weight-ratio of the liquefied waste polymer feed to the at least a portion of the first hydroconversion stage effluent from 1 :99 to 80:20, preferably from 5:95 to 50:50, more preferably from 10:90 to 30:70. Within these ratios lighter fraction(s), especially middle distillate(s) and lower-boiling hydrocarbons, with enriched circular hydrocarbon content are attainable, while still producing the heavy fractions(s) in reasonable amounts.

[0059] In certain embodiments, the first hydroconversion stage effluent obtained in step c) is subjected to an interstage separation to obtain a volatiles fraction and a non-volatiles fraction, and the non-volatiles fraction is fed to the second hydroconversion stage in step d). In certain preferred embodiments, at least a portion of the volatiles fraction is fed with the second hydroconversion stage effluent to the separation stage in step e) and / or at least a portion of the volatiles fraction is fed to one or more further conversion step(s), preferably to one or more catalytic conversion step(s), more preferably to one or more catalytic hydroprocessing step(s). Such further conversion may involve e.g. steam cracking or catalytic hydroprocessing with the at least a portion of the lighter fraction(s) in step f) described in the foregoing.

[0060] In certain embodiments, the volatiles fraction comprises at least compounds boiling below 300 °C at atmospheric pressure, and the non-volatiles fraction comprises at least compounds boiling above 300 °C at atmospheric pressure.

[0061] Having an interstage separation may provide several advantages. By removing a volatiles fraction, smaller equipment may suffice in the second hydroconversion stage. Alternatively, a higher (full) capacity is available in the second hydroconversion stage for converting the remaining heavy components, due to the reduced vapour load. The reduced vapour load enhances hydrogen purity and allows a higher hydrogen partial pressure in the second hydroconversion stage, thereby enhancing catalytic reactions so that the recovered fractions are purer and contain less olefins. Also, less pentane, heptane and similar saturated light compounds, that are poor solvents for asphaltenes, enter the second hydroconversion stage, thereby reducing the risk of precipitate formation. On the other hand, in embodiments where only the non-volatiles fraction continues to the second hydroconversion stage, the content of species prone to sediment formation may increase to a level inducing aggregation. Hence, in these embodiments utilising the LWP feed provided in step a) is even more advantageous, and / or utilising a petroleum feed whereof at least a portion has been subjected to deasphalting and / or comprising less than 50 wt.-% of compounds boiling above 565°C (EN 15199-2:2020), based on the total petroleum feed weight.

[0062] In the separation stage any separation technologies well known in the field of hydrocarbon fractionation, such as in petroleum refining, may be utilised. The separation stage may be carried out in a separation stage system comprising separation and / or fractionation units. For example, at least part of gaseous components may be separated in gas-liquid separator(s), whereafter other separation and / or fractionation unit(s) may follow. Separation unit(s) may be included e.g. to attain stabilisation which is one type of partial distillation for removing gaseous and most volatile liquid hydrocarbons to reduce vapour pressure, and which may be conducted for example using stripper(s) or distillation column(s). For fractionation for example distillation column(s) and / or evaporator(s) may be included. The one or more lighter fraction(s) such as a naphtha fraction, a middle distillate fraction, and / or a vacuum gas oil fraction, and the one or more heavy fraction(s) such as an atmospheric distillate, a vacuum distillate, an atmospheric bottom and / or a vacuum tower bottom, may be recovered e.g. using one or more distillation unit(s) and / or evaporation unit(s). The distillation and / or evaporation unit(s) may comprise atmospheric distillation and / or evaporation unit(s), and / or vacuum distillation and / or evaporation unit(s).

[0063] Similarly as in any typical petroleum processing, an aqueous solution such as water or aqueous amine solution may be introduced into the separation section so as to at least partly dissolve any formed ammonium chloride salts and / or hydrochloric acid. These may form by reaction between chloride ions generated by hydrogenation of chlorine-containing compounds present in the petroleum and / or LWP feeds forming HCI during the hydroconversion followed by dissolution in the water, and ammonium ions generated by hydrogenation of nitrogen-containing compounds in the petroleum and / or LWP feeds forming NH3 during the hydroconversion and / or provided by injection of an amine followed by dissolution in the water. As usual, this improves the removal of chlorine-containing impurities and reduces the risks of clogging caused by precipitation and accumulation of ammonium chloride salts.

[0064] Based on the conducted experiments it seems that the properties of the lighter fraction(s) obtained with and without the co-fed LWP feed were sufficiently similar so that e.g. downstream further conversion step(s) thereof do not necessarily require any process adaptation. This allows the present process to be run even in campaign mode, i.e. from time to time running with and without the co-fed LWP feed, and / or with varying shares of the LWP feed. In the present Examples it was also observed that co-processing LWP feed led to increase in total liquid yields, and especially yields of naphtha boiling range and middle distillates. In other words, with the present process more material can be produced for downstream upgrading to provide higher value products. The lighter fractions recovered in step e) had also elevated paraffins content, which is especially beneficial for use as steam cracker feeds, when plastics are converted back to plastics. Furthermore, the co-fed LWP appeared to dilute the impurities especially in the middle distillates range. Thanks to the higher paraffins content and lower impurity levels in the lighter fractions recovered in step e), catalytic upgrading thereof is foreseen easier e.g. in terms of less severe process conditions, slower catalyst deactivation, reduced coking and plugging, compared to upgrading streams with lower paraffins and e.g. higher cyclic hydrocarbon contents. Consequently, fixed bed reactors may be utilised in catalytic hydroprocessing such as hydrotreatment, hydrocracking, hydroisomerisation, and / or hydrodearomatisation. Also the risk of impurity slippage to the converted products is foreseen lower. Hence, in certain preferred embodiments, the process further comprises f) subjecting at least a portion of the lighter fraction(s) recovered in step e) to one or more further conversion step(s), preferably to one or more catalytic conversion step(s), more preferably to one or more catalytic hydroprocessing step(s), even more preferably to one or more catalytic fixed- bed hydroprocessing step(s) selected from hydrotreatment, hydrocracking, hydroisomerisation, and / or hydrodearomatisation. In view of circular economy, for example steam cracking and fluid catalytic cracking steps may be particularly desired for further conversion of naphtha boiling range hydrocarbons and heavier hydrocarbons, respectively, as providing polymerizable light olefins. On the other hand, hydroprocessing step(s), such as hydrotreatment, hydrocracking, hydroisomerisation, and / or hydrodearomatisation, may be especially advantageous for obtaining high-quality aviation fuel components, diesel components and / or solvents with good cold properties and / or reduced aromatics contents.

[0065] In certain embodiments, the one or more lighter fraction(s) recovered in step e) have T90 temperature (90 wt.-% recovered, ASTM D2887-2023) less than 500°C, preferably less than 480°C. The circular hydrocarbon content provided by the LWP feed reside predominantly, or even essentially completely in this boiling point range. In certain preferred embodiments, the one or more lighter fraction(s) recovered in step e) include one or more middle fraction(s) having T10 and T90 temperatures (10 wt.-% and 90 wt.-% recovered, respectively, ASTM D2887-2023) within a range from 50°C to 430°C, preferably from 140°C to 420°C. The circular hydrocarbon content provided by the LWP feed is enriched particularly in this boiling range. In certain particularly preferred embodiments, the one or more lighter fraction(s) recovered in step e) include one or more naphtha fraction(s) having T90 temperature (90 wt.-% recovered, ASTM D7096-2019) of at most 200°C, one or more middle distillate fraction(s) having T10 and T90 temperatures (10 wt.-% and 90 wt.-% recovered, respectively, ASTM D2887-2023) within a range from 140°C to 420°C, and optionally one or more vacuum gas oil fraction(s) having T10 temperature (10 wt.-% recovered, ASTM D2887-2023) of at least 330°C. Recovering several different and hence narrower boiling fractions provides circular hydrocarbon containing streams optimal for further conversion step(s) aiming at different high value products.

[0066] In the present process, the one or more heavy fraction(s) recovered in step e) have T10 temperature (10 wt.-% recovered, EN 15199-2:2020) of at least 350°C, preferably at least 380°C, more preferably at least 420°C. The higher the T10 temperature of the recovered heavy fraction(s), the more of the valuable lighter hydrocarbons may be recovered in the lighter fractions, such as in middle distillates or in a light vacuum gas oil fraction, usable in a wider range of applications than the heavy fraction(s). At the same time the heavy fraction(s) exhibit(s) reduced S content and reduced density, compared to heavy fraction(s) obtained by an otherwise similar process but without the LWP feed, providing profitability improvements discussed in the present disclosure. In certain preferred embodiments, the one or more heavy fraction(s) recovered in step e) include an atmospheric distillate, a vacuum distillate, an atmospheric bottom and / or a vacuum tower bottom, preferably at least a vacuum distillate and / or a vacuum tower bottom, having T10 temperature (10 wt.-% recovered, EN 15199-2:2020) within a range from 350°C to 530°C, preferably from 380°C to 510°C, more preferably from 420°C to 510°C. When the heavy fractions are recovered in this way, more of the valuable lighter hydrocarbons may be recovered in the lighter fraction(s), such as in middle distillates or in a light vacuum gas oil fraction, and in lower- boiling heavy fraction(s), such as in a heavy vacuum distillate. In other words, at least two heavy fractions usable in marine fuels may be recovered, the lower-boiling one(s) being usable in residual marine fuels even as such, or in distillate marine fuels as a substantial blending component. Furthermore, as the multi-stage processing according to the present process is effective in reducing the content of the heaviest molecules, typically the one or more heavy fraction(s) recovered in step e) include an atmospheric distillate, a vacuum distillate, an atmospheric bottom and / or a vacuum tower bottom, preferably at least a vacuum distillate and / or a vacuum tower bottom, having T10 and T50 temperatures (10 wt- % and 50 wt.-% recovered, respectively, EN 15199-2:2020) within a range from 350°C to 670°C, preferably from 380°C to 650°C, more preferably from 420°C to 650°C, contributing beneficially to the usability of the heavy fraction(s) in marine fuels.

[0067] In certain further preferred embodiments, the one or more heavy fraction(s) recovered in step e) has / have one or more of the following: a density at 15°C within a range from 850 to 1060 kg / m3, preferably from 900 to 1000 kg / m3 (EN ISO 12185-1996); and / or a viscosity at 80°C at least 30 mm2 / s, preferably at least 40 mm2 / s, more preferably at least 50 mm2 / s (EN 12595-2023), and a viscosity at 135°C at most 170 mm2 / s; and / or a total content of sulphur less than 1.0 wt.-%, preferably less than 0.6 wt.-%, more preferably less than 0.3 wt.-% (ASTM D7039-15a(2020)). All these properties of the heavy fraction(s) are advantageous for use in marine fuels, and attainable by the present process even when using crude oil vacuum distillation residue as the petroleum feed.

[0068] As discussed in the foregoing and shown in the present Examples, the at least one or more heavy fraction(s) recovered in step e) is / are particularly beneficial as blend components in marine fuels. Hence, according to the present disclosure, there is provided use of a heavy fraction selected from an atmospheric distillate, a vacuum distillate, an atmospheric bottom and a vacuum tower bottom, preferably a vacuum distillate or a vacuum tower bottom, obtainable by the process according to the first example aspect, as a blend component in a marine fuel, especially in a residual marine fuel meeting one or more characteristics laid down in ISO 8217:2024 Table 2, preferably in an amount of 1 vol-% to 90 vol-%, more preferably 1 vol-% to 80 vol-%, based on the marine fuel volume. The advantages of such use, for example the profitability benefits provided by the surprisingly low S content and reduced viscosity, are as discussed in connection with the process according to the present disclosure. In certain further preferred embodiments, the heavy fraction, preferably a vacuum distillate, has T10 temperature (10 wt.-% recovered, EN 15199-2:2020) within a range from 420°C to 500°C and preferably T10 and T90 temperatures (10 wt.-% and 90 wt- % recovered, respectively, EN 15199-2:2020) within a range from 420°C to 580°C. In certain other further preferred embodiments, the heavy fraction, preferably an atmospheric bottom or a vacuum tower bottom, has T10 temperature (10 wt.-% recovered, EN 15199-2:2020) of at least 500°C, preferably within a range from 500°C to 600°C.

[0069] Schematic presentation of the process

[0070] Fig. 1 schematically shows a process according to an example embodiment. In the process shown in Fig. 1 , a liquefied waste polymer feed LWP, and a heavy crude oil feed HCO comprising for example at least one or more of crude oil distillation residue(s) and / or crude oil vacuum distillate(s), optionally as solvent deasphalted (SDA), are provided. The heavy crude oil feed HCO is subjected to hydroconversion in the presence of a hydrotreatment catalyst in a first hydroconversion stage 100 to obtain a first hydroconversion stage effluent 10. Preferably the first hydroconversion stage comprises at least two hydroconversion zones in series each containing the hydrotreatment catalyst arranged in a moving catalyst bed, preferably in an ebullated bed. The first hydroconversion stage effluent 10 may be subjected to an interstage separation 150 to obtain a volatiles fraction 15 and a non-volatiles fraction 20. The first hydroconversion stage effluent 10 or a portion thereof, such as the non-volatiles fraction 20, is then subjected together with the liquefied waste polymer feed LWP to hydroconversion in the presence of a hydrotreatment catalyst in a second hydroconversion stage 200 to obtain a second hydroconversion stage effluent 30. Preferably the second hydroconversion stage comprises at least one hydroconversion zone containing the hydrotreatment catalyst arranged in a moving catalyst bed, preferably in an ebullated bed. The second hydroconversion stage effluent 30, optionally together with at least a portion of the volatiles fraction 15, is then fed to a separation stage 300. From the separation stage 300 at least one or more heavy fraction(s) having T10 temperature (10 wt.-% recovered, EN 15199-2:2020) of at least 420°C, such as a vacuum distillate 45, having T10 temperature (10 wt.-% recovered, EN 15199-2:2020) of at least 420°C, and a separation stage bottom 40, such as a vacuum tower bottom, having T10 (10 wt.-% recovered, EN 15199-2:2020) of at least 500°C, and one or more lighter fraction(s) 50, such as atmospheric and / or light vacuum distillate(s), are recovered. The one or more heavy fraction(s) 40, 45, such as an atmospheric or vacuum distillate and / or a separation stage bottom, are usable as marine fuel component(s). In certain preferred embodiments, at least a portion of the lighter fraction(s) 50 is subjected to one or more further conversion step(s) 400, 600, preferably to one or more catalytic conversion step(s), more preferably to one or more catalytic hydroprocessing step(s), even more preferably to one or more catalytic fixed- bed hydroprocessing step(s) selected from hydrotreatment, hydrocracking, hydroisomerisation, and / or hydrodearomatisation. In certain particularly preferred embodiments, at least a portion of the lighter fraction(s) 50 is subjected to catalytic fixed- bed hydroprocessing step(s) selected from hydrotreatment 400 to obtain a hydrotreatment effluent 60, followed by further separation stage 500 to recover a light hydrotreatment overhead 65, one or more hydrotreatment distillate(s) 80 and / or a hydrotreatment bottom 70, and subjecting at least a portion of the hydrotreatment distillate(s) 80 and / or of the hydrotreatment bottom 70 to further catalytic fixed-bed hydroprocessing step(s) selected from hydroisomerisation and / or hydrocracking 600 to provide fraction(s) 90 with enhanced properties, particularly cold properties, compared to the properties of the hydrotreatment distillate(s) 80 and / or the hydrotreatment bottom 70, respectively.

[0071] EXAMPLES

[0072] Example 1. Heavy crude oil and liquefied waste polymer feeds

[0073] Liquefied waste polymers (LWP) of varying qualities are commercially available from waste polymer pyrolyzing companies. Two different liquefied waste plastic qualities were purchased, both being waste plastic pyrolysis oils. One of the LWP:s was blended with heavy vacuum gas oil (straight-run HVGO fraction of crude oil) to obtain a blend of 75 wt.- % LWP and 25 wt.-% HVGO having reduced viscosity and easier pumpability (for simplicity referred to as LWP feed 1 in the Examples). The other LWP was subjected to selective hydrogenation to remove diolefins according to the procedure disclosed in FI130057B (120- 210°C, 1-50 barg, LHSV 1-5 h-1 using CoMo and / or NiMo catalyst), and subjected to gasliquid separation. For use in the test runs, one portion of the diolefin depleted LWP was subjected to stabilisation (vapour pressure reduction) to obtain a stabilised LWP feed (LWP feed 2) and another portion was subjected to distillation removing naphtha boiling range fraction (<180°C) to obtain a heavy LWP feed boiling above 180°C (LWP feed 3). Certain properties and content of certain impurities of the obtained LWP feeds 1-3 were measured and are reported in Table 1 .

[0074] Table 1. Certain properties and impurities of the LWP feeds used in the test runs.

[0075] * Inductively coupled plasma tandem mass spectrometer method for trace level elements from microwave digestion pretreated samples; NA=not analysed

[0076] One batch of heavy crude oil feeds were prepared by subjecting crude oil vacuum residue (VR) to a conventional solvent deasphalting (SDA) to provide a deasphalted oil (referred to as DAO), and an asphaltenes fraction that was set aside for later use as an additional blend component in the marine fuels. The DAO stream served as the petroleum feeds in the test runs. Certain properties of the DAO stream were analysed and are reported in Table 2.

[0077] Table 2. Certain properties of the DAO stream used in the test runs.

[0078] * Inductively coupled plasma tandem mass spectrometer method for trace level elements from microwave digestion pretreated samples

[0079] As can be seen from Table 2, DAO is a viscous, high-boiling and high-density feed having significant total content of Na, V, Fe, and Ni, and a high share of unsaturated compounds (especially aromatics), as well as high sulphur and nitrogen contents. This kind of heavy crude oil feeds are among the least valuable crude oil fractions, that require extensive processing e.g. at severe process conditions and / or in multiple steps to upgrade them to lower boiling products having higher value. Exemplary upgrading processes include those using plurality of ebullated bed reactors, for example as arranged in US2021371762 Figures 2C and 2D.

[0080] Example 2. Test runs and yields of the product fractions

[0081] For the test runs, a pilot system comprising two consecutive ebullated bed reactors in the first hydroconversion stage and one ebullated bed reactor in the second hydroconversion stage was utilised. The pilot system was equipped with an interstage separation (ISS) arranged between the first and the second hydroconversion stage (between the second and the last reactor, similarly as shown in US2021371762 Figure 2D) to flash away a volatiles fraction, providing a non-volatiles fraction which continued to the second hydroconversion stage. The reactors were arranged with a sulphided non-noble metal hydrotreatment catalyst (NiMo on alumina) suitable for use in ebullated beds. Unlike in commercial scale ebullated bed systems, for simplicity the catalyst was not renewed in the pilot systems. This may have had a somewhat negative influence on the results, e.g. lesser conversion of more persistent species due to the reduced catalyst activity towards the end of the test runs. Consequently, the advantages observed in these pilot test runs are even more significant. The test runs were conducted at stable conditions with a target resid conversion of about 75 wt%. The temperature in each reactor was about 410°C, and pressure about 165 bar. DAO feed prepared in Example 1 was used as the petroleum feed and fed to the first reactor at a rate of 100 g / h. Hydrogen was fed at a rate of 88 l / l of feed per hour split into the three reactors in a volume ratio of about 40:20:40. In the test runs according to the present disclosure, LWP feed as prepared in Example 1 was co-fed to the second hydroconversion stage (third reactor) together with the non-volatile fraction of the first hydroconversion stage effluent in an LWP amount of 15 wt.-%, which equalled to 20 wt.-% of LWP feed 1 and 15 wt.-% of LWP feeds 2 and 3, based on the weight of the feed to the first hydroconversion stage.

[0082] The test runs used a separation stage comprising a gas-liquid separator and batch distillation to recover a gaseous overhead, naphtha (targeted boiling point range: IBP- 200°C) and diesel range (targeted boiling point range: 200-360°C) fractions, whereafter the bottom of the batch distillation was further distilled continuously in a short path evaporator (SPE) to recover light vacuum gas oil (LVGO, targeted boiling point range: 360-480°C), heavy vacuum gas oil (HVGO, targeted boiling point range: 480-560°C) and heavy vacuum tower bottom (heavy VTB, targeted boiling point range: 560°C+) fractions. The liquid product fraction yields (naphtha, diesel, LVGO, HVGO and heavy VTB) of the reference test runs and test runs according to the present process are reported in Table 3.

[0083] As there is no direct way to measure the LWP content in the obtained product fractions, simulations were made based on the boiling point distribution (ASTM D2887-2023) of the products (3-day average): the value obtained with DAO was subtracted from the respective value obtained with DAO+LWP feed, according to DAO’s share in the feed. The obtained yield structures are reported in Table 3.

[0084] Table 3. Liquid product fractions from the reference test run and from the test runs according to the present process, as well as simulated amounts of DAO-originating and LWP feed originating material in the product fractions (reported in parenthesis). DAO1-3 refer to results obtained from three different test runs using the DAO feed prepared in Example 1.

[0085] *: the simulation result was slightly negative for LWP feed 3 in the fractions boiling above 480 °C, demonstrating uncertainties of the simulation.

[0086] In Table 3, the combined yields of liquid product fractions from naphtha to VTB fraction were about 80-84 wt.-%, the balance being gaseous overhead separated from the second hydroconversion stage effluent (not reported in Table 3).

[0087] In the first hydroconversion stage, the heaviest (HVGO and VTB range) hydrocarbons of the petroleum feed are reduced significantly, while naphtha, diesel range and LVGO range hydrocarbons are being formed (results after 1st hydroconversion stage not reported in table 3). However, the second hydroconversion stage is still required to reduce the heaviest hydrocarbons further, and to increase naphtha, diesel and LVGO range hydrocarbons further. At the same time in the first and the second hydroconversion stage metals are captured by the catalyst and heteroatoms cleaved.

[0088] Regarding the present process, Table 3 shows that co-feeding 15 wt.-% LWP to the second hydroconversion stage increased the combined yield of naphtha, diesel range and LVGO fractions by 13-17% when co-processing with DAO, compared to the corresponding reference test run with DAO alone. The yield of the most valuable hydrocarbons, namely diesel range fraction, increased by over 10% with LWP feed 1 and over 20% with LWP feeds 2 and 3, and also naphtha fraction increased by 55-58%, compared to the corresponding reference test run with DAO alone. The increase in the light distillates yield is surprisingly high, given that the LWP feeds were co-fed only to the second hydroconversion stage. In this way overcracking of the LWP feed to less valuable gaseous hydrocarbons can be reduced. The test run results revealed also a significant decrease in the combined yield of less valuable heavy hydrocarbons, namely heavy VGO and VTB fractions, compared to the corresponding reference test run with DAO.

[0089] Example 3. Certain properties of the naphtha range, diesel range and LVGO fractions recovered from the test runs

[0090] In the following are reported certain properties analysed from the naphtha range, diesel range, and LVGO fractions recovered from the test runs reported in Example 2.

[0091] The naphtha fractions obtained by co-feeding LWP had elevated T5 temperatures (5 wt.-% recovered by ASTM D7096-2019), densities and paraffins content, compared to the reference naphtha obtained by an otherwise similar process but using 100% DAO as the feed. Contents of heterocompounds were below detection limit (<0.01 wt.-%) in all naphtha fractions. The higher paraffins content is desired especially for use in steam cracking feeds. Certain properties of the recovered naphtha range fractions are reported in Table 4.

[0092] Table 4. Certain properties of the recovered naphtha range fractions (<200°C). The contents of paraffins, heterocompounds and aromatics were determined by GC-FID / GC- MS.

[0093] The diesel range fractions obtained by co-feeding LWP had similar boiling properties, reduced densities and contents of aromatics and heterocompounds (especially N- containing), and increased n-paraffins content, compared to the reference diesel range fraction obtained by an otherwise similar process but using 100% DAO as the feed. Cofeeding LWP led to poorer cloud points, due to the higher n-paraffins content. However, the elevated paraffins content will have a positive effect on cetane number in the diesel range fraction(s). Additionally, when the obtained diesel range fraction(s) is / are further processed in catalytic conversion step(s), particularly in catalytic hydroprocessing step(s), the observed changes in the diesel range fraction will have a positive effect in such catalytic conversion, as the reduced heteroatom content poses reduced load on the catalyst and hence slower catalyst deactivation. Furthermore, when processed in catalytic hydroprocessing step(s), particularly in catalytic fixed-bed hydroprocessing step(s) such as hydrotreatment, hydrocracking, hydroisomerisation, and / or hydrodearomatisation, the paraffins content causes less coking and plugging, compared to cyclic hydrocarbons, and is also helpful for reaching lower levels of aromatics upon hydrodearomatisation. Increased paraffins and reduced aromatics contents is also desired for use in steam cracking feeds.

[0094] Certain properties of the recovered diesel range fractions are reported in Table 5.

[0095] Table 5. Certain properties of the recovered diesel range fractions (200-360 °C).

[0096] Also the LVGO fractions obtained by co-feeding LWP had similar boiling properties, reduced densities and contents of aromatics and heterocompounds, compared to the reference LVGO fraction obtained by an otherwise similar process but using 100% DAO as the feed. S and N compounds are more abundant in the LVGO boiling range than in diesel range. Surprisingly, co-feeding LWP causes a decrease in the S content of the LVGO fraction, that is larger than the dilution effect of the LWP feed, even though the residence time for the DAO in the last reactor is shortened by the LWP feed addition. At the same time the content of N compounds, that are one of the biggest impurities in the LVGO fraction, decreases substantially by the dilution brought by the co-fed LWP feed.

[0097] When the obtained LVGO fraction(s) is / are further processed in catalytic conversion step(s), the observed changes in the LVGO fraction, the reduced heteroatom content, particularly N content, and elevated paraffins content will have a positive effect in such catalytic conversion, as discussed in the foregoing in connection with the diesel range fraction(s). Certain properties of the recovered LVGO fractions are reported in Table 6.

[0098] Table 6. Certain properties of the recovered LVGO fractions (360-480 °C).

[0099] Example 4. Certain properties of the HVGO and heavy VTB fractions recovered from the test runs and their suitability for use in marine fuels

[0100] Certain properties of the HVGO and heavy VTB fractions were analysed and compared with ISO 8217:2024 (Table 2) specification requirements for residual marine fuels. The results are reported in Tables 7 and 8, below.

[0101] Table 7. Certain properties of the HVGO fractions obtained from the test runs without and with LWP feed, and certain ISO 8217:2024 (Table 2) specification requirements for residual marine fuel.

[0102] Statutory requirement set by IMO (International Maritime Organisation)

[0103] As can be seen from Table 7, co-feeding LWP led to reduced sulfur contents in the HVGO fractions (by 8-35%), even though the residence time for the DAO in the last reactor is shortened by the LWP feed addition. This is highly desired for use in marine fuels, as in the marine fuel market, a premium is paid for reduced sulfur content. Another substantial finding is the decrease in density. With the addition of LWP to the feed, the HVGO density is decreased by up to ~15 kg / m3 despite cut points being rather similar. This decrease in density can be seen as a benefit for the use of the HVGO fractions in marine fuels, because marine fuels are often limited by density. A lower density will allow more asphaltenes e.g. from the SDA unit to be blended into the marine fuel, further increasing the profitability of the product. The cetane index of the fraction also improves when co-processing LWP feed. This is likely due to the increased paraffinicity, and can be seen as a benefit to the use of the fuel due to improved ignition and combustion behavior.

[0104] Table 8. Certain properties of the heavy VTB fractions obtained from the test runs without and with LWP feed, and certain ISO 8217:2024 (Table 2) specification requirements for residual marine fuel.

[0105] Statutory requirement set by IMO (International Maritime Organisation); NA: not analysed

[0106] As can be seen from Table 7, co-feeding LWP led to reduced sulphur contents also in the VTB fractions (by 10-20%), even though the residence time for the DAO in the last reactor is shortened by the LWP feed addition. This is highly desired for use in marine fuels, as in the marine fuel market, a premium is paid for reduced sulphur content. Another substantial finding is the decrease in density, allowing more asphaltenes e.g. from the SDA unit to be blended into the marine fuel, further increasing the profitability of the product. Also nitrogen content is seen to decrease.

[0107] Next, sediments and aged sediments of blend compositions were determined. For these tests, 70 wt-% of a vacuum tower bottom (VTB) fraction obtained with the present process was mixed with 30 wt -% of conventional petroleum-based FCC gas oil. The VTB originated from a test run using the earlier described pilot system fed with a 50:50 blend of DAO and crude oil vacuum residue (VR) as the petroleum feed, LWP feed 1 co-fed to give LWP level of 15 wt.-% after the interstage separation section to the second hydroconversion stage (3rd reactor). For reference tests similar blend of 70 wt.-% of an otherwise similar VTB but obtained from a process fed with 100% 50:50 DAO:VR blend, and 30 wt.-% of FCC gas oil was prepared. The sediment tests were performed according to ISO10307-1 :2009, and the aged sediment tests were performed according to ISO10307-2:2009 A. No increase in the sediment levels was observed in the blend containing the VTB fraction obtained according to the present process, compared to the reference blend. To the contrary, both the blend sediment and the blend aged sediment results were halved when using the blend containing the VTB fraction obtained according to the present process. This is a further confirmation that even a crude i.e. non-hydrotreated LWP feed, despite of containing compounds prone to react and possibly induce asphaltenes-formation, does not need to be co-fed to a resid hydroconversion process from the very beginning together with the heavy petroleum feed, but can successfully be co-fed to a later stage in the process without a risk of sediment formation in the heavy fractions.

[0108] Various embodiments have been presented. It should be appreciated that in this document, words comprise, include and contain are each used as open-ended expressions with no intended exclusivity.

[0109] The foregoing description has provided by way of non-limiting examples of particular implementations and embodiments of the invention a full and informative description of the best mode presently contemplated by the inventors for carrying out the invention. It is however clear to a person skilled in the art that the invention is not restricted to details of the embodiments presented in the foregoing, but that it can be implemented in other embodiments using equivalent means or in different combinations of embodiments without deviating from the characteristics of the invention.

[0110] Furthermore, some of the features of the afore-disclosed embodiments of this invention may be used to advantage without the corresponding use of other features. As such, the foregoing description shall be considered as merely illustrative of the principles of the present invention, and not in limitation thereof. Hence, the scope of the invention is only restricted by the appended patent claims.

Claims

CLAIMS1 . A process for producing hydrocarbon fractions, the process comprising: a) providing a liquefied waste polymer (LWP) feed; b) providing a petroleum feed containing at least 10 wt.-%, preferably at least 30 wt.-%, more preferably at least 50 wt.-%, of hydrocarbons boiling above 480°C (EN 15199-2:2020), based on the total petroleum feed weight; c) subjecting the petroleum feed to hydroconversion in the presence of a hydrotreatment catalyst in a first hydroconversion stage comprising one or more hydroconversion zone(s) to obtain a first hydroconversion stage effluent; d) subjecting at least a portion of the first hydroconversion stage effluent and the liquefied waste polymer feed to hydroconversion in the presence of a hydrotreatment catalyst in a second hydroconversion stage comprising one or more hydroconversion zone(s) to obtain a second hydroconversion stage effluent; and e) feeding the second hydroconversion stage effluent to a separation stage and recovering from the separation stage at least one or more heavy fraction(s) having T10 temperature (10 wt.-% recovered, EN 15199-2:2020) of at least 350°C, preferably at least 380°C, more preferably at least 420°C, and one or more lighter fraction(s).

2. The process according to claim 1 , wherein in step d) the second hydroconversion stage comprises at least one hydroconversion zone containing the hydrotreatment catalyst arranged in a moving catalyst bed, wherein the moving catalyst bed is preferably an ebullated bed.

3. The process according to claim 1 or 2, wherein in step c) the first hydroconversion stage comprises at least one hydroconversion zone containing the hydrotreatment catalyst arranged in a moving catalyst bed, preferably at least two hydroconversion zones in series each containing the hydrotreatment catalyst arranged in a moving catalyst bed, wherein the moving catalyst bed is preferably an ebullated bed.

4. The process according to any one of the preceding claims, wherein the hydrotreatment catalyst in step c) and / or step d) includes one or more hydrotreatment catalysts selected independently for each hydroconversion zone from sulfided hydrotreatment catalysts comprising at least one or more metals from Group VIII of the Periodic Table and / or from Group VI B of the Periodic Table, preferably at least one or moreof Ni, Mo, W, and / or Co, even more preferably at least one or more of Ni and / or Co and Mo and / or W, such as NiMo, CoMo, NiCoMo, NiW, and / or NiMoW, preferably on a support such as alumina and / or silica.

5. The process according to any one of the preceding claims, wherein each hydroconversion zone in step c) and step d) is operated at a temperature (as determined at the zone inlet), selected independently from each other, within a range from 350 °C to 480 °C, preferably from 370 °C to 460 °C, and / or at a pressure (as determined at the zone outlet), selected independently from each other, within a range from 8 MPa to 20 MPa, preferably from 10 MPa to 20 MPa.

6. The process according to any one of the preceding claims, wherein the petroleum feed comprises a heavy petroleum feed component in an amount of at least 25 wt.-%, preferably at least 50 wt.-%, more preferably at least 75 wt.-%, even more preferably the petroleum feed consists essentially of a heavy petroleum feed component, wherein the heavy petroleum feed component preferably comprises at least 50 wt.-%, preferably at least 60 wt.-%, more preferably at least 70 wt.-% of compounds boiling above 565°C (EN 15199- 2:2020), based on the heavy petroleum feed component weight, and / or has a density at 15°C within a range from 900 kg / m3 to 1150 kg / m3 (EN ISO 12185-1996), preferably within a range from 920 kg / m3 to 1100 kg / m3, more preferably within a range from 950 kg / m3 to 1050 kg / m3, and / or has a viscosity at 135°C within a range from 20 mm2 / s to 200 mm2 / s (EN 12595-2023), preferably within a range from 40 mm2 / s to 180 mm2 / s, more preferably within a range from 50 mm2 / s to 160 mm2 / s.

7. The process according to claim 6, wherein the heavy petroleum feed component comprises distillation residue(s) and / or crude oil heavy vacuum distillate(s), preferably as solvent deasphalted (SDA).

8. The process according to any one of the preceding claims, wherein providing the liquefied waste polymer feed in step a) includes depolymerizing waste polymer by pyrolysis to provide waste polymer pyrolysis oil and / or by hydrothermal liquefaction to provide waste polymer hydrothermal liquefaction oil, wherein the waste polymer preferably comprises at least mixed waste plastics and / or end of life tires (ELT).

9. The process according to any one of the preceding claims, wherein the liquefied waste polymer feed provided in step a):- comprises at least 5 wt.-%, preferably at least 10 wt.-%, more preferably at least 20 wt.- % of compounds boiling above 360°C (ASTM D2887-2023), based on the total LWP feed weight; and / or- comprises at least 1 wt.-%, preferably at least 3 wt.-%, more preferably at least 5 wt.-% of compounds boiling above 480°C (ASTM D2887-2023), based on the total LWP feed weight; and / or- has a T10 temperature (10 wt-% recovered, ASTM D2887-2023) at least 150°C, preferably at least 180°C, more preferably at least 200°C; and / or- has a Bromine number more than 1 g Br / 100g of the LWP feed, preferably more than 5 g Br / 100g, more preferably more than 30 g Br / 100g feed (ISO 3839-1996).

10. The process according to any one of the preceding claims, wherein in step d) the liquefied waste polymer feed and the at least a portion of the first hydroconversion stage effluent are fed to the second hydroconversion stage within a weight-ratio of the liquefied waste polymer feed to the at least a portion of the first hydroconversion stage effluent from 1 :99 to 80:20, preferably from 5:95 to 50:50, more preferably from 10:90 to 30:70.

11. The process according to any one of the preceding claims, wherein the first hydroconversion stage effluent obtained in step c) is subjected to an interstage separation to obtain a volatiles fraction and a non-volatiles fraction, and the non-volatiles fraction is fed to the second hydroconversion stage in step d); and preferably at least a portion of the volatiles fraction is fed with the second hydroconversion stage effluent to the separation stage in step e) and / or at least a portion of the volatiles fraction is fed to one or more further conversion step(s), preferably to one or more catalytic conversion step(s), more preferably to one or more catalytic hydroprocessing step(s).

12. The process according to claim 11 , wherein the volatiles fraction comprises at least compounds boiling below 300 °C at atmospheric pressure, and the non-volatiles fraction comprises at least compounds boiling above 300 °C at atmospheric pressure.

13. The process according to any one of the preceding claims, wherein the process further comprises f) subjecting at least a portion of the lighter fraction(s) recovered in step e) to one or more further conversion step(s), preferably to one or more catalytic conversion step(s), more preferably to one or more catalytic hydroprocessing step(s), even morepreferably to one or more catalytic fixed-bed hydroprocessing step(s) selected from hydrotreatment, hydrocracking, hydroisomerisation, and / or hydrodearomatisation.

14. The process according to any one of the preceding claims, wherein the one or more lighter fraction(s) recovered in step e)- have T90 temperature (90 wt.-% recovered, ASTM D2887-2023) less than 500°C, preferably less than 480°C; and / or- include one or more middle fraction(s) having T10 and T90 temperatures (10 wt.-% and 90 wt.-% recovered, respectively, ASTM D2887-2023) within a range from 50°C to 430°C, preferably from 140°C to 420°C; and / or- include one or more naphtha fraction(s) having T90 temperature (90 wt.-% recovered, ASTM D7096-2019) of at most 200°C, one or more middle distillate fraction(s) having T10 and T90 temperatures (10 wt.-% and 90 wt.-% recovered, respectively, ASTM D2887-2023) within a range from 140°C to 420°C, and optionally one or more vacuum gas oil fraction(s) having T10 temperature (10 wt.-% recovered, ASTM D2887-2023) of at least 330°C.

15. The process according to any one of the preceding claims, wherein the one or more heavy fraction(s) recovered in step e) include an atmospheric distillate, a vacuum distillate, an atmospheric bottom and / or a vacuum tower bottom, preferably at least a vacuum distillate and / or a vacuum tower bottom, having T10 temperature (10 wt.-% recovered, EN 15199-2:2020) within a range from 350°C to 530°C, preferably from 380°C to 510°C, more preferably from 420°C to 510°C, and / or T10 and T50 temperatures (10 wt.-% and 50 wt.-% recovered, respectively, EN 15199-2:2020) within a range from 350°C to 670°C, preferably from 380°C to 650°C, more preferably from 420°C to 650°C.

16. The process according to any one of the preceding claims, wherein the one or more heavy fraction(s) recovered in step e) has / have one or more of the following:- a density at 15°C within a range from 850 to 1060 kg / m3, preferably from 900 to 1000 kg / m3 (EN ISO 12185-1996); and / or- a viscosity at 80°C at least 30 mm2 / s, preferably at least 40 mm2 / s, more preferably at least 50 mm2 / s (EN 12595-2023), and a viscosity at 135°C at most 170 mm2 / s; and / or- a total content of sulphur less than 1.0 wt.-%, preferably less than 0.6 wt.-%, more preferably less than 0.3 wt.-% (ASTM D7039-15a(2020)).

17. Use of a heavy fraction selected from an atmospheric distillate, a vacuum distillate, an atmospheric bottom and a vacuum tower bottom, preferably a vacuum distillate or a vacuum tower bottom, obtainable by the process according to any one of claims 1-16, as a blend component in a marine fuel, especially in a residual marine fuel meeting one or more characteristics laid down in ISO 8217:2024 Table 2, preferably in an amount of 1 vol-% to 90 vol-%, more preferably 1 vol-% to 80 vol-%, based on the marine fuel volume.

18. Use according to claim 17, wherein the heavy fraction, preferably a vacuum distillate, has T10 temperature (10 wt.-% recovered, EN 15199-2:2020) within a range from 420°C to 500°C and preferably T10 and T90 temperatures (10 wt.-% and 90 wt.-% recovered, respectively, EN 15199-2:2020) within a range from 420°C to 580°C, or wherein the heavy fraction, preferably an atmospheric bottom or a vacuum tower bottom, has T10 temperature (10 wt.-% recovered, EN 15199-2:2020) of at least 500°C, preferably within a range from 500°C to 600°C.

Images