Process for producing a hydrocarbon fraction with a sustainable content and a hydrocarbon fraction obtainable by said process

Abstract

A method for producing hydrocarbon fractions with sustainable content is provided. In this method, a hydrotreating feed having petroleum content and renewable and / or recycled content is hydrotreated to obtain a hydrotreated effluent, which is then fed to a separation section from which at least three different distillates and separation section bottoms are recovered. Residual marine fuel components are further recovered from the separation section bottoms. A hydrocracking feed containing a portion of the separation section bottoms is then hydrocracking to obtain a hydrocracking effluent, which is co-fed with the hydrotreating effluent to the separation section.

Description

Technical Field

[0001] This disclosure generally relates to methods for producing hydrocarbon fractions with sustainable content. This disclosure particularly, but not exclusively, relates to methods for producing at least three different distillates, as well as the bottoms of a separation section. This disclosure also relates to naphtha fractions, aviation fuel range fractions, light gas oil fractions, intermediate gas oil fractions, heavy gas oil fractions, and residual marine fuel components, preferably obtainable by the methods of this disclosure. Background Technology

[0002] This section provides useful background information, but does not acknowledge that any techniques described herein represent prior art.

[0003] There is a persistent need to reduce greenhouse gas (GHG) emissions and / or carbon footprint in the transportation and petrochemical industries. Consequently, there is growing interest in sustainable materials that can be used in these sectors.

[0004] Various methods have been proposed for the production of sustainable materials. First-generation biofuels, such as biodiesel (FAME) and bioethanol, are typically based on energy crops, limiting their environmental benefits in terms of GHG emissions. Incompatibility issues when blended with fossil materials and in combustion systems are also a concern. The reported drawbacks of FAME, such as high viscosity, low energy content, high oxygen and water content, and poor cold properties such as a poor cloud point and pour point, impose technical limitations on its usability and also hinder its use as aviation fuel.

[0005] Due to the drawbacks of first-generation biofuels, alternative biofuel technologies are being explored, including concepts specifically designed for processing non-petroleum feedstocks and co-processing concepts. For example, there is increasing interest in co-processing biomass-derived streams in existing refineries, largely because existing infrastructure allows for immediate implementation and lower investment costs. One of the most studied technologies for co-processing is fluid catalytic cracking (FCC), a widely used method in refineries for converting heavy fractions of crude oil into gasoline and propylene as key products. However, this technology is not well-suited for producing higher-value products, such as fractions that can be used for jet fuel. Furthermore, the catalyst regeneration inherent in FCC units involves high CO2 emissions, sometimes accounting for 25-35% of total CO2 emissions in conventional refineries. Summary of the Invention

[0006] The aim is to address or mitigate at least some of the problems associated with existing technologies, including reducing GHG emissions and dependence on petroleum resources, particularly in the transportation and petrochemical sectors. Another aim is to provide methods with improved overall economics. A further aim is to provide methods for producing a product composition with higher total value and improved flexibility for recyclable products. A further aim is to improve the yield of fractions with sustainable (i.e., renewable and / or recyclable) content.

[0007] The appended claims define the scope of protection. Any embodiments and technical descriptions of products, methods, and / or uses not covered by the claims in the specification and / or drawings are presented as examples for understanding the invention.

[0008] According to the first example, a method for producing hydrocarbon fractions is provided, the method comprising: a) In a pre-hydroconversion reactor, in the presence of a pre-hydroconversion catalyst, at least one or more of vegetable oils, animal fats, microbial oils, lignocellulose-derived biocrude oils, and / or liquefied organic waste are pre-hydroconverted to obtain a pre-hydroconversion effluent, and a petroleum feed is co-fed into the pre-hydroconversion reactor, and / or the petroleum feed is combined with at least a portion of the pre-hydroconversion effluent to obtain a hydrotreated feed having petroleum content and renewable and / or recyclable content. b) Hydrotreating the feedstock in the presence of a hydrotreating catalyst in a hydrotreating reactor to obtain a hydrotreating effluent. c) Introducing at least a portion of the hydrotreated effluent into a separation section and recovering at least three different distillates and a separation section bottoms product from the separation section, the bottoms product having an initial boiling point of at least 300°C, such as in the range of 300°C to 420°C, preferably at least 320°C, such as in the range of 320°C to 410°C, more preferably at least 340°C, such as in the range of 340°C to 400°C (EN ISO 3405-2019). d) Recovering residual marine fuel components from the bottom of the separation section, preferably by separating a portion of the bottom of the separation section. e) In a hydrocracking reactor, in the presence of a hydrocracking catalyst, a hydrocracking feed containing a portion of the bottom product of the separation section is hydrocracking to obtain a hydrocracking effluent, and at least a portion of the hydrocracking effluent and the hydrotreated effluent are co-fed into the separation section.

[0009] The inventors have discovered that the method and its implementations of the present invention offer certain advantages compared to existing methods that co-process petroleum feedstocks and sustainable (i.e., renewable and / or cyclic) feedstocks. These advantages involve, for example, reduced GHG emissions and reduced dependence on dwindling petroleum resources (particularly in transportation and in the petrochemical sector), as well as improved overall economics of the method, improved flexibility regarding available feedstocks and products, and a higher overall value in product composition. Further advantages involve improved yields of fractions with sustainable (i.e., renewable and / or cyclic) content. The pre-hydrogenation conversion may include pre-hydrogenation treatment and / or pre-hydrocracking, thus involving at least partial cracking of the carbon skeleton of molecules in vegetable oils, animal fats, microbial oils, lignocellulose-derived biocrude oils, and / or liquefied organic waste. This method processes the pre-hydroconversion effluent (including hydrotreating and hydrocracking steps) to further distribute the renewable and / or recyclable content over a wider boiling point range, allowing virtually all fractions recovered from the separation section to have, and even significantly, renewable and / or recyclable content. Because the process steps can be carried out at high hydrogen pressures, the presence and formation of olefins are minimized, resulting in product fractions with good stability. Further benefits of this method include virtually no limitation on the amount of renewable and / or recyclable content that can be incorporated into the hydrotreating feed, from the perspective of mitigating the exothermic reaction of the hydrotreating reactor and / or reducing the risk of corrosion, as pre-hydroconversion effectively reduces the content of heteroatoms and other impurities, and thus reduces acidity, which can cause corrosion problems. In this way, even highly challenging renewable and / or recyclable feedstocks can be introduced into conventional refinery units after pre-hydroconversion.

[0010] The aforementioned advantages can be achieved at reduced costs, particularly when utilizing existing refinery assets. This method is well-suited for operation in conventional or existing refinery units. The pre-hydroconversion reactor alone may require a higher metallurgical grade than typical refinery units. Therefore, in some preferred embodiments, at least one or more, preferably at least two or more, more preferably at least three or more, of the hydrotreatment reactor, hydrotreatment catalyst, separation section, hydrocracking reactor, and / or hydrocracking catalyst are configured as initially for processing petroleum feedstock.

[0011] When needed, the pre-hydroconversion effluent can be fed into a pre-hydroconversion fractionation to recover at least one or more pre-hydroconversion distillates and pre-hydroconversion fractionation bottoms, such that only a portion of the pre-hydroconversion effluent, preferably the pre-hydroconversion fractionation bottoms, is incorporated into the hydrotreatment feed. These implementations involve the additional benefit of directing other fractions recovered from the pre-hydroconversion fractionation to other value-added uses or methods. Optimal use and value-added of recyclable and / or recyclable content can be achieved by appropriately selecting the cut-off point in the pre-hydroconversion fractionation.

[0012] Therefore, in some preferred embodiments, step a) includes: feeding the pre-hydroconversion effluent to a pre-hydroconversion fractionation to recover one or more pre-hydroconversion distillates and pre-hydroconversion fractionation bottoms, and combining the petroleum feed with the pre-hydroconversion fractionation bottoms to obtain the hydrotreating feed; the method further includes: f) Feeding the one or more pre-hydrogenated conversion distillates to a catalytic conversion, preferably to a catalytic conversion including at least hydroisomerization, more preferably to a catalytic conversion including at least hydrotreatment and hydroisomerization, optionally co-feeding with at least one or more of vegetable oils, animal fats, microbial oils, lignocellulose-derived biocrude oils and / or liquefied organic waste to obtain catalytic conversion effluent; and g) Optionally, at least aviation fuel components and / or diesel fuel components are recovered from the catalytic conversion effluent. These embodiments involve the additional benefit that the conversion effluent may consist substantially of renewable and / or cyclic hydrocarbons, and aviation and / or diesel fuel components with extremely high isomerization and excellent cold properties can be obtained.

[0013] According to the second example aspect, a naphtha fraction is provided having a boiling point range of 1 BP to 230°C, preferably 20°C to 220°C (ASTM D7096-2019), and optionally, the difference between T90 and T10 temperatures is in the range of 30°C to 150°C, preferably 50°C to 120°C (ASTM D7096-2019), and optionally, based on the total weight (TC) of carbon in the fraction, the biogenic carbon content is in the range of 1 to 50 wt.-%, preferably 3 to 40 wt.-%, (EN 16640:2017), wherein the naphtha fraction has at least one or more additional properties defined in the embodiments of the first example aspect, and is preferably obtainable by the method according to the first example aspect.

[0014] According to the third example aspect, an aviation fuel boiling range fraction is provided having a boiling point range of 120°C to 310°C, preferably 130°C to 300°C (EN ISO 3405-2019), a difference between T90 and T10 temperatures in the range of 40°C to 200°C, preferably 60°C to 180°C (EN ISO 3405-2019), and optionally, based on the total weight (TC) of carbon in the fraction, a bio-based carbon content in the range of 5 to 50 wt.-%, preferably 10 to 40 wt.-%, (EN 16640:2017), wherein the aviation fuel boiling range fraction has at least one or more additional properties as defined in the embodiments of the first example aspect, and is preferably obtainable by the method according to the first example aspect.

[0015] According to the fourth example aspect, a light gas oil fraction is provided having a boiling point range of 120°C to 330°C, preferably 130°C to 320°C (EN ISO 3405-2019), a temperature difference between T90 and T10 of 50°C to 200°C, preferably 80°C to 190°C (EN ISO 3405-2019), and optionally, a biogenic carbon content of 5 to 60 wt.-%, preferably 10 to 40 wt.-%, based on the total weight (TC) of carbon in the fraction (EN 16640:2017), wherein the light gas oil fraction has at least one or more additional properties as defined in the embodiments of the first example aspect, and is preferably obtainable by the method according to the first example aspect.

[0016] According to the fifth example aspect, an intermediate gas oil fraction is provided having a boiling point range of 190°C to 390°C, preferably 200°C to 380°C (EN ISO 3405-2019), a temperature difference between T90 and T10 of 50°C to 200°C, preferably 80°C to 200°C (EN ISO 3405-2019), and optionally, a biogenic carbon content of 5 to 80 wt.-%, preferably 10 to 70 wt.-%, based on the total weight (TC) of carbon in the fraction (EN 16640:2017), wherein the intermediate gas oil fraction has at least one or more additional properties as defined in the embodiments of the first example aspect, and is preferably obtainable by the method according to the first example aspect.

[0017] According to the sixth example aspect, a heavy gas oil fraction is provided having a boiling point range of 270°C to 430°C, preferably 280°C to 410°C (EN ISO 3405-2019), a temperature difference between T90 and T10 of 5°C to 140°C, preferably 10°C to 100°C (EN ISO 3405-2019), and optionally, a biogenic carbon content of 5 to 80 wt.-%, preferably 10 to 70 wt.-%, based on the total weight (TC) of carbon in the fraction (EN 16640:2017), wherein the heavy gas oil fraction has at least one or more additional properties defined in the embodiments of the first example aspect, and is preferably obtainable by the method according to the first example aspect.

[0018] According to the seventh example aspect, a residual marine fuel component is provided having an initial boiling point of at least 300°C, such as in the range of 300°C to 420°C, preferably at least 320°C, such as in the range of 320°C to 410°C, more preferably at least 340°C, such as in the range of 340°C to 400°C (EN ISO 3405-2019), and optionally, based on the total weight (TC) of carbon in the fraction, a bio-based carbon content in the range of 5 to 50 wt.-%, preferably 8 to 40 wt.-%, (EN 16640:2017), wherein the residual marine fuel component has at least one or more additional properties defined in the embodiments of the first example aspect, and is preferably obtainable by the method according to the first example aspect.

[0019] The foregoing has described various non-binding aspects and implementations. The foregoing implementations are merely illustrative of selected aspects or steps that may be used in different implementations. Some implementations may be presented with reference only to certain aspect examples. It should be understood that corresponding implementations may also be applicable to other aspect examples. Attached Figure Description

[0020] Some exemplary embodiments will be described with reference to the accompanying drawings, in which: Figure 1 An exemplary embodiment of the method is illustrated schematically. Detailed Implementation

[0021] In the following description, the same reference numerals denote the same elements or steps. Unless otherwise indicated, all standards mentioned herein are the most recent revisions available as of the submission date.

[0022] Unless otherwise specified, for distillation characteristics such as initial boiling point (IBP), final boiling point (FBP), T10 temperature (10 vol-% recovery), T90 temperature (90 vol-% recovery), and boiling point range (from IBP to FBP, unless otherwise specified), refer to EN ISO 3405-2019. IBP is the temperature at the instant the first drop of condensate falls from the bottom of the condenser, and FBP is the maximum thermometer reading obtained during the test, typically occurring after all liquid has evaporated from the bottom of the flask. For boiling point distribution, also refer to the GC-based method (simulated distillation) ASTM D2887-19e1, or for hydrocarbons in the gasoline range, refer to ASTM D7096-19.

[0023] As used in this disclosure, an aviation fuel boiling range fraction or pool (blending pool, blending component) refers to a hydrocarbon composition suitable (at least as a blending component) for use in fuels that meet aviation fuel standard specifications, such as those specified in ASTM D1655-2023. Typically, such an aviation fuel boiling range fraction has a boiling point (i.e., having both IBP and FBP) in the range of about 120°C to about 310°C, preferably in the range of about 130°C to about 300°C, as determined according to EN ISO 3405-2019.

[0024] As used in the context of this disclosure, a diesel fuel range fraction or pool refers to a hydrocarbon composition suitable (at least as a blend component) for use in fuels that meet diesel fuel standard specifications, such as EN 590:2022 or EN 15940:2023. Typically, such a diesel fuel range fraction, as determined according to EN ISO 3405-2019, boils in the range of about 130°C to about 380°C, such as in the range of about 160°C to about 380°C. In this document, the diesel fuel range fraction or pool (or fuel) for temperate climates refers to a diesel fuel range fraction or pool (or fuel) that meets one or more of the cold filter clogging point (CFPP) requirements set forth in Table 2 of EN 590:2022, and in this document, the diesel fuel range fraction or pool (or fuel) for cold and / or winter climates refers to a diesel fuel range fraction or pool (or fuel) that meets one or more of the CFPP requirements and / or cloud point (CP) requirements set forth in Table 3 of EN 590:2022 for diesel fuels in cold and severe winter climates.

[0025] As used in the context of this disclosure, a gasoline fuel range fraction or pool, or naphtha fraction, refers to a hydrocarbon composition suitable (as is or after stabilization) for use as at least as a blend component in fuels that meet standard gasoline fuel specifications (such as those specified in EN 228:2012 + A1:2017). Typically, stabilized, such a gasoline fuel range or naphtha fraction, as determined according to EN ISO 3405-2019, has a boiling range (i.e., having IBP and FBP) in the range of about 20°C to about 220°C, preferably about 25°C to about 210°C. Hereinafter, a light naphtha fraction refers to a fraction containing C4 or heavier components and having an FBP of up to about 180°C, which typically requires stabilization before use in gasoline fuels.

[0026] As used in the context of this disclosure, a marine fuel range fraction or component refers to a hydrocarbon composition suitable for use in fuels that meet standard marine fuel specifications (such as those specified in ISO 8217-2017) (at least as a blend component). Typically, such a marine fuel range fraction or component boils, i.e., has a boiling point at IBP and FBP, starting at about 180°C or higher, for example, in the range from about 180°C to about 600°C, as determined according to EN ISO 3405-2019. Marine fuel range components suitable for use in residual marine fuels (referred to herein as residual marine fuel components) may contain even very high-boiling compounds, and such marine fuel range components can be characterized by their kinematic viscosity (KV) at 50°C, instead of FBP. Suitable marine fuel composition for use as residual marine fuel, i.e., residual marine fuel composition, has a kinematic viscosity (KV) at 50°C, as determined according to EN ISO 3104-2020, for example, up to 750 mm² / s or up to 700 mm² / s. Therefore, hydrocarbons having IBP and KV at 50°C within these ranges can be considered suitable for use as marine fuel.

[0027] Regarding various fractionation methods and systems involving, for example, distillation, it should be understood that fractionation precision can vary, and in fact, even the boiling ranges (i.e., having IBP and FBP) of adjacent (consecutive) fractions recovered from the separation section may partially overlap. Typically, any adjacent fractions have different T50 temperatures (EN ISO 3405-2019). More specifically, the T60 temperature (EN ISO 3405-2019) of the fraction recovered from the separation section may be lower than the T40 temperature (EN ISO 3405-2019) of the adjacent higher-boiling fraction. Preferably, the T70 temperature (EN ISO 3405-2019) of the fraction recovered from the separation section may be lower than the T30 temperature (EN ISO 3405-2019) of the adjacent higher-boiling fraction.

[0028] As used herein, hydrocarbons refer to compounds composed of carbon and hydrogen, including alkanes, n-alkanes, isoalkanes, monobranched isoalkanes, polybranched isoalkanes, alkenes, cycloalkanes, and aromatics. In this context, oxygen-containing hydrocarbons refer to hydrocarbons containing covalently combined oxygen atoms.

[0029] As used herein, alkanes refer to acyclic alkanes, that is, linear (n-alkanes, n-chain alkanes) or branched (iso-alkanes, iso-chain alkanes) acyclic open-chain saturated hydrocarbons. In other words, in this document, alkanes refer to n-chain alkanes and / or iso-chain alkanes.

[0030] In the context of this disclosure, isoparaffins refer to branched noncycloalkanes having one or more alkyl side chains. Hereinafter, isoparaffins having one alkyl side chain or branch are referred to as monobranched isoparaffins, and isoparaffins having two or more alkyl side chains or branch are referred to as polybranched isoparaffins. In other words, isoparaffins as used herein refer to monobranched and / or polybranched isoparaffins. The alkyl side chains of isoparaffins may be, for example, C1-C9 alkyl side chains, preferably methyl side chains. The amounts of monobranched and polybranched isoparaffins may be given separately. The term "isoparaffin" refers to the total amount of any monobranched isoparaffin and any polybranched isoparaffin (if present), representing the total amount of any present isoparaffin regardless of the number of branches. Accordingly, "isoparaffin" refers to the total amount of any n-chain alkane, any monobranched and any polybranched isoparaffin (if present).

[0031] In the context of this 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.

[0032] As used herein, cyclic hydrocarbons refer to all hydrocarbons containing a cyclic structure, including cycloalkenes, cycloalkanes, and aromatics. Cycloalkanes, as used herein, refer to cyclic alkanes, i.e., saturated hydrocarbons containing at least one cyclic structure with or without side chains. Because cycloalkanes are saturated compounds, they are compounds lacking aromatic ring structures. Aromatic hydrocarbons, as used herein, refer to hydrocarbons containing at least one aromatic ring structure, i.e., a cyclic structure with delocalized, alternating π bonds throughout the circumference of the cyclic structure.

[0033] In the context of this disclosure, for compositions with a boiling point < 250°C (at standard atmospheric pressure), the content of n-alkanes, isoalkanes, monobranched isoalkanes, various multibranched isoalkanes, alkenes, cycloalkanes and aromatics is expressed as weight-% (wt-%) relative to the weight of the composition under discussion, or, when so defined, as weight-% (wt-%) relative to the (total) weight of alkanes or (total) weight of isoalkanes in the composition under discussion. The contents described herein can be determined by GC-FID / GC-MS methods, preferably as follows: GC-FID is performed using the following parameters as disclosed in ASTM D6839: column ZB-1 60m, ID 0.25mm, df 1.0 μm, or similar; column temperature program 0°C (2 min) - 1.5°C / min 300°C (5 min); inlet and detector 300°C; carrier gas helium 1.0 ml / min; detector gases H2 35 ml / min and air 350 ml / min; compensation gas helium flow rate 30 ml / min; split 165:1 (165 ml / min). Each compound is identified using GC-MS (operating parameters: ion source 230°C; inlet 280°C; scan 25-280 m / z; scan rate 303; scan event time 0.88). The detected compounds or hydrocarbon groups were identified using commercial tools (Shimadzu LabSolutions / GCMSSolutions and Agilent OpenLab), and their mass concentrations were determined by applying a response factor relative to n-heptane to the detection peak area, followed by normalization to 100 wt% (for liquid volume concentrations: a density factor was applied to the calculated detection peak concentration, followed by normalization to 100 vol%). Cycloalkenes were grouped together with cycloalkanes. The limit of quantitation for a single compound was 0.1 wt%.

[0034] Unless otherwise stated, in the context of this disclosure, for compositions with a boiling point of 36°C or higher at standard atmospheric pressure, the content of n-alkanes, isoalkanes, monobranched isoalkanes, polybranched isoalkanes, cycloalkanes, and aromatics is expressed as a weight percent (wt.-%) relative to the degassed weight of the composition under discussion, or, when so defined, as a weight percent (wt.-%) relative to the total weight of alkanes or isoalkanes in the composition under discussion. This content can be determined by GCxGC-FID / GCxGC-MS methods, preferably performed by running a GCxGC (2D GC) method, as commonly disclosed in the experimental section of UOP 990-2011 and Nousiainen M's master's thesis, *Comprehensive two-dimensional gas chromatography with mass spectroscopy and flame ionization detector in petroleum chemistry, University of Helsinki*, with the following modifications. The GCxGC was run in reverse-phase mode, using a semi-polar column (Rxi17Sil) followed by a non-polar column (Rxi5Sil), then through an FID detector, with the following operating parameters: carrier gas helium 31.7 cm / s (column flow rate 1.60 ml / min at 40°C); split ratio 1:350; injection port 280°C; column temperature program 40°C (0 min) - 5°C / min - 250°C (0 min) - 10°C / min - 300°C (5 min), run time 52 min; modulation period 10 s; detector 300°C, H2 40 ml / min and air 400 ml / min; makeup helium flow 30 ml / min; sampling rate 250 Hz, injection volume 0.2 μL. Compounds were identified using GCxGC-MS with the following MS parameters: ion source 230°C; interface 300°C; scan range 25–500 amu; event time (seconds) 0.05; scan rate 20,000. Data processing was performed using commercial tools (Shimadzu's LabSolutions, Zoex's GC Image), including the identification of detected compounds or hydrocarbon groups and their mass concentrations determined by applying a response factor relative to n-heptane to the detected peak volume, followed by normalization to 100 wt.-%. Alkenes were grouped together with cycloalkanes unless reported separately, and heteroatomic substances were grouped together with aromatics. The limit of quantitation for a single compound was 0.1 wt.-%.

[0035] In chemistry, the renewable or non-renewable source (such as petroleum) of any organic compound (including hydrocarbons) can be determined by methods used to analyze the carbon content from renewable sources, such as DIN 51637:2014-02, ASTM D6866-2022, or EN 16640:2017. These methods are based on the fact that renewable or biologically derived carbon atoms comprise a higher number of unstable radioactive carbon (14C) atoms compared to those from fossil sources. Therefore, carbon compounds derived from renewable or biological sources and those derived from non-renewable sources (such as petroleum) can be distinguished by analyzing the ratio of 12C to 14C isotopes. Thus, a specific ratio of these isotopes can be used as a “tag” to identify renewable carbon compounds and differentiate them from non-renewable ones. The isotopic ratio does not change during chemical reactions. Therefore, isotopic ratios can be used to identify renewable carbon compounds and distinguish them from non-renewable carbon compounds in feeds, (pre)hydrotreated feeds, co-feeds, fractions, or compositions or their various blends. Numerically, bio-based carbon content can be expressed as the percentage of bio-based carbon in a material relative to the total weight (TC) of carbon in the material (according to ASTM D6866-2022 or EN 16640:2017).

[0036] As used herein, the term "cycle" in relation to content or materials (such as (co)feed, fraction, or composition) refers to content or materials based on or containing reused and / or recycled non-biological carbon, but may additionally contain bio-based carbon. Typical exemplary sources of non-biological carbon used for reuse and / or recycling (which may also contain at least some bio-based carbon) include recycled organic commodities, particularly waste plastics, end-of-life tires, waste lubricants, and / or municipal solid waste.

[0037] Based on their origin and impact on environmental issues, renewable, circular, and petroleum-based materials, feedstocks, fractions, or compositions are considered distinct from each other. Therefore, they may be treated differently within a legislative and regulatory framework. Typically, renewable, circular, and petroleum-based materials are distinguished based on their origin and information provided by the manufacturer.

[0038] In the context of this disclosure, CX hydrocarbons, alkanes, or the like refer to hydrocarbons, alkanes, or the like having at least X carbon atoms, where X is any feasible integer; CX-CY (or CX to CY) hydrocarbons, alkanes, or the like refer to hydrocarbons, alkanes, or the like having at least X and at most Y carbon atoms. It should be understood that not every compound with a carbon number falling within this definition exists, and compounds with carbon numbers falling outside this definition may also exist.

[0039] Hydrotreating, sometimes also called hydroprocessing, refers in this paper to catalytic methods for treating organic materials with molecular hydrogen. Hydrotreating reactions can include the removal of oxygen from oxygenated hydrocarbons as water (HDO), the removal of sulfur from organosulfur compounds as hydrogen sulfide (H2S) (HDS), the removal of nitrogen from organonitrogen compounds as ammonia (NH3) (HDN), the removal of halogens, such as the removal of chlorine from organochlorine compounds as hydrogen chloride (HCl) (HDCl), and / or the removal of metals by hydrodemetallization; and / or the hydrogenation of alkene bonds to saturated bonds and / or the hydrogenation of aromatics to cycloalkanes. For example, depending on the composition of the hydrotreating feedstock, different reactions may occur and / or different reactions may predominate in hydrotreating. Generally, hydrotreating can convert hydrotreating feedstocks of varying compositions into purer materials by reducing the content of heteroatoms, metals, olefins, aromatics, and / or other less desirable compounds in the hydrotreating feedstock. Hydrotreating may also include certain side reactions, such as hydrocracking, which may actually be beneficial in the (pre)hydrotreating of this method.

[0040] Hydrocracking, as defined herein, refers to a catalytic process that treats organic materials in the presence of molecular hydrogen, resulting in the cracking of feedstock molecules into smaller, lower-boiling-point compounds. The presence of hydrogen ensures a reduction in olefin formation. Hydrocracking may also involve ring-opening of cyclic feedstock components and the breaking of heteroatoms. Isomerization reactions may also occur during hydrocracking, depending on the feedstock composition, hydrocracking conditions, and the catalyst used. Unlike hydrotreatment catalysts, hydrocracking catalysts require at least some acidity, which can be obtained, for example, by using acidic materials and / or incorporating promoters such as certain metals, as known in the art.

[0041] As used herein, regardless of whether the reaction steps are defined as taking place in a “reactor” (such as a hydrotreatment reactor and a hydrocracking reactor), the description is primarily for illustrative purposes. Those skilled in the art will understand that any “reactor” in practice is implemented as a reactor system that can consist of one or more reactors. Whether a reactor is actually arranged in a single reactor or several reactors is an engineering matter and may be affected by practical issues such as the maximum height of the equipment on site, the reactor diameter, on-site management and maintenance issues, on-site wind conditions, and / or available equipment. Similarly, “separation” or “separation sections” can occur in separation systems, which typically include, for example, separators and distillation units, which can be arranged according to conventional engineering practices in the art.

[0042] Regarding various separation and / or fractionation methods and systems, including, for example, distillation, it should be understood that the precision of separation and / or fractionation may vary, and in fact, even adjacent liquid fractions recovered from the separation section may boil within a partially overlapping range, i.e., having IBP and FBP. Typically, any adjacent liquid fractions have different T50 temperatures. More specifically, the liquid fraction recovered from the separation section may have a T60 temperature lower than the T40 temperature of the adjacent higher boiling point fraction. Preferably, the liquid fraction recovered from the separation section may have a T70 temperature lower than the T30 temperature of the adjacent higher boiling point fraction.

[0043] This disclosure provides a method for producing hydrocarbon fractions, the method comprising: a) In a pre-hydroconversion reactor, in the presence of a pre-hydroconversion catalyst, at least one or more of vegetable oils, animal fats, microbial oils, lignocellulose-derived biocrude oils, and / or liquefied organic waste are pre-hydroconverted to obtain a pre-hydroconversion effluent, and a petroleum feed is co-fed into the pre-hydroconversion reactor, and / or the petroleum feed is combined with at least a portion of the pre-hydroconversion effluent to obtain a hydrotreated feed having petroleum content and renewable and / or recyclable content. b) Hydrotreating the feedstock in the presence of a hydrotreating catalyst in a hydrotreating reactor to obtain a hydrotreating effluent. c) Introducing at least a portion of the hydrotreated effluent into a separation section and recovering at least three different distillates and a separation section bottoms product from the separation section, the separation section bottoms product having an initial boiling point of at least 300°C, such as in the range of 300°C to 420°C, preferably at least 320°C, such as in the range of 320°C to 410°C, more preferably at least 340°C, such as in the range of 340°C to 400°C (EN ISO 3405-2019). d) Recovering residual marine fuel components from the bottom of the separation section, preferably by separating a portion of the bottom of the separation section. e) In a hydrocracking reactor, in the presence of a hydrocracking catalyst, a hydrocracking feed containing a portion of the bottom product of the separation section is hydrocracking to obtain a hydrocracking effluent, and at least a portion of the hydrocracking effluent and the hydrotreated effluent are co-fed into the separation section.

[0044] This method allows for the production of several hydrocarbon fractions with renewable and / or cyclic content, for example, for use in fuel compositions, in good yields and quality. The method improves the overall economics of the process and provides flexibility in product mix design and higher overall value. Simultaneously, it reduces GHG emissions and dependence on dwindling petroleum resources. The advantages involve the finding that renewable and / or cyclic content can be virtually unrestricted in the hydrotreating feed through the pre-hydroconversion step, particularly in mitigating the exothermic and / or corrosion risks of the hydrotreating reactor, and that this content can be further distributed over a wider boiling point range through subsequent hydrotreating and hydrocracking steps, enabling the recovery of several product fractions with significant renewable and / or cyclic content. It also enhances the flexibility regarding the selection of renewable and / or cyclic feeds, allowing even highly challenging renewable and / or cyclic feeds to be introduced via pre-hydroconversion into conventional refinery units.

[0045] In the method of this invention, renewable and / or recycled content is incorporated into the hydrotreating feed. The renewable and / or recycled content in the hydrotreating feed originates from renewable and / or recycled feed undergoing pre-hydrogenation conversion, i.e., at least one or more vegetable oils, animal fats, microbial oils, lignocellulose-derived biocrude oils, and / or liquefied organic waste. Typical vegetable oils, animal fats, microbial oils, lignocellulose-derived biocrude oils, and / or liquefied organic wastes may contain, for example, fatty acids, fatty acid glycerides, fatty acid alkyl esters, fatty alcohols, resin acids, resin esters, other oxygenated hydrocarbons, olefins, and / or cyclic hydrocarbons. Exemplary vegetable oils that can be used in this method include rapeseed oil, low-erucic acid rapeseed oil, soybean oil, coconut oil, sunflower oil, palm oil, palm kernel oil, peanut oil, flaxseed oil, sesame oil, corn oil, poppy seed oil, cottonseed oil, soybean oil, tall oil, crude tall oil (CTO), corn oil, castor oil, jatropha oil, jojoba oil, olive oil, flaxseed oil, camellia oil, safflower oil, babassu oil, seed oil of any Brassica species or subspecies (e.g., Ethiopian mustard seed oil, mustard seed oil, cabbage seed oil, black mustard seed oil, European rapeseed seed oil, turnip (Brassicarapa) seed oil, carrot (Brassica hirta) seed oil, and white mustard (Brassica alba) seed oil, and rice bran oil), and / or fractions or residues of said vegetable oils (e.g., palm oil extract). The product may include: olein, palm stearin, palm fatty acid distillate (PFAD), purified tall oil, tall oil fatty acids, tall oil resin acids, distilled tall oil, tall oil unsaponifiables, tall oil pitch (TOP), and / or waste cooking oil of plant origin; exemplary animal fats may include beef tallow, lard, yellow fat, palm fat, fish fat, poultry fat, and / or waste cooking oil of animal origin; and exemplary microbial oils may include algal lipids, fungal lipids, and / or bacterial lipids.Lignocellulose-derived biocrude oil may comprise lignocellulose liquefied by thermal methods (e.g., hydrothermal or via pyrolysis) or catalytic methods (e.g., thermocatalytic liquefaction), wherein exemplary lignocellulose may include lignocellulosic biomass and residues (such as wood chips, sawdust, forestry thinnings, road trimmings, bark, branches, garden waste, and weeds), energy crops (such as dwarf trees, willows, Miscanthus, and giant reeds); agricultural (by-products) (e.g., grass, straw, stalks, husks, cob and husks from wheat, rye, corn, rice, and / or sunflowers; empty fruit clusters from palm oil production; palm oil mill wastewater; residues from sugar production (e.g., bagasse, distiller's grains, molasses, and / or greenhouse waste)); energy crops (e.g., Miscanthus, switchgrass, sorghum, and / or Jatropha); and / or lignocellulose industrial waste streams (e.g., papermaking sludge, substandard fibers from paper production, residues and by-products from food production (e.g., juice or wine production, vegetable oil production, food waste)). Liquefied organic waste can include organic waste liquefied by thermal methods (e.g., hydrothermal or via pyrolysis) or catalytic methods (e.g., thermocatalysis). Organic waste can include waste plastics, end-of-life tires (ELT), waste lubricants, and / or municipal solid waste (MSW). Clearly, due to its mixed waste nature, liquefied organic waste has a non-biogenic carbon content and often also has a biogenic carbon content. For example, due to the presence of biomass waste in MSW, the biogenic carbon content of MSW can vary considerably, but is typically significant, for example, from 40 to 70 wt.-%, based on the total weight of carbon (TC) in the MSW. Similarly, due to the presence of natural rubber, for example, in ELT, the biogenic carbon content of ELT can vary, but is typically significant, for example, from 15 to 40 wt.-%, based on the total weight of carbon (TC) in the ELT. Furthermore, due to the low proportion of bio-based plastics in waste plastics, the biogenic carbon content of liquefied waste plastics can vary; however, this may change over time as the production of bio-based plastics increases.

[0046] The renewable and / or recycled feedstocks illustrated above are readily available in the quantities and qualities suitable for use in this method, and various well-established pretreatment techniques exist for purifying these materials. If at least one or more of the vegetable oils, animal fats, microbial oils, lignocellulose-derived biocrude oils, and / or liquefied organic wastes contain impurities or species that are intolerant or preferred in pre-hydrogenation conversion, the content of said impurities can be reduced to an acceptable limit using pretreatment methods known in the art. Exemplary pretreatment methods suitable for this disclosure include treatment with inorganic acids, degumming, treatment with hydrogen, heat treatment, deodorization, washing with water, treatment with alkali, demetallization, distillation, solids removal, bleaching, and any combination thereof.

[0047] Vegetable oils, animal fats, microbial oils, and lignocellulose-derived biocrude oils are essentially biologically derived and are therefore preferred feedstocks in step a). On the other hand, typical fatty materials such as vegetable oils, animal fats, and / or microbial oils, as well as liquefied organic waste, tend to form alkanes during pre-hydroconversion and / or hydrotreatment, with well over 50 wt.% being n-alkanes, which are excellent cetane enhancers. Alkanes are also more readily cracked than cyclic hydrocarbons, which may be abundant, for example, in lignocellulose-derived biocrude oils. Vegetable oils, animal fats, and / or microbial oils can be considered further preferred feedstocks in step a) due to the renewable propane formed from the glycerol backbone typically present in these lipid materials. The resulting propane can be separated from the pre-hydroconversion effluent and, for example, purified for the production of renewable propylene, or used in other light hydrocarbons for the production of renewable hydrogen in a hydrogen production unit. Therefore, in some preferred embodiments, the method includes a) pre-hydrogenating at least one or more of vegetable oils, animal fats, microbial oils and / or liquefied organic waste, preferably at least one or more of vegetable oils, animal fats and / or microbial oils.

[0048] The petroleum content of the hydrotreating feed can vary over a wide range, for example, from 1 to 99% by weight. In some preferred embodiments, the petroleum content of the hydrotreating feed is 5-95% by weight, preferably 10-95% by weight, more preferably 15-90% by weight, and even more preferably 20-85% by weight. By using a pre-hydroconverted renewable and / or recycled feed, the petroleum content can be kept very low without the significant metallurgy corrosion problems associated with the hydrotreating reactor, and also varies flexibly over a wide range depending on, for example, the availability and / or quality fluctuations of the renewable and / or recycled feed. By incorporating petroleum content into the hydrotreating feed, the hydrotreating catalyst can remain adequately sulfided and thus remain active even without separate sulfur incorporation. Petroleum contains hydrocarbons of various alkanes, cycloalkanes, and aromatics, and has a very wide molecular weight range. Therefore, certain petroleum contents can also be considered beneficial due to product properties, for example, by providing recycled compounds to gasoline fuel range fractions, thereby improving octane numbers.

[0049] Furthermore, since renewable and / or recycled content is introduced into the hydrotreating feed in the form of pre-hydroconversion, the efficiency of hydrotreating steps, such as reducing heteroatom content, olefin saturation, and dearomatization, is not compromised. Compared to other similar methods that use 100% petroleum feed, hydrotreating efficiency can even be increased, and / or lower-quality petroleum co-feeds can be used.

[0050] Typically, based on the total weight of the petroleum feed, the petroleum feed contains greater than 30 wt.-%, preferably greater than 40 wt.-%, more preferably greater than 50 wt.-%, of hydrocarbons boiling in the range of 100°C to 400°C (ASTM D2887-2023), and greater than 10 wt.-%, preferably at least 20 wt.-%, more preferably at least 30 wt.-%, of hydrocarbons boiling above 380°C (ASTM D2887-2023). The choice of petroleum feed is not particularly limited, but components of lower quality and / or with limited applicability in high-value applications may be preferred over, for example, straight-run petroleum distillates. In this way, the overall value of the product composition of the entire refinery can be optimized. Therefore, in some preferred embodiments, the petroleum feed includes at least one or more of the following: atmospheric distillation bottoms; vacuum distillate; atmospheric and / or vacuum distillate from (hydro)cracking atmospheric and / or vacuum distillation bottoms; atmospheric distillation bottoms from (hydro)cracking atmospheric and / or vacuum distillation bottoms; atmospheric and / or vacuum distillate from (hydro)cracking vacuum distillate; and / or atmospheric bottoms from (hydro)cracking vacuum distillate of crude oil. In embodiments where the petroleum feed is co-fed at several locations to, for example, two or more pre-hydroconversion reactors, pre-hydroconversion fractionation reactors, and hydrotreating reactors, different petroleum feed masses may be co-fed at different locations. For example, the petroleum feed to the pre-hydroconversion reactor may contain other, and even heavier, materials besides those exemplified above, such as crude oil vacuum distillate and / or preferably deasphalted vacuum distillation bottoms, while the petroleum feed to the hydrotreating reactor is preferably as exemplified above. To further enhance the sustainability of the hydrotreating feedstock, additional renewable and / or recycled feedstocks can be co-fed into the hydrotreating reactor as a small amount of pre-hydroconversion and / or even without pre-hydroconversion.

[0051] In some preferred embodiments, step a) comprises: pre-hydroconverting at least one or more of vegetable oils, animal fats, microbial oils, lignocellulose-derived biocrude oils, and / or liquefied organic waste in a pre-hydroconversion reactor in the presence of a pre-hydroconversion catalyst to obtain a pre-hydroconversion effluent, and mixing a petroleum feedstock with at least a portion of the pre-hydroconversion effluent to obtain a hydrotreated feedstock having a petroleum content and a renewable and / or recyclable content. In the absence of a petroleum feedstock in the pre-hydroconversion step, sulfur may be present only in a limited amount, e.g., only to maintain the sulfidation and activity of the pre-hydroconversion catalyst. The overall pre-hydroconversion capacity and conditions can be optimized for processing renewable and / or recyclable content without being consumed by HDS reactions required for, for example, fossil feedstocks.

[0052] Typically, when the hydrotreating feed has a renewable content, i.e., contains bio-based carbon, particularly at least one or more of the aviation fuel boiling range fractions, light gas oil fractions, intermediate gas oil fractions, and / or heavy gas oil fractions recovered from the separation section, can have a higher bio-based carbon content than the hydrotreating feed (EN16640:2017). The bio-based carbon content in the recovered fractions is affected by the bio-based carbon content in the hydrotreating feed, the choice of cut-off point value in the separation section, and the choice of cut-off point value for the pre-hydroconversion fraction. Similar considerations apply to the circulating carbon content; however, no analytical method exists for this circulating carbon content.

[0053] In some preferred embodiments, in step a), at least one or more vegetable oils, animal fats, microbial oils and / or lignocellulose-derived bio-oil (preferably at least one or more vegetable oils, animal fats and / or microbial oils) are pre-hydrogenated and the petroleum feed and at least a portion of the pre-hydrogenated effluent are incorporated into the hydrotreated feed at a weight ratio of 5:95 to 95:5, preferably 10:90 to 95:5, more preferably 15:85 to 90:10, or even more preferably 20:80 to 85:15; and each of the at least three different distillates recovered in step c) and the residual marine fuel components recovered in step d) have a bio-based carbon content (EN 16640:2017). Typically, in these embodiments, based on the total weight (TC) of carbon in the distillate / component (EN 16640:2017), the bio-source carbon content in each of the at least three different distillates recovered in step c) and the residual marine fuel component recovered in step d) is in the range of 1.5 to 99.0 wt.-%, preferably 3.0 to 95.0 wt.-%, more preferably 5.0 to 90.0 wt.-%.

[0054] This method relates to a) pre-hydroconverting at least one or more of vegetable oils, animal fats, microbial oils, lignocellulose-derived biocrude oils, and / or liquefied organic waste in a pre-hydroconversion reactor in the presence of a pre-hydroconversion catalyst to obtain a pre-hydroconversion effluent. The pre-hydroconversion is carried out in the presence of added hydrogen. Preferably, the pre-hydroconversion includes pre-hydrotreating and / or pre-hydrocracking (more preferably at least pre-hydrotreating) in a pre-hydroconversion reactor in the presence of a pre-hydrotreating and / or pre-hydrocracking catalyst (preferably at least a pre-hydrotreating catalyst) to obtain a pre-hydroconversion effluent. Pre-hydrotreating is particularly preferred to reduce heteroatom content, while the benefits of pre-hydrocracking include a more sustainable content distribution over a wider boiling range, thereby more effectively ultimately entering each recovered product fraction.

[0055] Pre-hydrocracking can be carried out as described below regarding hydrocracking. Pre-hydrotreatment can be carried out as described below regarding hydrotreatment or under slightly milder conditions. Therefore, in some preferred embodiments, pre-hydroconversion includes pre-hydrotreatment in a pre-hydroconversion reactor, wherein the pre-hydrotreatment is carried out in the presence of a pre-hydrotreatment catalyst under the following conditions: temperature in the range of 300°C to 420°C, preferably 320°C to 380°C; pressure in the range of 3 MPa to 15 MPa, preferably 4 MPa to 10 MPa; H2 partial pressure at the inlet of the pre-hydroconversion reactor in the range of 3 MPa to 15 MPa, preferably 4 MPa to 10 MPa; weight hourly space velocity in the range of 0.1 to 10, preferably 0.2 to 8 kg pre-hydroconversion feed / kg catalyst / hour; and H2 to pre-hydroconversion feed ratio in the range of 50 to 2000, preferably 100 to 1500 standard liters of H2 / liter of pre-hydroconversion feed. In some embodiments, pre-hydrocracking is carried out in one or more fluidized bed catalysts. In these embodiments, the temperature and / or pressure may be as described above, or even slightly higher.

[0056] Choosing the pressure and / or temperature in the pre-hydroconversion process to be on the higher side of pressure and / or on the lower side of temperature can further suppress deoxygenation via decarboxylation / decarbonylation reactions, thereby controlling the formation of carbon oxides and their content in the gas phase of the pre-hydroconversion effluent.

[0057] The pre-hydrotreating catalyst can be any conventional hydrotreating catalyst well known in the art, such as any of those described below regarding hydrotreating catalysts. The pre-hydrocracking catalyst can be any conventional hydrocracking catalyst well known in the art, such as any of those described below regarding hydrocracking catalysts. A sulfurized pre-hydroconversion catalyst is preferred. By incorporating petroleum content into the pre-hydroconversion feedstock, the pre-hydroconversion catalyst (including pre-hydrotreating and / or pre-hydrocracking catalysts) can remain adequately sulfurized and therefore adequately active, even without the need for separate sulfur incorporation. Alternatively or additionally, the pre-hydroconversion feedstock can be incorporated with additional sulfur to maintain adequate catalyst sulfurization and activity.

[0058] By pre-hydroconverting renewable and / or recycled feedstocks, particularly through pre-hydrotreating and / or pre-hydrocracking, the formation of carbon dioxide and carbon monoxide in hydrotreating step b) can be minimized or even eliminated. While conventional purification techniques, such as desulfurization (sweetening to remove both H2S and CO2), can be used to effectively remove CO2 from the gas phase of the reactor effluent, CO can accumulate in the recycled hydrogen stream, which can be recovered from the stream separated from the pre-hydroconversion effluent. This limits, for example, how much of the recycled hydrogen stream can actually be recycled back to the various hydrotreating and / or hydrocracking units in the refinery. By pre-hydroconverting renewable and / or recycled feedstocks, conditions in the pre-hydroconversion reactor can be optimized so that hydrodeoxygenation reactions take precedence over decarboxylation / decarbonylation reactions, for example, by limiting the presence of sulfur compounds, limiting the temperature, and / or increasing the pressure in the pre-hydroconversion reactor. Using a separate pre-hydrogenation conversion step also allows for special treatment of the gas stream separated from the pre-hydrogenation conversion effluent to mitigate problems associated with CO accumulation in the recycle hydrogen stream recovered from the gas stream.

[0059] Optional prehydroconversion fractionation of the prehydroconversion effluent may include any conventionally used fractionation technique and may be arranged similarly to the combined separation section described below. However, since only the regenerative and / or recycled content to be incorporated into the hydrotreatment feed needs to be prehydroconverted, prehydroconversion fractionation can be smaller and / or simpler, thus involving lower investment and operating costs. In some embodiments, gas-liquid separation and optional stabilization alone may be sufficient for the prehydroconversion effluent, thereby further reducing the investment and operating costs of prehydroconversion fractionation and maximizing the yield of regenerative and / or recycled molecules to be hydrotreated.

[0060] In some preferred embodiments, the pre-hydroconversion effluent is fed into a pre-hydroconversion fractionation to recover at least one or more pre-hydroconversion distillates and pre-hydroconversion fractionation bottoms, such that only a portion of the pre-hydroconversion effluent, preferably the pre-hydroconversion fractionation bottoms, is introduced into the hydrotreating feed. These embodiments involve additional benefits: other fractions recovered from the pre-hydroconversion fractionation can be directed to other value-added uses or methods. By appropriately selecting the cut-off point in the pre-hydroconversion fractionation, optimized utilization and value-added processing of recyclable and / or recyclable content can be achieved.

[0061] In some preferred embodiments, step a) includes feeding the pre-hydroconversion effluent into a pre-hydroconversion fractionation to recover one or more pre-hydroconversion distillates and pre-hydroconversion fractionation bottoms, and combining the petroleum feed with the pre-hydroconversion fractionation bottoms to obtain the hydrotreating feed; the method further includes: f) Feeding the one or more pre-hydrogenated conversion distillates to a catalytic conversion, preferably to a catalytic conversion including at least hydroisomerization, more preferably to a catalytic conversion including at least hydrotreatment and hydroisomerization, optionally co-feeding with at least one or more of vegetable oils, animal fats, microbial oils, lignocellulose-derived biocrude oils and / or liquefied organic waste to obtain catalytic conversion effluent; and g) Optionally, at least aviation fuel components and / or diesel fuel components are recovered from the catalytic conversion effluent. Since the pre-hydroconversion fraction bottoms containing the heaviest compounds are removed, processing the pre-hydroconversion distillate in subsequent catalytic conversion is easier, including, for example, reducing the risk of pulverization in the catalyst bed and / or pressure drop on the fixed catalyst bed. Furthermore, the pre-hydroconversion distillate is a good diluent for oxygenated hydrocarbons in hydrotreatment and helps control the exothermic and / or corrosive risks of hydrotreatment. Embodiments involving hydroisomerization allow for the recovery of aviation fuel components and / or diesel fuel components with high isomerization degrees, for example, when required due to increased market demand at a given time. The high isomerization degrees achieved are anticipated to improve the cold properties, flowability, pumping and mixing characteristics, and blendability of the recovered components and / or products. These are generally desired and beneficial properties, not limited to fuel purposes but for a wide range of applications, particularly involving spraying, injection, and / or mixing with other components.

[0062] In some further preferred embodiments, step a) includes: subjecting at least one or more of vegetable oils, animal fats, and / or microbial oils to the pre-hydroconversion process, feeding the pre-hydroconversion effluent to a pre-hydroconversion fractionation to recover one or more pre-hydroconversion distillates and pre-hydroconversion fractionation bottoms, and combining the petroleum feed with the pre-hydroconversion fractionation bottoms to obtain the hydrotreating feed; and

[0063] f) Feeding the one or more pre-hydrogenated conversion distillates to a catalytic conversion, preferably to a catalytic conversion including at least hydroisomerization, more preferably to a catalytic conversion including at least hydrotreatment and hydroisomerization, optionally co-feeding with at least one or more of vegetable oils, animal fats and / or microbial oils to obtain a catalytic conversion effluent; and

[0064] g) Optionally, at least aviation fuel components and / or diesel fuel components are recovered from the catalytic conversion effluent. These embodiments relate to the further benefit of providing some products with a bio-based carbon content of 100 wt.-% and the further benefit of forming renewable propane from the glycerol backbone typically present in these lipid materials. The formed propane can be isolated and used, for example, to produce renewable propylene or to produce renewable hydrogen in a hydrogen production unit. In these embodiments, hydrotreating can be performed, for example, as described below with respect to hydrotreating or above with respect to pre-hydrotreating, and hydroisomerization can be performed, for example, as described in FI100248B, EP1741768A1, EP1741768A1, EP2155838B1, FI129220B1, EP1396531A2 or EP0985010A1.

[0065] Hydrotreating is carried out in the presence of added hydrogen. Hydrotreating can be carried out, for example, using any hydrotreating reactor, conditions, and catalyst known to those skilled in the art and / or conventionally used in refineries. Hydrotreating in the hydrotreating reactor can be carried out, for example, in the presence of a hydrotreating catalyst under the following conditions: temperature in the range of 300°C to 450°C, preferably 350°C to 420°C; pressure in the range of 6 MPa to 20 MPa, preferably 10 MPa to 18 MPa; H2 partial pressure at the inlet of the hydrotreating reactor in the range of 6 MPa to 20 MPa, preferably 10 to 18 MPa; weight hourly space velocity in the range of 0.1 to 10, preferably 0.2 to 8 kg hydrotreating feed / kg catalyst / hour; and H2 to hydrotreating feed ratio in the range of 50 to 2000, preferably 100 to 1500 standard liters of H2 / liter of hydrotreating feed. Under these conditions, the efficiency of the hydrotreatment step can be further improved with respect to the selectivity and / or activity of the hydrotreatment reactions (including reduction of heteroatom content, olefin saturation, and dearomatization), catalyst deactivation is controlled, and undesirable side reactions are suppressed. For example, the relatively high hydrogen pressure in hydrotreatment helps minimize the presence and formation of olefins, thereby contributing to improved stability of the product fraction.

[0066] The hydrotreating catalyst can be any conventionally used hydrotreating catalyst or a combination thereof, and no special catalyst is required. Exemplary hydrotreating catalysts include those described in various handbooks in the field, such as the Handbook of Petroleum Processing, edited by Jones and Pujado, Springer 2006, Chapter 8 “Hydrotreating, Catalysts”, pp. 334-344; in Petroleum Refining, Volume 3 Conversion Processes, Technip Press, 2001, edited by P. Leprince, Chapter 16 Hydrotreating, pp. 546-549; and the Handbook of Petroleum Refining, edited by James G. Speight, CRC Press 2017, Chapter 10 Hydrotreating Methods, pp. 423-424; or in patent publications, particularly in FI100248B, EP1741768A1, EP2155838B1, or FI129220B1. Therefore, in some embodiments, the hydrotreating catalyst comprises at least one or more metals selected from Group VIII and / or Group VIB 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 with a small amount of silica or phosphorus optionally added to a support (such as alumina and / or silica, more preferably γ-alumina). These hydrotreating catalysts are efficient, readily available, commonly used for HDS of, for example, petroleum feedstocks and also for HDO of, for example, fatty feedstocks, and are well resistant to the typical impurities of the hydrotreating feedstocks used in this method.

[0067] Catalysts comprising acidic porous materials, particularly zeolites and / or zeolite-type materials with suitable shape-selective framework types, and optionally also having metal sites for catalytic (de)hydrogenation reactions, such as those described in Chapter 12.3.5 Catalytic Dewaxing Process, pp. 548-550, of Handbook of Petroleum Refining, edited by James G. Speight, CRC Press 2017, can also be used as co-catalysts for hydrotreatment, at least in one catalyst bed of the hydrotreatment reactor, to reduce the content of long-chain alkanes and increase the content of iso-chain alkanes and / or cracked alkanes in the hydrotreatment effluent. These catalysts are referred to herein as dewaxing catalysts. Thus, in some preferred embodiments, in step b), the hydrotreatment reactor further comprises a dewaxing catalyst to obtain the hydrotreatment effluent.

[0068] The separation section of this method can utilize any conventional separation and / or fractionation techniques. The separation section can be carried out in a separation section system comprising one or more separation and / or fractionation units. For example, at least a portion of the gas can be separated in a gas-liquid separation, as described below. Subsequently, another separation and / or fractionation unit, such as a stabilization unit, can be used to further separate at least a portion of the remaining gas (e.g., fuel gases) and, for example, a light naphtha fraction. Stabilization, a type of partial distillation used to remove gaseous and most volatile liquid hydrocarbons to reduce vapor pressure, can be carried out, for example, using a stripper or distillation column, while fractionation can be carried out, for example, using a distillation column. Further distillates such as heavy naphtha fractions, aviation fuel boiling range fractions, light gas oil fractions, intermediate gas oil fractions, and / or heavy gas oil fractions, and the bottoms of the separation section can be recovered, for example, using one or more distillation units. The distillation unit can include atmospheric distillation and / or vacuum distillation units. In alternative embodiments, a single fractionation unit can be used.

[0069] As described above, gas-liquid separation can be performed on hydrotreatment effluents, pre-hydroconversion effluents, and / or hydrocracking effluents. The gas-liquid separation of hydrotreatment effluents, pre-hydroconversion effluents, and / or hydrocracking effluents can be performed, for example, as an integral step within their respective reactors, or subsequently using, for example, high-pressure-high-temperature, high-pressure-medium-temperature, or similar separators. Typically, gas-liquid separation is carried out at temperatures ranging from 0°C to 500°C, such as 15°C to 300°C, or 15°C to 150°C, preferably 15°C to 65°C, such as 20°C to 60°C, and preferably at pressures substantially the same as the pressure of the reactor from which the effluents originate. Typically, the pressure during the gas-liquid separation process can range from 0.1 MPa to 20 MPa, preferably 1 MPa to 18 MPa, or from 3 MPa to 15 MPa. Gas-liquid separation allows the recovery of compounds that are in a gaseous state under separation conditions (referred to as gas stream in this paper) from the respective reactor effluents.

[0070] Exemplary compounds retained in the gas stream separated from the respective reactor effluents may include at least one or more of residual hydrogen, hydrogen disulfide, ammonia, and / or light hydrocarbons. Some carbon monoxide, carbon dioxide, and / or water may even be present, although these are more abundant in the gas stream optionally separated from the pre-hydrogenation conversion effluent. Depending on the composition of the gas stream, the separated gas stream may be conventionally treated, such as desulfurization, recovery of the recycle hydrogen feed, and / or recovery of light hydrocarbons. Light hydrocarbons, such as C1-C3 hydrocarbons, optionally recovered, for example, from the gas stream, from the overhead distillate of a steam stripper and / or distillation column, and / or from the stabilization of any distillate, are collectively referred to herein as fuel gas. On the other hand, the light naphtha fraction may contain at least hydrocarbons heavier than the fuel gas that can be recovered from, for example, the overhead distillate of a steam stripper and / or distillation column and / or from the stabilization of any distillate. In some preferred embodiments, the recycle hydrogen stream, fuel gas, and / or light naphtha fraction are further recovered from the separation section, and at least a portion of the fuel gas and / or light naphtha fraction is fed into the hydrogen production unit, preferably into the steam reforming unit, to obtain syngas, from which a makeup hydrogen stream is subsequently recovered; and optionally, at least a portion of the recycle hydrogen stream and / or makeup hydrogen stream is recycled to the pre-hydrogenation conversion in step a), the hydrotreating in step b), and / or the hydrocracking in step e). The use of such a recycle hydrogen stream and / or makeup hydrogen stream enhances the economics of this method.

[0071] This method also includes a hydrocracking step, converting the bottoms of the separation section into shorter hydrocarbons, thereby further increasing the distillate yield and further distributing the renewable and / or recycle content over a wider boiling range. By hydrocracking only the bottoms of the separation section, the vapor load is reduced, allowing for smaller equipment or enabling higher (full) capacity for converting heavy molecules in the hydrocracking step. Although significant hydrogen consumption and the resulting gaseous cracking products reduce the H2 partial pressure, the reduced vapor load enhances hydrogen purity and allows for higher hydrogen partial pressures in the hydrocracking step (even towards the end of the reactor). In this way, residual olefins and heteroatoms are minimized and catalytic reactions are enhanced, resulting in a purer and more stable recovered fraction.

[0072] Hydrocracking is carried out in the presence of added hydrogen. Hydrocracking can be carried out, for example, using any hydrocracking reactor, conditions, and catalyst known to those skilled in the art and / or, for example, conventionally used in refineries. Hydrocracking in the hydrocracking reactor can be carried out in the presence of a hydrocracking catalyst under the following conditions: a temperature in the range of 280°C to 450°C, preferably 300°C to 420°C; a pressure in the range of 8 MPa to 20 MPa, preferably 12 MPa to 18 MPa; a partial pressure of H2 at the inlet of the hydrocracking reactor in the range of 8 MPa to 20 MPa, preferably 12 MPa to 18 MPa; a weight hourly space velocity in the range of 0.1 to 10, preferably 0.2 to 8 kg hydrocracking feed / kg catalyst / hour; and an H2 to hydrocracking feed ratio in the range of 50 to 2000, preferably 500 to 1500 standard liters of H2 per liter of hydrocracking feed. Under these conditions, the efficiency of the hydrocracking step can be further enhanced regarding the selectivity and / or activity of the hydrocracking reaction, the deactivation of the hydrocracking catalyst is controlled, unwanted side reactions are suppressed, and the desired conversion level is achieved. For example, the relatively high hydrogen pressure in hydrocracking helps minimize the presence and / or formation of olefins, thereby contributing to improved stability of the product fraction.

[0073] Hydrocracking catalysts can be any conventionally used hydrocracking catalyst or a combination thereof, without the need for special catalysts. For example, any bifunctional hydrocracking catalyst known in the refining and renewable fuel production sectors, containing metal sites for catalytic (de)hydrogenation and acid sites for catalytic cracking, can be utilized. Typical hydrocracking catalysts contain elemental noble metals such as molybdenum and / or palladium, or sulfide base metals such as nickel, cobalt, tungsten, and / or molybdenum; acidic porous materials, typically zeolites and / or zeolite-type materials exhibiting high cracking activity and possessing a suitable framework type, or amorphous silica-alumina; and optionally, refractory supports such as alumina, silica, and / or titanium dioxide. Hydrocracking catalysts may also contain other components such as boron or phosphorus. Exemplary hydrocracking catalysts used in this method include, for example, those described in Handbook of Petroleum Refining, CRC Press 2017, edited by James G. Speight, Chapter 11 Hydrocracking, pages 423-424; or in patent publications, particularly those described in WO 2020083989 or WO 2011007046. Therefore, in some embodiments, the hydrocracking catalyst is a bifunctional hydrocracking catalyst, preferably a non-sulfurized bifunctional hydrocracking catalyst, comprising at least one or more metals selected from Ni, Mo, Co, W, Pt and / or Pd, more preferably Pt and / or Pd; and at least one or more acidic porous materials selected from zeolites, zeolite-type materials and / or amorphous silica-alumina, wherein preferably at least one or more zeolites or zeolite-type materials have a framework type selected from MFI, BEA, FAU, AFI, ATO, AFO, MTT and / or TON, and preferably at least one or more acidic porous materials selected from SAPO-5, SAPO-31, SAPO-41, ZSM-22, ZSM-23, ZSM-5, β-zeolite, Y-type zeolite and / or amorphous silica-alumina; and optionally at least one or more of alumina, silica, and / or titanium dioxide. The non-sulfurized noble metal hydrocracking catalyst is active at lower temperatures. Since the hydrocracking process in step b) effectively cracks the S and N molecules combined in the feedstock to form H2S and NH3 gases, and only the bottom product of the separation section (a portion thereof) continues hydrocracking, there is no need to worry about the rapid deactivation of the noble metal hydrocracking catalyst.

[0074] The hydroisomerization catalyst can be used as a co-catalyst in the hydrocracking process of step e), at least in one catalyst bed of the hydrocracking reactor, to reduce the content of n-alkanes and increase the content of isoalkanes in the hydrocracking effluent, thereby improving the cold characteristics of the product fraction. Therefore, in some preferred embodiments, the hydrocracking reactor further comprises a hydroisomerization catalyst in step e). Any bifunctional hydroisomerization catalyst known in the refining and renewable fuel production fields, comprising a metal site for catalytic (de)hydrogenation and an acid site for catalytic isomerization, can be utilized, such as the hydroisomerization catalysts described in FI100248B, EP1741768A1, EP1741768A1, EP2155838B1, FI129220B1, EP1396531A2, or EP0985010A1, preferably a non-sulfurized noble metal hydroisomerization catalyst.

[0075] The advantages of this method can be achieved at a reduced cost, especially when utilizing existing assets of an oil refinery. This method is well-suited for operation in conventional or existing refinery units. The pre-hydroconversion reactor alone may require a higher metallurgical grade than that of a conventional refinery unit. Therefore, in some preferred embodiments, at least one or more, preferably at least two or more, more preferably at least three or more, of the hydrotreatment reactor, hydrotreatment catalyst, separation section, hydrocracking reactor, and / or hydrocracking catalyst are configured as initially to process the oil feed.

[0076] After recovering at least three different distillates, as well as residual marine fuel components, additional steps may be included. These may include, for example, hydropolishing, dearomatization, stabilization, and a few other examples. Typically, such additional process steps are designed to better control the desired properties of the recovered fractions.

[0077] This method offers high flexibility regarding the recovery of different products and high yields of distillates, especially middle distillates. The inventors have discovered that by separating a portion of the bottom product from the separation section at least periodically and preferably by splitting, the accumulation of the heaviest components and / or hydrocracking resistant components in the circulation loop can be reduced, thereby ensuring smooth operation of the hydrocracking unit and the separation section, and advantageously contributing to the quality and distribution of all fractions recovered from the separation section. This is particularly achievable when the bottom product of the separation section has an initial boiling point of at least 300°C, preferably at least 320°C, more preferably at least 340°C (EN ISO 3405-2019). Typically, the bottom product of the separation section has an initial boiling point in the range of 300°C to 420°C, preferably 320°C to 410°C, more preferably 340°C to 400°C (EN ISO 3405-2019).

[0078] Furthermore, it is noted that the separation section meets several or substantially all of the specifications for at least one residual marine fuel category as specified in Table 2 of ISO 8217-2017, preferably at least the RMD category, more preferably at least the RMB category, or even the RMA category. This can be achieved simply by separating a portion from the bottom of the separation section. This method allows at least a portion of the renewable and / or recycled content, which is also desired in the marine fuel industry, to ultimately enter the bottom of the separation section. Therefore, recovering residual marine fuel components from the bottom of the separation section further improves the overall value of the product composition of this method. In some preferred embodiments, the residual marine fuel components are recovered from the bottom of the separation section based on the total weight of the bottom of the separation section at a rate ranging from 3 wt.-% to 30 wt.-%, preferably 3 wt.-% to 20 wt.-%, more preferably 5 wt.-% to 15 wt.-%. When the recovery rate of the residual marine fuel components is fixed, i.e., kept substantially constant, the hydrocracking conversion rate can be varied and increased, for example, by increasing the hydrocracking temperature and / or decreasing the WHSV. Alternatively, the recovery rate of the residual marine fuel components can preferably be varied within a specified range while aiming at a fixed hydrocracking conversion rate.

[0079] In some preferred embodiments, the at least three different distillates include naphtha fractions and at least: -Boiling range fractions of aviation fuel and heavy gas oil fractions, or - Light gas oil fraction and heavy gas oil fraction, or - Aviation fuel boiling range fraction and intermediate gas oil fraction Preferably, the at least three different distillates include naphtha fraction, heavy gas oil fraction, and aviation fuel boiling range fraction or light gas oil fraction. Surprisingly, this method has been found to allocate sustainable content to each recovered fraction / component, from naphtha fraction to residual marine fuel components.

[0080] In some preferred embodiments, the at least three different distillates include at least three or more of the following: - Naphtha fraction having a boiling point range of 1 BP to 230°C, preferably 20°C to 220°C (ASTM D7096-2019), and optionally, the difference between T90 and T10 temperatures is in the range of 30°C to 150°C, preferably 50°C to 120°C (ASTM D7096-2019). - Aviation fuel boiling range fraction, having a boiling point range of 120°C to 310°C, preferably 130°C to 300°C (EN ISO 3405-2019), and optionally, the difference between T90 and T10 temperatures is in the range of 40°C to 200°C, preferably 60°C to 180°C (EN ISO 3405-2019). - Light gas oil fraction, having a boiling point range of 120°C to 330°C, preferably 130°C to 320°C (EN ISO 3405-2019), and optionally, the difference between T90 and T10 temperatures is in the range of 50°C to 200°C, preferably 80°C to 190°C (EN ISO 3405-2019). - Intermediate gas oil fraction, having a boiling point range of 190°C to 390°C, preferably 200°C to 380°C (EN ISO 3405-2019), and optionally, the difference between T90 and T10 temperatures is in the range of 50°C to 200°C, preferably 80°C to 200°C (EN ISO 3405-2019); and / or - Heavy gas oil fraction, having a boiling point range of 270°C to 430°C, preferably 280°C to 410°C (EN ISO 3405-2019), and optionally, the difference between T90 and T10 temperatures is in the range of 5°C to 140°C, preferably 10°C to 100°C (EN ISO 3405-2019).

[0081] These fractions are available in good yields and cut widths and can be used in a variety of applications and / or downstream processing.

[0082] In some preferred embodiments, at least a naphtha fraction is recovered from the separation section, wherein the naphtha fraction preferably has a boiling point range of 20°C to 200°C, more preferably 85°C to 190°C (ASTM D7096-2019), and at least a portion thereof is fed into a catalytic naphtha reformer to obtain a reformed gasoline fraction. Surprisingly, the inventors have found that naphtha fractions obtained by this method are particularly suitable as co-feed to catalytic naphtha reformers due to their high cycloalkane content, thereby allowing the production of reformed gasoline fractions with good aromatic content, wherein a measurable portion may be of bio-derived origin. By appropriately selecting the initial boiling point of the naphtha fraction, for example at least 85°C (ASTM D7096-2019), the cyclohexane content can be kept low, resulting in less or virtually no benzene formation from the naphtha fraction in the naphtha reformer.

[0083] Therefore, in some embodiments, at least a naphtha fraction is recovered from the separation section, preferably as a stabilized naphtha fraction, wherein the naphtha fraction has at least one or more of the following properties: - The density at 15°C is in the range of 730 to 790 kg / m3, preferably 735 to 785 kg / m3 (EN ISO12185-1996). - The sulfur content is up to 20 mg / kg, preferably up to 15 mg / kg (ASTM D5623-2019). - The weight ratio of cycloalkanes to aromatics is at least 6.0, preferably at least 8.0 (GC-FID / GC-MS). - The aromatic content is in the range of 0.5 to 15.0 wt.-%, preferably 1.0 to 10.0 wt.-%, (GC-FID / GC-MS). - The cycloalkane content is in the range of 40.0 to 90.0 wt.-%, preferably 40.0 to 80.0 wt.-%, (GC-FID / GC-MS). - Cyclohexane content less than 5.0 wt.-%, preferably less than 2.0 wt.-%, (GC-FID / GC-MS), and / or - Based on the total weight of carbon in the fraction (TC), the bio-based carbon content is in the range of 1 to 50 wt.-%, preferably 3 to 40 wt.-%, (EN 16640:2017).

[0084] Middle fractions typically represent the most valuable product in a refinery's product plate, especially when they possess renewable and / or recyclable content and sufficient quality for use in aviation or diesel fuels. Aviation fuel boiling range fractions obtainable by this method, even on their own, meet several or substantially all of the specifications for aviation fuels outlined in Table 1 of ASTM D1655-2023. Light gas oil fractions obtainable by this method can, even on their own, meet several or substantially all of the specifications for diesel fuels outlined in EN 590:2022.

[0085] In some preferred embodiments, at least an aviation fuel boiling range fraction is recovered from the separation section, wherein the aviation fuel boiling range fraction has at least one or more of the following properties: - The temperature difference between T50 and T10 is at least 20°C, preferably at least 40°C (EN ISO 3405-2019). - The T10 temperature (EN ISO 3405-2019) is up to 205°C, preferably up to 190°C. - The kinematic viscosity at -20°C is at most 10.0 mm² / s, preferably at most 8.0 mm² / s (EN ISO 3104-2020). - The density at 15°C is in the range of 775 to 840 kg / m3, preferably 780 to 830 kg / m3 (EN ISO12185-1996). - Flash point is at least 38°C, preferably at least 40°C (IP 170-2013, Abel closed cup method). - The sulfur content is up to 20 mg / kg, preferably up to 10 mg / kg (EN ISO 20846-2019). - The cycloalkanes content is in the range of 40.0 to 80.0 wt.-%, preferably 50.0 to 75.0 wt.-%, (GCxGC-FID / GCxGC-MS). - The weight ratio of the total amount of cycloalkanes and isoalkanes to the amount of n-alkanes is in the range of 4.0 to 25.0, preferably 5.0 to 20.0 (GCxGC-FID / GCxGC-MS). - Freezing point up to -30°C, preferably up to -35°C (IP 529-2016), and / or - Based on the total weight of carbon in the fraction (TC), the bio-based carbon content is in the range of 5 to 50 wt.-%, preferably 10 to 40 wt.-%, (EN 16640:2017).

[0086] In some preferred embodiments, at least a light gas oil fraction is recovered from the separation section, wherein the light gas oil fraction has at least one or more of the following properties: - The kinematic viscosity at 40°C is in the range of 1.2 to 4.5 mm² / s, preferably 1.5 to 4.0 mm² / s (ENISO 3104-2020). - The density at 15°C is in the range of 795 to 860 kg / m3, preferably 810 to 845 kg / m3 (EN ISO12185-1996). - Flash point of at least 50°C, preferably at least 55°C (EN ISO 2719-2016 Pensky-Martens closed cup method). - The aromatic content is up to 25.0 wt.-%, preferably up to 20.0 wt.-%, (GCxGC-FID / GCxGC-MS). - The weight ratio of cycloalkanes to alkanes is in the range of 0.8 to 3.0, preferably 1.0 to 2.5 (GCxGC-FID / GCxGC-MS). - The cetane number is at least 43.0, preferably at least 44.0 (EN 15195:2023). - Cloud point up to +5°C, preferably up to -5°C (ASTM D7689-2021), and / or - Based on the total weight of carbon in the fraction (TC), the bio-based carbon content is in the range of 5 to 60 wt.-%, preferably 10 to 40 wt.-%, (EN 16640:2017).

[0087] Maritime transport is a mainstay of international trade, accounting for approximately 80% of global transport volume. It also contributes 2-3% of global GHG emissions. Zeroing these emissions is a significant challenge. The range of marine fuel components with renewable and / or cyclical content obtainable through this method will contribute to reducing GHG emissions and achieving the goal of a 50% reduction by 2050. The residual marine fuel components obtainable through this method can even meet several or most of the specifications for at least one residual marine fuel category as specified in Table 2 of ISO 8217-2017, preferably at least the RMD category, more preferably at least the RMB category, or even the RMA category. Furthermore, the heavy gas oil fraction and intermediate gas oil fraction obtainable through this method can be used for marine fuel. The recovered neutralized / or heavy gas oil fraction can even meet several or most of the specifications for at least one distillate marine fuel category as specified in Table 1 of ISO 8217-2017, preferably at least the DMB category, more preferably at least the DMZ category, or even the DMA or DMX category. Furthermore, the recovered intermediate gas oil fraction, even on its own, can meet several or substantially all of the specifications for diesel fuel stipulated in EN 590:2022.

[0088] Therefore, in some preferred embodiments, at least an intermediate gas oil fraction is recovered from the separation section, wherein the intermediate gas oil fraction has at least one or more of the following properties: - The kinematic viscosity at 40°C is in the range of 2.0 to 11.0 mm² / s, preferably 3.0 to 6.0 mm² / s (ENISO 3104-2020). - The density at 15°C is in the range of 815 to 900 kg / m3, preferably 820 to 860 kg / m3 (EN ISO12185-1996). - Flash point of at least 60°C, preferably at least 80°C (EN ISO 2719-2016 Pensky-Martens closed cup method). - The sulfur content is up to 50 mg / kg, preferably up to 5 mg / kg (EN ISO 20846-2019). - The aromatic content is up to 30.0 wt.-%, preferably up to 25.0 wt.-%, (GCxGC-FID / GCxGC-MS). - The weight ratio of cycloalkanes to alkanes is in the range of 0.8 to 2.5, preferably 1.0 to 2.0 (GCxGC-FID / GCxGC-MS). - The cetane number is at least 51.0, preferably at least 55.0 (EN 15195:2023). - Cloud point up to +10°C, preferably up to +5°C (ASTM D7689-2021), and / or - Based on the total weight of carbon in the fraction (TC), the bio-based carbon content is in the range of 5 to 80 wt.-%, preferably 10 to 70 wt.-%, (EN 16640:2017).

[0089] These implementations can provide improved yields and / or quality of intermediate gas oil fractions that can be used in diesel fuels and / or marine distillate fuels.

[0090] In some preferred embodiments, at least a heavy gas oil fraction is recovered from the separation section, wherein the heavy gas oil fraction has at least one or more of the following properties: - The kinematic viscosity at 40°C is in the range of 4.0 to 12.0 mm² / s, preferably 5.0 to 11.0 mm² / s (ENISO 3104-2020). - The density at 15°C is in the range of 820 to 900 kg / m3, preferably 840 to 890 kg / m3 (EN ISO12185-1996). - Flash point of at least 80°C, preferably at least 100°C (EN ISO 2719-2016 Pensky-Martens closed cup method). - The sulfur content is up to 100 mg / kg, preferably up to 10 mg / kg (EN ISO 20846-2019). - The aromatic content is up to 35.0 wt.-%, preferably up to 25.0 wt.-%, (GCxGC-FID / GCxGC-MS). - The weight ratio of cycloalkanes to alkanes is in the range of 0.5 to 1.5, preferably 0.8 to 1.5 (GCxGC-FID / GCxGC-MS). - The cetane number is at least 51.0, preferably at least 55.0 (EN 15195:2023). - Cloud point up to +25°C, preferably up to +20°C (ASTM D7689-2021), and / or - Based on the total weight of carbon in the fraction (TC), the bio-based carbon content is in the range of 5 to 80 wt.-%, preferably 10 to 70 wt.-%, (EN 16640:2017).

[0091] In some preferred embodiments, the residual marine fuel components recovered from the bottom of the separation section by separating a portion of it preferably have at least one or more of the following properties: - The kinematic viscosity at 40°C is in the range of 15 to 80 mm² / s, preferably 20 to 50 mm² / s (EN ISO3104-2020). - The density at 15°C is in the range of 850 to 975 kg / m3, preferably 860 to 920 kg / m3 (EN ISO12185-1996). - Flash point of at least 100°C, preferably at least 120°C (EN ISO 2719-2016 Pensky-Martens closed cup method). - The sulfur content is up to 150 mg / kg, preferably up to 15 mg / kg (EN ISO 20846-2019). - The nitrogen content is up to 10,000 mg / kg, preferably up to 8,000 mg / kg (ASTM D5762-2018a). - The aromatic content is up to 50.0 wt.-%, preferably up to 30.0 wt.-% (ASTM D2549-02 (2017)). - Lubricity expressed in high-frequency reciprocating test (HFRR) values ​​is up to 520 µm / 60°C, preferably up to 300 µm / 60°C (EN ISO 12156-1-2023), and / or - Based on the total weight of carbon in the fraction (TC), the bio-derived carbon content is in the range of 5 to 50 wt.-%, preferably 8 to 40 wt.-%, (EN 16640:2017).

[0092] According to the second example aspect, a naphtha fraction is provided having a boiling point range of 1 BP to 230°C, preferably 20°C to 220°C (ASTM D7096-2019), and optionally, the difference between T90 and T10 temperatures is in the range of 30°C to 150°C, preferably 50°C to 120°C (ASTM D7096-2019), and optionally, based on the total weight (TC) of carbon in the fraction, the biogenic carbon content is in the range of 1 wt.-% to 50 wt.-%, preferably 3 wt.-% to 40 wt.-% (EN 16640:2017), wherein the naphtha fraction has at least one or more additional properties as defined in the embodiments of the first example aspect, and is preferably obtainable by the method according to the first example aspect.

[0093] According to the third example aspect, an aviation fuel boiling range fraction is provided, having a boiling point range of 120°C to 310°C, preferably 130°C to 300°C (EN ISO 3405-2019), and optionally, the difference between T90 and T10 temperatures is in the range of 40°C to 200°C, preferably 60°C to 180°C (EN ISO 3405-2019), and optionally, based on the total weight (TC) of carbon in the fraction, the bio-based carbon content is in the range of 5 wt.-% to 50 wt.-%, preferably 10 wt.-% to 40 wt.-% (EN 16640:2017), wherein the aviation fuel boiling range fraction has at least one or more additional properties as defined in the embodiments of the first example aspect, and is preferably obtainable by the method according to the first example aspect.

[0094] According to the fourth example aspect, a light gas oil fraction is provided having a boiling point range of 120°C to 330°C, preferably 130°C to 320°C (EN ISO 3405-2019), and optionally, the difference between the T90 and T10 temperatures is in the range of 50°C to 200°C, preferably 80°C to 190°C (EN ISO 3405-2019), and optionally, based on the total weight (TC) of carbon in the fraction, the biogenic carbon content is in the range of 5 wt.-% to 60 wt.-%, preferably 10 wt.-% to 40 wt.-% (EN 16640:2017), wherein the light gas oil fraction has at least one or more additional properties as defined in the embodiments of the first example aspect, and is preferably obtainable by the method according to the first example aspect.

[0095] According to the fifth example aspect, an intermediate gas oil fraction is provided having a boiling point range of 190°C to 390°C, preferably 200°C to 380°C (EN ISO 3405-2019), and optionally, the difference between the T90 and T10 temperatures is in the range of 50°C to 200°C, preferably 80°C to 200°C (EN ISO 3405-2019), and optionally, based on the total weight (TC) of carbon in the fraction, the biogenic carbon content is in the range of 5 wt.-% to 80 wt.-%, preferably 10 wt.-% to 70 wt.-% (EN 16640:2017), wherein the intermediate gas oil fraction has at least one or more additional properties as defined in the embodiments of the first example aspect, and is preferably obtainable by the method according to the first example aspect.

[0096] According to the sixth example aspect, a heavy gas oil fraction is provided having a boiling point range of 270°C to 430°C, preferably 280°C to 410°C (EN ISO 3405-2019), and optionally, the difference between the T90 and T10 temperatures is in the range of 5°C to 140°C, preferably 10°C to 100°C (EN ISO 3405-2019), and optionally, the biogenic carbon content based on the total weight (TC) of carbon in the fraction is in the range of 5 wt.-% to 80 wt.-%, preferably 10 wt.-% to 70 wt.-% (EN16640:2017), wherein the heavy gas oil fraction has at least one or more additional properties as defined in the embodiments of the first example aspect, and is preferably obtainable by the method according to the first example aspect.

[0097] According to the seventh example aspect, a residual marine fuel component is provided having an initial boiling point of at least 300°C, such as in the range of 300°C to 420°C, preferably at least 320°C, such as in the range of 320°C to 410°C, more preferably at least 340°C, such as in the range of 340°C to 400°C (EN ISO 3405-2019), and optionally, based on the total weight (TC) of carbon in the fraction, the bio-based carbon content is in the range of 5 wt.-% to 50 wt.-%, preferably 8 wt.-% to 40 wt.-% (EN 16640:2017), wherein the residual marine fuel component has at least one or more additional properties as defined in the embodiments of the first exemplary aspect, and is preferably obtainable by the method according to the first example aspect.

[0098] The recovered at least one or more of at least three different distillates, preferably selected from naphtha fractions and at least: aviation fuel boiling range fractions and heavy gas oil fractions, or light gas oil fractions and heavy gas oil fractions, or aviation fuel boiling range fractions and intermediate gas oil fractions, can be used in a wide range of applications, such as in transportation fuels, in feedstocks for industrial conversion processes, preferably in thermal cracking feedstocks, such as in steam cracking feedstocks, and / or in catalytic cracking feedstocks, in transformer oils, in heat transfer media, in switchgear oils, in shock absorber oils, in insulating oils, in hydraulic fluids, in gear oils, in transmission fluids, in degreasing compositions, in permeated oils, and in corrosion inhibitors. In compounds, multipurpose oils, metalworking fluids, rolling oils (especially for aluminum), cutting oils, drilling fluids, solvents, lubricants, filler oils, carriers, dispersant compositions, demulsifiers, extractants, coating compositions, coating fluids or pastes, adhesives, resins, varnishes, printing pastes or inks, detergents, cleaning agents, plasticizers, turbine oils, hydrophobic compositions, in agriculture, in crop protection solutions, in construction, in concrete release formulations, in electronic devices, in medical devices, in compositions for automotive, electrical, textile, and packaging industries, in the paper, cosmetic, and / or pharmaceutical industries, and / or in intermediates used to manufacture them. The increased renewable and / or recycled content, especially the bio-based carbon content (which may be particularly abundant in the range of recovered middle distillate fractions), brings added value to all these applications.

[0099] Schematic diagram of the method

[0100] Figure 1 A method according to an exemplary embodiment is illustrated schematically. Figure 1Alternative methods for providing hydrotreated feedstock HTF with petroleum content and renewable and / or recycled content are also shown. A sustainable (renewable and / or recycled) feedstock S, comprising at least one or more of vegetable oils, animal fats, microbial oils, lignocellulose-derived biocrude oil, and / or liquefied organic waste, is optionally introduced into the pre-hydroconversion reactor 100 along with petroleum feedstock P1. Alternatively or additionally, petroleum feedstock P2 may be combined with the pre-hydroconversion effluent, and / or petroleum feedstock P3 may be combined with a pre-hydroconversion distillate fraction (preferably a fraction of the pre-hydroconversion bottoms obtained by pre-hydroconversion fractionation 110 of the pre-hydroconversion effluent). In the hydrotreated reactor 200, the hydrotreated feedstock HTF is hydrotreated in the presence of a hydrotreated catalyst and optionally a dewaxing catalyst to obtain a hydrotreated effluent, at least a portion of which is introduced into the separation section 300. At least three different distillates 410, 420, and 430 and the separator bottoms 440 are recovered from the separator 300. Residual marine fuel component 440a is recovered from the separator bottoms 440, preferably by separating a portion therefrom. The hydrocracking feed containing a portion of the separator bottoms 440b is hydrocracking in the hydrocracking reactor 500 in the presence of a hydrocracking catalyst and optionally a hydroisomerization catalyst to obtain hydrocracking effluent 510, at least a portion of which is co-fed with the hydrotreated effluent to the separator 300.

[0101] Example

[0102] Example 1. Pre-hydrogenation conversion and co-hydrogenation treatment with petroleum feedstock of three different renewable feedstocks

[0103] A feed containing conventionally purified crude tall oil (CTO) or a mixture thereof with conventionally purified animal fat (AF) is prepared. The CTO contains about 48 wt.% fatty acids (e.g., oleic acid), about 29 wt.% resin acids (e.g., rosin acid), and about 23 wt.% neutrals (e.g., sterols). The feed is pre-hydrogenated using a conventional NiMo hydrotreating catalyst. The conditions for the pre-hydrotreating step are as follows: a temperature of about 310 to about 340°C, a pressure of about 50 to about 60 bar (absolute), and a WHSV of about 0.8 to about 1.2 L / h. The pre-hydrotreating effluent is subjected to gas-liquid separation. A portion of the liquid stream is mixed with the pre-hydrotreating feed as a diluent (product recycling), and the resulting saturated and deoxygenated regenerable hydrocarbon stream is distilled to recover the pre-hydrotreating distillate and the pre-hydrotreating fraction bottoms with approximately 320°C (approximately 340°C for 100% CTO) IBP. The pre-hydrotreating fraction bottoms are used as a regenerable component in the hydrotreating feed, i.e., co-fed with the petroleum feed into subsequent hydrotreating. Tables 1A and 1B summarize the petroleum-only content (petroleum reference P) R Hydrogenation of feedstocks and their components for testing the content of petroleum and sustainable (here: renewable) content (P+S).

[0104] Table 1A. Brief description of hydrotreating feed.

[0105] Distillate from crude oil vacuum distillate and hydrocracking mixture of deasphalted vacuum distillate bottoms Table 1B. Brief description of certain hydrotreating feed components.

[0106]

[0107] The hydrotreating feed is 100 wt.-% of petroleum reference feed (P R The feedstock consists of 75 wt.-% petroleum feed (P) co-feeded with 25 wt.-% sustainable components S1, S2, or S3. In the hydrotreating reactor, the feedstock is hydrotreated using a conventional alumina-supported NiMo hydrotreating catalyst under the following conditions: pressure approximately 16 MPa, temperature approximately 340-390°C, and LHSV approximately 0.8-1.0 h. - ¹.

[0108] A gaseous stream containing gaseous and low-boiling hydrocarbons is removed from the hydrocracking effluent to obtain a liquid hydrocarbon stream, which is then distilled to obtain gasoline boiling range fractions, middle distillate fractions, and separator bottoms. A portion of the separator bottoms is separated as bleed. This helps maintain the quality of the recycle stream (i.e., the remaining portion of the separator bottoms to be fed into the hydrocracking process). The amount of bleed is affected by the content of heavy substances and the severity of the hydrocracking conditions. For example, at relatively low hydrocracking temperatures, some heavy components may remain under hydrocracking conditions, thus increasing the bleed amount.

[0109] The remaining portion of the bottoms from the separation section is then fed into a hydrocracking reactor for hydrocracking using a conventional hydrocracking catalyst (including a noble metal on an acidic porous material) and carried out under the following conditions: pressure approximately 16 MPa, temperature approximately 340–390°C, and LHSV approximately 0.8–1.0 h. -1 A gas stream containing gaseous and low-boiling hydrocarbons is removed from the hydrocracking effluent to obtain a liquid hydrocarbon stream, which is co-fed with the degassed hydrotreatment effluent to distillation. This cycle continues throughout the pilot run. The product fraction is recovered after reaching steady state. Reference P is used when using only petroleum feed. R The yield and variation (%) of the recovered fraction compared to the pilot run as a hydrotreating feed are reported in Table 2.

[0110] Table 2. Comparison with petroleum reference feed P used alone R Compared to feed for hydrotreating, the yield and change (%) of the recovered fraction.

[0111]

[0112] As shown in Table 2, compared to the reference feedstock for processing petroleum, processing 25 wt.-% of sustainable components S1, S2, or S3 yields a 5-6 wt.-% higher middle distillate yield, equivalent to an increase of approximately 9%. Simultaneously, gasoline-range hydrocarbon yields are 4-7 wt% lower (i.e., a reduction of approximately 40%), while the yield of the separator bottoms is the same or at most 1-2 wt% higher (i.e., an increase of up to approximately 10%). This combination of increased middle distillate yield and decreased gasoline-range hydrocarbon yield is desirable because middle distillates typically have higher value compared to lighter hydrocarbons. Furthermore, as shown in Examples 5-8, the middle distillate range products were found to have highly desirable properties, making their increased yields even more valuable. Separator bottoms were also found to have improved value because they not only have a sustainable content but are also suitable for use as residual marine fuel or as components for distillate marine fuel, as shown in Example 9. Surprisingly, when the renewable feedstock included animal fats, the co-processing of the sustainable components also affected gas formation, reducing it by approximately 50%. This can be considered beneficial because light gases have a lower value compared to liquid-range products.

[0113] Based on the results shown in Table 2, it appears that product composition can be easily fine-tuned by selecting how sustainable content is introduced. Gasoline-range hydrocarbon yields can be controlled by pre-hydrogenating and fractionating renewable and / or recycled feedstocks, and by co-feeding only bottom fractions to the hydrotreatment process. Gasoline-range hydrocarbon yields can be reduced, maintained, or even increased by co-feeding pre-hydrogenated effluents only in a degassed and optionally stabilized form (without further fractionation), or by co-feeding, for example, fatty feedstocks that have not undergone pre-hydrogenation. In typical refineries, adjusting the performance of the petroleum components of hydrotreatment feedstocks can be more difficult because such adjustments affect all other relevant upstream and downstream refining units, requiring multiple additional adjustments at the refinery and also involving the risk of negative impacts. The method of the process of this invention offers interesting possibilities for balancing the contribution of sustainable content to product composition, while allowing even very high incorporation rates of sustainable content without substantially compromising the efficiency of the hydrotreatment step. This is important for ensuring sufficient saturation levels and heteroatom removal to obtain products that meet various applications or downstream processing requirements, such as very low sulfur and nitrogen content. Therefore, the incorporation of sustainable content not only provides a higher-value product due to its presence, but also offers an easy and effective way to optimize product composition, for example, based on market demand, the availability of sustainable co-feeds, and / or their quality.

[0114] Example 2. Alternative, renewable, and / or recyclable feed

[0115] In addition, for illustrative purposes, two sustainable feedstocks are provided: recyclable feedstock R1 and recycled feedstock C1. R1 is a conventionally purified glycerol ester feedstock of animal fats / vegetable oils, and C1 is a conventionally purified liquefied waste plastic (obtained from the thermal degradation / pyrolysis of polyolefin waste plastics). R1 ​​is mixed with a pre-hydrogenated liquid stream (product recycling) as a diluent for catalytic pre-hydrogenation, followed by gas-liquid separation. C1 is then subjected to catalytic pre-hydrogenation, followed by gas-liquid separation and further fractionation. Certain characteristics of the resulting pre-hydrogenated recyclable feedstock R1 and pre-hydrogenated recycled feedstock C1 are then analyzed and reported in Table 3.

[0116] Table 3. Some characteristics of the pre-hydrogenated regenerative feed R1 and the pre-hydrogenated recycle feed C1. The contents of n-chain alkanes, iso-chain alkanes, cycloalkanes, and aromatics, as well as certain carbon number ranges, were determined by GCxGC-FID / GCxGC-MS.

[0117]

[0118] In addition, for illustrative purposes, two sustainable feedstocks are provided: recyclable feedstock R1 and recycled feedstock C1. R1 is a conventionally purified glycerol ester feedstock of animal fats / vegetable oils, and C1 is a conventionally purified liquefied waste plastic (obtained from the thermal degradation / pyrolysis of polyolefin waste plastics). R1 ​​was mixed with a pre-hydrogenated liquid stream (product recycling) as a diluent for catalytic pre-hydrogenation, followed by gas-liquid separation. C1 was subjected to catalytic pre-hydrogenation, followed by gas-liquid separation and further fractionation. Certain characteristics of the resulting pre-hydrogenated recyclable feedstock R1 and pre-hydrogenated recycled feedstock C1 were then analyzed and reported in Table 3.

[0119] Table 3. Some characteristics of the pre-hydrogenated regenerative feed R1 and the pre-hydrogenated recycle feed C1. The contents of n-chain alkanes, iso-chain alkanes, cycloalkanes, and aromatics, as well as certain carbon number ranges, were determined by GCxGC-FID / GCxGC-MS.

[0120] Example 3. Yield of recoverable fraction / product

[0121] The yields of exemplary fractions / products that can be recovered from this method (using the feed and method disclosed in Example 1) are given below. The properties of the recovered fractions and their suitability for certain applications are also investigated and reported in Examples 4 through 9.

[0122] Table 4. Estimated yields (wt.-%) of recoverable fractions from this method and approximate boiling ranges (IBP-FBP, °C), with hydrotreating feed containing 75 wt.-% petroleum feed and 25 wt.-% sustainable feed S2 or S3.

[0123]

[0124] Example 4. Naphtha fraction - heavy naphtha

[0125] Table 5. Heavy naphtha fractions obtained by this method using three different renewable pre-hydrogenated feedstocks and by other similar methods using petroleum reference feedstock P. R Certain characteristics of the obtained heavy naphtha fraction. The contents of alkanes, cycloalkanes, alkenes, heteroatomic compounds, and aromatics were determined by GC-FID / GC-MS.

[0126]

[0127] The research octane number (RON) of a pure naphtha fraction or a naphtha fraction blended with another gasoline component having a known octane number can be measured and then given as blended RON (bRON). As used throughout, bRON refers to the corrected bRON, i.e., the corrected value obtained by subtracting 0.2 from the measured value (according to Section 5.6 of EN 228:2012 as amended 2017). Throughout this document, clean research octane number refers to the octane number achieved without the use of octane-enhancing additives. Standard methods for RON measurement are given, for example, in ASTM D2699-2022 or EN ISO 5164-2014. The measurement and calculation of bRON are known in the art and have been disclosed, for example, in US4244704A. Due to the small sample volume, the octane number here is determined by blending with a commercial gasoline component (alkylate) having a high isoparaffin content (referred to as the "second component"). The blended octane number of the bRON sample is calculated using the following equation: Surprisingly, as reported in the table above, incorporating renewable content leads to an increase in bRON value compared to the 100% petroleum reference, thereby enhancing the value of naphtha fractions obtainable through this method as blend components in gasoline fuels. The results show that the higher the CTO content in the pre-hydrotreated feed, the higher the bRON of the naphtha fraction.

[0128] As can also be seen from the table above, compared to a 100% petroleum reference, this method can produce naphtha fractions with renewable content without substantially altering their other properties. From a process point of view, it is highly advantageous to incorporate renewable content, for example, as an intermediate stream used as (co)feed in another process unit, without substantially altering it in other ways, thereby reducing or avoiding the need for adjustments to the downstream process. Enhanced flexibility is achieved, allowing petroleum-feed-dominant refineries to periodically co-feed with renewable and / or recycled feedstocks, or at least partially sustainable refineries to periodically revert to petroleum-feed-only feedstocks, for example, depending on the availability of suitable renewable and / or recycled feedstocks, without requiring back-and-forth adjustments to the downstream process. By appropriately selecting the IBP, for example, the content of cyclohexane (boiling point around 81°C) can be minimized to, for example, << 1 wt.-%, making the naphtha fractions obtainable by this method an excellent (co)feed for reforming units, where high cycloalkane content can be converted to high aromatic content without a significant increase in benzene content. This is advantageous for using the reformed products obtained as gasoline fuel components.

[0129] The naphtha fraction obtained through this method also offers advantages over 100% renewable gasoline fuel range components (HVO gasoline) produced by HDO and isomerization of fatty feedstocks. Typical HVO gasoline has a very high alkane content (…). 90 wt.-%), high content of n-chain alkanes ( The naphtha fractions obtained by this method have very low cycloalkanes (< 10 wt.-%), very low cycloalkanes (< 10 wt.-%), and are essentially free of aromatics, limiting their octane numbers and thus their blending ratios. Despite having biogenic carbon content of 8 to 20 wt.-% based on the total weight of carbon in the fraction (TC), the naphtha fractions obtained by this method have cycloalkanes content at least as high as 100% petroleum references, and their aromatic content is also comparable.

[0130] Example 5. Boiling Range Fraction of Aviation Fuel

[0131] Table 6. Certain properties of aviation fuel boiling range fractions (Bio-AFC), 100% fossil JETA1 aviation fuel and its two blends obtained by this method using CTO as a pre-hydrogenated feedstock, and certain aviation fuel specification properties specified in ASTM D1655-23, Table 1, and Table A1.1. Alkane, cycloalkanes, and aromatics contents were determined by GCxGC-FID / GCxGC-MS (unless otherwise specified).

[0132] EN ISO 3405, Calculation of values ​​measured by ASTM D2887-2022e1 ASTM D7236-16a (2021) (Small Scale Closed Cup Method) # ASTM D1655-23 Table A1.1 Extended Requirements As can be seen from the table above, this method not only produces aviation fuel boiling range fractions with renewable content but also possesses other desired properties for blend components used in aviation fuels. For example, the density of 100% renewable aviation fuel components (HVO SAFs) produced from fatty feedstocks via HDO and isomerization is typically at or below the lower limit required in Table 1 of ASTM D7566-2021, limiting their blending ratio. Typical HVO SAFs also have a lower volumetric net heat of combustion compared to fossil aviation fuel components. The aviation fuel boiling range fractions obtained by this method have significantly higher densities and higher volumetric net heat of combustion, comparable to fossil aviation fuel components. For high-performance, volume-constrained aircraft, the net heat of combustion per unit mass and the volume of fuel loaded determine the overall safety margin. Furthermore, proper operation of aircraft engines requires maximum net combustion energy per unit volume of aviation fuel. Therefore, incorporating blend components with renewable content without reducing the volumetric net heat of combustion of the fuel would be highly advantageous. Incorporating the aviation fuel boiling range fractions obtainable through this method effectively increases the net heat of combustion of the aviation fuel. Furthermore, the aviation fuel boiling range fractions provided by this invention have a very low naphthalene content, but, unlike, for example, HVO SAF, a higher aromatic content of approximately 9 wt.-%, which in no way limits its incorporation as a blend component, but rather helps to meet the extended specification of a minimum of 8.4 wt.-% aromatics as specified in Table A1.1 of ASTM D1655-23.

[0133] WO 2021105557 discloses aviation fuel boiling range fractions that can be obtained by methods somewhat similar to those disclosed herein, however using a hydrotreated feedstock comprising unhydrotreated tall oil asphalt (TOP) and petroleum feed. The aviation fuel boiling range fractions obtained in WO 2021105557 have been found suitable as blending components in aviation fuels, but they must be recovered to a relatively narrow range (T50–T10 14°C; T90–T10 30°C) and their final boiling point must also be limited (FBP 250°C) to control their properties, such as flowability, to allow them to be incorporated into aviation fuels while still meeting, for example, the kinematic viscosity specifications at -20°C listed in Table 1 of ASTM D1655-2023. As can be seen from the table above, this method can recover aviation fuel boiling range fractions with a much wider boiling point fraction and higher FBP, and still has sufficient fluidity for kinematic viscosity at -20°C to allow it to be incorporated into aviation fuel at an increased blending ratio.

[0134] Example 6. Light Gas Oil (LGO) Fraction

[0135] Table 7. Some characteristics of light gas oil fractions obtained by this method using three different renewable pre-hydrogenated feedstocks, and by other similar methods using petroleum reference feedstock P. R Certain characteristics of the obtained light gas oil fraction, and certain diesel fuel specifications specified in EN 590:2022. Chemical composition, i.e., the content of alkanes, cycloalkanes, and aromatics, was determined by GCxGC-FID / GCxGC-MS. Table 2 of EN 590:2022 refers to the climate-related requirements for diesel fuels in temperate climates, and Table 3 of EN 590:2022 refers to the climate-related requirements for diesel fuels in cold and frigid winter climates.

[0136]

[0137] As can be seen from the table above, the introduction of renewable content leads to an increase in cetane number. Therefore, less or no cetane number improver may be needed to meet cetane number specifications, such as those proposed in EN 590:2022. A decrease in cloud point and CFPP was observed, but only when using a renewable pre-hydrotreated feed containing 70 wt.-% animal fat. When using 100 wt.-% CTO, the cloud point and CFPP remained essentially the same as for a 100% petroleum reference. The fraction can be recovered with a wide boiling range and has a significant biogenic carbon content (17-23 wt.-%, based on the total weight of carbon (TC) in the fraction).

[0138] The above shows that the light gas oil fraction obtained by this method meets the diesel fuel specifications of EN 590:2022 (except for the flash point) in pure form; however, this can be easily addressed by slightly adjusting the cut-off point (IBP). Therefore, the results indicate that the light gas oil fraction obtained by this method can be used as a blend component or even as a pure product for diesel fuel: the fraction obtained using a pre-hydrotreated feedstock containing 30 wt.-% CTO is suitable for use as a pure product in temperate climate diesel fuels (EN 590:2022 Tables 1 and 2), and the fraction obtained using a pre-hydrotreated feedstock with a higher CTO content is suitable for use as a pure product in frigid and Arctic winter climate diesel fuels (EN 590:2022 Tables 1 and 3). Given the significant biogenic carbon content, it is surprising that such good cold properties can be achieved without isomerization.

[0139] Example 7. Medium Gas Oil (MGO) Fraction

[0140] Table 8. Some characteristics of intermediate gas oil fractions obtained by this method using three different renewable pre-hydrogenated feedstocks, and by other similar methods using petroleum reference feedstock P. R Certain characteristics of the obtained intermediate gas oil fraction, as well as certain diesel fuel specifications specified in EN 590:2022 and certain marine fuel specifications specified in Table 1 (Distillate Marine Fuels) of ISO 8217-2017 (e.g., DMA category). The content of alkanes, cycloalkanes, and aromatics was determined by GCxGC-FID / GCxGC-MS. Table 2 of EN 590:2022 refers to the climate-related requirements for diesel fuels in temperate climates, and Table 3 of EN 590:2022 refers to the climate-related requirements for diesel fuels in cold and frigid winter climates.

[0141]

[0142] As can be seen from the table above, the incorporation of renewable content leads to increased kinematic viscosity, higher cetane number, and lower aromatic content. A decrease in cold properties (including cloud point and CFPP) was also observed.

[0143] The table above also shows the intermediate gas oil fractions obtained by this method that meet or exceed the marine fuel specifications for categories DMA, DMZ, and DMB in all respects of ISO 8217-2017 Table 1. Surprisingly, this is achieved through a high biomass carbon content in the intermediate gas oil fractions. Due to their high quality, these fractions can be used to improve the performance of marine fuel fractions and / or to optimize the economics of the blend, for example, by blending with fractions that do not meet the requirements of ISO 8217-2017 Table 1 for DMA, DMZ, or DMB, or by blending these fractions with other components / fractions to produce fuels that meet the requirements of DMX, DMA, DMZ, RMA, RMB, RMD, RME, RMG, or RMK as specified in ISO 8217-2017.

[0144] Furthermore, the table above shows that the intermediate gas oil fraction obtained by this method meets all the properties required by the diesel fuel specifications of EN 590:2022, except for the density when using a pre-hydrotreated feed containing 60 wt.% or more CTO. However, the density can be easily adjusted, for example, by limiting the distillation endpoint (FBP). Therefore, the results indicate that the intermediate gas oil fraction obtained by this method can be used as a blend component, or even in pure form for diesel fuel.

[0145] The results of blending tests with 100% renewable winter-grade HVO diesel (NRD) and 100% petroleum-grade cold-weather diesel (DIR) are reported below. The density, viscosity, bio-based carbon content, and chemical composition of the blends are presented in the table below. Viscosity was calculated based on measurements of the blend components in pure form (EN ISO 3104-2020) using Walther empirical correlation and viscosity mixing rules. Other properties were calculated using linear equations based on measurements of the blend components in pure form (density at 15°C by EN ISO 12185-1996, bio-based carbon content by EN 16640:2017, and the contents of n-alkanes (nP), isoalkanes (iP), cycloalkanes (N), and aromatics (A) determined by GCxGC-FID / GCxGC-MS).

[0146] Table 9. 100% Renewable Winter Grade HVO Diesel (NRD) and 100% Petroleum Cold-Region Grade Diesel (DIR), and their comparison with intermediate gas oil fractions obtained by this method using three different renewable feedstocks (MGO obtained with P+S1, P+S2, or P+S3), and those obtained by other similar methods using petroleum reference feedstock P. RThe density, viscosity, biogenic carbon content, and chemical composition of the blends obtained from the intermediate gas oil fraction were determined. Blend amount is expressed as vol-% (%). Density, kinematic viscosity, biogenic carbon content, and the contents of n-alkanes (nP), iso-alkanes (iP), cycloalkanes (N), and aromatics (A) were obtained as described above.

[0147]

[0148] As shown in the table above, the intermediate gas oil fraction obtained by this method can be used as a blending component within a wide blending ratio range, for example, with 100% petroleum cold-climate diesel (DIR) and 100% renewable winter-grade HVO diesel (NRD). Based on the above data, the intermediate gas oil fraction obtained by this method can, for example, be blended with 100% renewable winter-grade HVO diesel at a volume ratio of about 55:45 to about 95:5 to meet the EN 590 temperate climate diesel specification requirements, and with 100% petroleum cold-climate diesel (DIR) at a volume ratio of about 20:80 to about 90:10. Furthermore, when blended with 100% petroleum cold-climate diesel, all intermediate gas oil fractions obtained by this method help control the total aromatics content, and when blended with 100% renewable winter-grade HVO diesel, they help increase the density to the desired level. By using the intermediate gas oil fraction obtained by this method and 100% renewable winter-grade HVO diesel as blending components, a very high bio-source carbon content was achieved while still meeting the density requirements for diesel fuel in Table 1 of EN 590:2022.

[0149] Example 8. Heavy Gas Oil (HGO) Fraction

[0150] Table 10. Some characteristics of heavy gas oil fractions obtained by this method using three different renewable pre-hydrogenated feedstocks, and by other similar methods using petroleum reference feedstock P. R Certain characteristics of the obtained heavy gas oil fraction, as well as certain diesel fuel specifications as specified in EN 590:2022 and certain marine fuel specifications as specified in ISO 8217-2017, Table 1 (for distillate marine fuels) (DMB category). The content of alkanes, cycloalkanes, and aromatics was determined by GCxGC-FID / GCxGC-MS. Table 2 of EN 590:2022 refers to the climate-related requirements for diesel fuels in temperate climates, and Table 3 of EN 590:2022 refers to the climate-related requirements for diesel fuels in cold and frigid winter climates.

[0151]

[0152] As can be seen from the table above, the heavy gas oil fraction obtained by this method meets or exceeds the marine fuel specifications for DMB category in Table 1 of ISO 8217-2017 in all respects. The pour point of the sample was not measured. However, based on the cloud point and CFPP results, the pour point should not be an issue for DMB (ISO 8217-2017 limits the summer class to +6°C). Surprisingly, this was achieved with a high biogenic carbon content (42-49 wt.-%, based on the total weight of carbon (TC) in the fraction) in the heavy gas oil fraction. Due to their high quality, these fractions can therefore be used to improve the performance of fractional marine fuels and / or to optimize the economics of blends, for example by blending with fractions that do not meet the requirements for DMB in ISO 8217-2017, or by blending these fractions with other components / fractions to produce fuels that meet the requirements for DMX, DMA, DMZ, RMA, RMB, RMD, RME, RMG or RMK as specified in ISO 8217-2017.

[0153] Furthermore, the table above shows that the heavy gas oil fraction obtained by this method meets all other properties required by the diesel fuel specifications of EN 590:2022, except for density and viscosity. Therefore, the results indicate that the intermediate gas oil fraction obtained by this method can be used as a blending component in diesel fuel and can be used with other blending components having lower density and viscosity, such as with cold-weather diesel.

[0154] The results of blending tests with 100% petroleum cold-weather grade diesel (DIR) are reported below. The density, viscosity, bio-based carbon content, and chemical composition of the blends are presented in the table below. Viscosity was calculated based on measurements of the blend components in pure form (EN ISO 3104-2020) using Walther empirical correlation and viscosity mixing rules. Other properties were calculated using linear equations based on measurements of the blend components in pure form (density at 15°C according to EN ISO 12185-1996, bio-based carbon content according to EN 16640:2017, and the contents of n-alkanes (nP), isoalkanes (iP), cycloalkanes (N), and aromatics (A) as determined by GCxGC-FID / GCxGC-MS).

[0155] Table 11. 100% petroleum cold-weather grade diesel (DIR), and their comparison with heavy gas oil fractions obtained by this method using three different renewable feedstocks (HGO obtained by processing P+S1, P+S2, or P+S3), and those obtained by other similar methods using petroleum reference feedstock P. RThe density, viscosity, biogenic carbon content, and chemical composition of the obtained blends of heavy gas oil fractions were determined. Blend amount is expressed as vol-% (%). Density, kinematic viscosity, biogenic carbon content, and the contents of n-alkanes (nP), iso-alkanes (iP), cycloalkanes (N), and aromatics (A) were obtained as described above.

[0156]

[0157] As shown in the table above, the heavy gas oil fraction obtained by this method can be used as a blending component within a wide blending ratio range, for example, blending with 100% petroleum cold-water diesel (DIR). Based on the above data, the heavy gas oil fraction obtained by this method can be blended with 100% petroleum cold-water grade diesel (DIR) at a volume ratio of approximately 20:80 to approximately 70:30. Furthermore, when blended with 100% petroleum cold-water diesel, the heavy gas oil fraction obtained by this method can help control the total aromatics content. By using the heavy gas oil fraction obtained by this method and 100% petroleum cold-water diesel as blending components, a bio-based carbon content of at least 30 wt.% based on the total weight (TC) of carbon in the fraction is achieved, while still meeting the density and viscosity requirements for diesel fuels in Table 1 of EN 590:2022.

[0158] Example 9. Separation section bottom material - residual marine fuel components

[0159] Table 12. Certain characteristics of residual marine fuel components obtained using this method with three different renewable pre-hydrogenated feedstocks, and using petroleum reference feedstock P through other similar methods. R Certain properties of the obtained residual marine fuel components, and certain marine fuel specification properties specified in Table 2 (Residual Marine Fuels) (Category RMB) of ISO 8217-2017.

[0160]

[0161] As can be seen from Table 12, this method can produce marine fuel range components that not only have an unexpectedly high renewable content, but also have other properties required for blending components of residual marine fuels (i.e., residual marine fuel components).

[0162] Most of the results reported in Table 12 meet the requirements of ISO 8217-2017 Table 2 for residual marine fuel grade RMB. In fact, the obtained residual marine fuel components can also be used as blending components for distillate marine fuels according to ISO 8217-2017 Table 1 DMB category. The flash point increases when renewable content is incorporated into the hydrotreated feed, which is advantageous for marine fuels. The pour point and kinematic viscosity at 50°C are above specification limits. However, this is not a concern, as these properties can be adjusted to specifications, for example, with other blending components. Furthermore, the pour point is generally not an issue for ships using residual fuel grades, as these ships heat the fuel for onboard processing before use. The sulfur, nitrogen, and oxygen content of the residual marine fuel components recovered from this method is significantly reduced. This is beneficial for fuel use. One of the most important findings is the unexpectedly high bio-based carbon content in the recovered residual marine fuel components, with the total carbon weight (TC) in the component reaching as high as 33 wt.%. The results showed that the higher the CTO content in the pre-hydrotreated feed, the higher the bio-based carbon content in the recovered residual marine fuel components. In addition to the high bio-based carbon content, another important finding was improved lubricity and free lubricity reduction (HFRR). Higher CTO content in the pre-hydrotreated feed resulted in better HFRR results. The HFRR result based entirely on petroleum-based residual marine fuel components (reference) was 210 µm / 60°C. When 60 wt.% of the renewable feed used in pre-hydrotreated was CTO, the result improved by 28 µm / 60°C to 182 µm / 60°C, and when the renewable feed in pre-hydrotreated was 100 wt.% CTO, the result improved by 73 µm / 60°C (compared to the reference), yielding a result of 137 µm / 60°C.

[0163] WO 2022129681 discloses a range of marine fuel components that can be obtained by pre-hydrogenating and distilling tall oil bitumen (TOP) to recover the pre-hydrogenated distillate bottoms. The pre-hydrogenated distillate bottoms obtained in WO 2022129681 were found suitable as blend components in residual marine fuels, but had >16 times higher nitrogen content and 2.5-3.5 times higher aromatic content compared to the marine fuel range components obtained by this method. High aromatic content in fuels is generally associated with increased soot and smoke formation and higher nitrogen content in NOx formation during combustion. This method enables the provision of residual marine fuel components with renewable content, possessing improved properties for marine fuels, particularly due to their very low S and N content, low aromatic content, high flash point, and good lubricity in terms of HFRR.

[0164] Various implementation methods have been presented. It should be understood that in this document, the words “including,” “comprising,” and “containing” are each used as open-ended expressions and are not intended to be exclusive.

[0165] The foregoing description, through non-limiting examples of specific implementations and embodiments of the invention, has provided a complete and informative description of the best mode currently conceived by the inventors for carrying out the invention. However, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing embodiments, but can be implemented in other embodiments or different combinations of embodiments using equivalent means without departing from the characteristics of the invention.

[0166] Furthermore, some features of the disclosed embodiments of the present invention can be used advantageously without the need for corresponding use of other features. Therefore, the foregoing description should be considered merely illustrative of the principles of the invention and not limiting of them. Thus, the scope of the invention is limited only by the appended claims.

Claims

1. A method for producing hydrocarbon fractions, the method comprising: a) In a pre-hydroconversion reactor, in the presence of a pre-hydroconversion catalyst, at least one or more of vegetable oils, animal fats, microbial oils, lignocellulose-derived biocrude oils, and / or liquefied organic wastes are pre-hydroconverted to obtain a pre-hydroconversion effluent, and a petroleum feed is co-fed into the pre-hydroconversion reactor, and / or the petroleum feed is combined with at least a portion of the pre-hydroconversion effluent to obtain a hydrotreated feed having petroleum content and renewable and / or recyclable content. b) The hydrotreatment feed is hydrotreated in a hydrotreatment reactor in the presence of a hydrotreatment catalyst to obtain a hydrotreatment effluent. c) Introducing at least a portion of the hydrotreated effluent into a separation section and recovering at least three different distillates and a separation section bottoms product from the separation section, the separation section bottoms product having an initial boiling point of at least 300°C, such as in the range of 300°C to 420°C, preferably at least 320°C, such as in the range of 320°C to 410°C, more preferably at least 340°C, such as in the range of 340°C to 400°C (EN ISO 3405-2019). d) Recovering residual marine fuel components from the bottom of the separation section, preferably by separating a portion of the bottom of the separation section. e) In a hydrocracking reactor, in the presence of a hydrocracking catalyst, a hydrocracking feed containing a portion of the bottom product of the separation section is hydrocracking to obtain a hydrocracking effluent, and at least a portion of the hydrocracking effluent and the hydrotreated effluent are co-fed into the separation section.

2. The method according to claim 1, wherein, The at least three different distillates include naphtha fractions and at least: - Aviation fuel boiling range fraction and heavy gas oil fraction, or - Light gas oil fraction and heavy gas oil fraction, or - Aviation fuel boiling range fraction and intermediate gas oil fraction - Preferably, the at least three different distillates include naphtha fraction, heavy gas oil fraction, and aviation fuel boiling range fraction or light gas oil fraction.

3. The method according to claim 1 or 2, wherein, The at least three different distillates include at least three or more of the following: - Naphtha fraction having a boiling point range of 1 BP to 230°C, preferably 20°C to 220°C (ASTM D7096-2019), and optionally, having a difference between T90 and T10 temperatures in the range of 30°C to 150°C, preferably 50°C to 120°C (ASTM D7096-2019). - Boiling range fraction of aviation fuel, having a boiling point range of 120°C to 310°C, preferably 130°C to 300°C (EN ISO 3405-2019), and optionally, having a difference between T90 and T10 temperatures in the range of 40°C to 200°C, preferably 60°C to 180°C (EN ISO 3405-2019). - Light gas oil fraction, having a boiling point range of 120°C to 330°C, preferably 130°C to 320°C (EN ISO 3405-2019), and optionally, having a difference between T90 and T10 temperatures in the range of 50°C to 200°C, preferably 80°C to 190°C (EN ISO 3405-2019). - Intermediate gas oil fraction, having a boiling point range of 190°C to 390°C, preferably 200°C to 380°C (EN ISO 3405-2019), and optionally, having a difference between T90 and T10 temperatures in the range of 50°C to 200°C, preferably 80°C to 200°C (EN ISO 3405-2019); and / or - Heavy gas oil fraction, having a boiling point range of 270°C to 430°C, preferably 280°C to 410°C (EN ISO 3405-2019), and optionally, having a difference between T90 and T10 temperatures in the range of 5°C to 140°C, preferably 10°C to 100°C (EN ISO 3405-2019).

4. The method according to any one of the preceding claims, wherein, Based on the total weight of the bottom material of the separation section, the residual marine fuel components are recovered from the bottom material of the separation section at a rate ranging from 3 wt.-% to 30 wt.-%, preferably from 3 wt.-% to 20 wt.-%, and more preferably from 5 wt.-% to 15 wt.-%.

5. The method according to any one of the preceding claims, wherein, The recirculated hydrogen stream, fuel gas, and / or light naphtha fraction are further recovered from the separation section, and at least a portion of the fuel gas and / or light naphtha fraction is fed to a hydrogen production unit, preferably to a steam reforming unit, to obtain syngas, from which a supplementary hydrogen stream is subsequently recovered; and optionally, at least a portion of the recirculated hydrogen stream and / or the supplementary hydrogen stream is recycled to the pre-hydrogenation conversion in step a), the hydrotreating in step b), and / or the hydrocracking in step e).

6. The method according to any one of the preceding claims, wherein, At least a naphtha fraction is recovered from the separation section, wherein the naphtha fraction preferably has a boiling point range of 20°C to 200°C, more preferably 85°C to 190°C (ASTM D7096-2019), and at least a portion of the naphtha fraction is fed into a catalytic naphtha reformer to obtain a reformed gasoline fraction.

7. The method according to any one of the preceding claims, wherein, The hydrotreating feedstock has a petroleum content in the range of 5 to 95 wt.-%, preferably 10 to 95 wt.-%, more preferably 15 to 90 wt.-%, and even more preferably 20 to 85 wt.-%.

8. The method according to any one of the preceding claims, wherein, Based on the total weight of the petroleum feed, the petroleum feed comprises: greater than 30 wt.-%, preferably greater than 40 wt.-%, more preferably greater than 50 wt.-%, of hydrocarbons with a boiling point in the range of 100°C to 400°C (ASTM D2887-2023); and greater than 10 wt.-%, preferably at least 20 wt.-%, more preferably at least 30 wt.-%, of hydrocarbons with a boiling point above 380°C (ASTM D2887-2023); and / or at least one or more of the following from crude oil: atmospheric distillation bottoms, vacuum distillate, atmospheric and / or vacuum distillate from (hydrocracking) atmospheric and / or vacuum distillation bottoms, atmospheric and / or vacuum distillate from (hydrocracking) atmospheric and / or vacuum distillate, and / or atmospheric bottoms from (hydrocracking) vacuum distillate.

9. The method according to any one of the preceding claims, wherein, The method includes a) performing the pre-hydrogenation conversion on at least one or more of vegetable oils, animal fats, microbial oils and / or liquefied organic waste, preferably at least one or more of vegetable oils, animal fats and / or microbial oils.

10. The method according to any one of the preceding claims, wherein, At least a naphtha fraction, preferably a stabilized naphtha fraction, is recovered from the separation section, wherein the naphtha fraction has at least one or more of the following properties: - The density at 15°C is in the range of 730 to 790 kg / m3, preferably 735 to 785 kg / m3 (EN ISO 12185-1996). - The sulfur content is up to 20 mg / kg, preferably up to 15 mg / kg (ASTM D5623-2019). - The weight ratio of cycloalkanes to aromatics is at least 6.0, preferably at least 8.0 (GC-FID / GC-MS). - The aromatic content is in the range of 0.5 to 15.0 wt.-%, preferably 1.0 to 10.0 wt.-%, (GC-FID / GC-MS). - The cycloalkane content is in the range of 40.0 to 90.0 wt.-%, preferably 40.0 to 80.0 wt.-%, (GC-FID / GC-MS). - Cyclohexane content less than 5.0 wt.-%, preferably less than 2.0 wt.-%, (GC-FID / GC-MS), and / or - Based on the total weight of carbon (TC) in the fraction, the bio-based carbon content is in the range of 1 to 50 wt.-%, preferably 3 to 40 wt.-%, (EN 16640:2017).

11. The method according to any one of the preceding claims, wherein, At least one aviation fuel boiling range fraction is recovered from the separation section, wherein the aviation fuel boiling range fraction has at least one or more of the following properties: - The temperature difference between T50 and T10 is at least 20°C, preferably at least 40°C (EN ISO 3405-2019). - T10 temperature is up to 205°C, preferably up to 190°C (EN ISO 3405-2019). - The kinematic viscosity at -20°C is at most 10.0 mm² / s, preferably at most 8.0 mm² / s (EN ISO 3104-2020). - The density at 15°C is in the range of 775 to 840 kg / m3, preferably 780 to 830 kg / m3 (EN ISO 12185-1996). - Flash point is at least 38°C, preferably at least 40°C (IP 170-2013, Abel closed cup method). - The sulfur content is up to 20 mg / kg, preferably up to 10 mg / kg (EN ISO 20846-2019). - The cycloalkanes content is in the range of 40.0 to 80.0 wt.-%, preferably 50.0 to 75.0 wt.-%, (GCxGC-FID / GCxGC-MS). - The weight ratio of the total amount of cycloalkanes and isoalkanes to the amount of n-alkanes is in the range of 4.0 to 25.0, preferably 5.0 to 20.0 (GCxGC-FID / GCxGC-MS). - Freezing point up to -30°C, preferably up to -35°C (IP 529-2016), and / or - Based on the total weight of carbon (TC) in the fraction, the bio-based carbon content is in the range of 5 to 50 wt.-%, preferably 10 to 40 wt.-%, (EN 16640:2017).

12. The method according to any one of the preceding claims, wherein, At least a light gas oil fraction is recovered from the separation section, wherein the light gas oil fraction has at least one or more of the following properties: - The kinematic viscosity at 40°C is in the range of 1.2 to 4.5 mm² / s, preferably 1.5 to 4.0 mm² / s (EN ISO3104-2020). - The density at 15°C is in the range of 795 to 860 kg / m3, preferably 810 to 845 kg / m3 (EN ISO 12185-1996). - Flash point of at least 50°C, preferably at least 55°C (EN ISO 2719-2016 Pensky-Martens closed cup method). - The aromatic content is up to 25.0 wt.-%, preferably up to 20.0 wt.-%, (GCxGC-FID / GCxGC-MS). - The weight ratio of cycloalkanes to alkanes is in the range of 0.8 to 3.0, preferably 1.0 to 2.5 (GCxGC-FID / GCxGC-MS). - The cetane number is at least 43.0, preferably at least 44.0 (EN 15195:2023). - Cloud point up to +5°C, preferably up to -5°C (ASTM D7689-2021), and / or - Based on the total weight of carbon (TC) in the fraction, the bio-based carbon content is in the range of 5 to 60 wt.-%, preferably 10 to 40 wt.-%, (EN 16640:2017).

13. The method according to any one of the preceding claims, wherein, At least an intermediate gas oil fraction is recovered from the separation section, wherein the intermediate gas oil fraction has at least one or more of the following properties: - The kinematic viscosity at 40°C is in the range of 2.0 to 11.0 mm² / s, preferably 3.0 to 6.0 mm² / s (EN ISO3104-2020). - The density at 15°C is in the range of 815 to 900 kg / m3, preferably 820 to 860 kg / m3 (EN ISO 12185-1996). - Flash point of at least 60°C, preferably at least 80°C (EN ISO 2719-2016 Pensky-Martens closed cup method). - The sulfur content is up to 50 mg / kg, preferably up to 5 mg / kg (EN ISO 20846-2019). - The aromatic content is up to 30.0 wt.-%, preferably up to 25.0 wt.-%, (GCxGC-FID / GCxGC-MS). - The weight ratio of cycloalkanes to alkanes is in the range of 0.8 to 2.5, preferably 1.0 to 2.0 (GCxGC-FID / GCxGC-MS). - The cetane number is at least 51.0, preferably at least 55.0 (EN 15195:2023). - Cloud point up to +10°C, preferably up to +5°C (ASTM D7689-2021), and / or - Based on the total weight of carbon (TC) in the fraction, the bio-based carbon content is in the range of 5 to 80 wt.-%, preferably 10 to 70 wt.-%, (EN 16640:2017).

14. The method according to any one of the preceding claims, wherein, At least a heavy gas oil fraction is recovered from the separation section, wherein the heavy gas oil fraction has at least one or more of the following properties: - The kinematic viscosity at 40°C is in the range of 4.0 to 12.0 mm² / s, preferably 5.0 to 11.0 mm² / s (EN ISO3104-2020). - The density at 15°C is in the range of 820 to 900 kg / m3, preferably 840 to 890 kg / m3 (EN ISO 12185-1996). - Flash point of at least 80°C, preferably at least 100°C (EN ISO 2719-2016 Pensky-Martens closed cup method). - The sulfur content is up to 100 mg / kg, preferably up to 10 mg / kg (EN ISO 20846-2019). - The aromatic content is up to 35.0 wt.-%, preferably up to 25.0 wt.-%, (GCxGC-FID / GCxGC-MS). - The weight ratio of cycloalkanes to alkanes is in the range of 0.5 to 1.5, preferably 0.8 to 1.5 (GCxGC-FID / GCxGC-MS). - The cetane number is at least 51.0, preferably at least 55.0 (EN 15195:2023). - Cloud point up to +25°C, preferably up to +20°C (ASTM D7689-2021), and / or - Based on the total weight of carbon (TC) in the fraction, the bio-based carbon content is in the range of 5 to 80 wt.-%, preferably 10 to 70 wt.-%, (EN 16640:2017).

15. The method according to any one of the preceding claims, wherein, The residual marine fuel components recovered from the bottom of the separation section, preferably obtained by separating a portion from the bottom of the separation section, have at least one or more of the following properties: - The kinematic viscosity at 40°C is in the range of 15 to 80 mm² / s, preferably 20 to 50 mm² / s (EN ISO 3104-2020). - The density at 15°C is in the range of 850 to 975 kg / m3, preferably 860 to 920 kg / m3 (EN ISO 12185-1996). - Flash point of at least 100°C, preferably at least 120°C (EN ISO 2719-2016 Pensky-Martens closed cup method). - The sulfur content is up to 150 mg / kg, preferably up to 15 mg / kg (EN ISO 20846-2019). - The nitrogen content is up to 10,000 mg / kg, preferably up to 8,000 mg / kg (ASTM D5762-2018a). - The aromatic content is up to 50.0 wt.-%, preferably up to 30.0 wt.-% (ASTM D2549-02 (2017)). - Lubricity expressed in high-frequency reciprocating test (HFRR) values ​​is up to 520 µm / 60°C, preferably up to 300 µm / 60°C (EN ISO 12156-1-2023), and / or - Based on the total weight of carbon (TC) in the fraction, the bio-based carbon content is in the range of 5 to 50 wt.-%, preferably 8 to 40 wt.-%, (EN 16640:2017).

16. The method according to any one of the preceding claims, wherein, Step a) includes: feeding the pre-hydroconversion effluent to a pre-hydroconversion fractionation to recover one or more pre-hydroconversion distillates and pre-hydroconversion fractionation bottoms, and combining the petroleum feed with the pre-hydroconversion fractionation bottoms to obtain the hydrotreating feed; the method further includes: f) Feeding the one or more pre-hydrogenated conversion distillates to a catalytic conversion, preferably to a catalytic conversion including at least hydroisomerization, more preferably to a catalytic conversion including at least hydrotreatment and hydroisomerization, optionally co-feeding with at least one or more of vegetable oils, animal fats, microbial oils, lignocellulose-derived biocrude oils and / or liquefied organic waste to obtain catalytic conversion effluent; and g) Optionally, at least aviation fuel components and / or diesel fuel components are recovered from the catalytic conversion effluent.

17. The method according to any one of the preceding claims, wherein, In step a), the prehydroconversion includes: in the prehydroconversion reactor, performing prehydroconversion and / or prehydrocracking, preferably at least prehydroconversion, in the presence of a prehydroconversion catalyst and / or a prehydrocracking catalyst, preferably at least prehydroconversion, to obtain the prehydroconversion effluent.

18. The method according to any one of the preceding claims, wherein, In step b), the hydrotreatment reactor further includes a dewaxing catalyst; and / or in step e), the hydrocracking reactor further includes a hydroisomerization catalyst.

19. The method according to any one of the preceding claims, wherein, The hydrotreating in the hydrotreating reactor is carried out under the following conditions: a temperature in the range of 300°C to 450°C, preferably 350°C to 420°C; a pressure in the range of 6 MPa to 20 MPa, preferably 10 MPa to 18 MPa; an H2 partial pressure at the inlet of the hydrotreating reactor in the range of 6 MPa to 10 MPa, preferably 10 MPa to 18 MPa; a weight hourly space velocity in the range of 0.1 to 10, preferably 0.2 to 8 kg hydrotreating feed / kg catalyst / hour; and an H2 to hydrotreating feed ratio in the range of 50 to 2000, preferably 100 to 1500 standard liters of H2 / liter of hydrotreating feed; and / or The hydrocracking in the hydrocracking reactor is carried out under the following conditions: temperature in the range of 280°C to 450°C, preferably 300°C to 420°C; pressure in the range of 8 MPa to 20 MPa, preferably 12 MPa to 18 MPa; H2 partial pressure at the inlet of the hydrocracking reactor in the range of 8 MPa to 20 MPa, preferably 12 MPa to 18 MPa; weight hourly space velocity in the range of 0.1 to 10, preferably 0.2 to 8 kg hydrocracking feed / kg catalyst / hour; and H2 to hydrocracking feed ratio in the range of 50 to 2000, preferably 500 to 1500 standard liters of H2 / liter of hydrocracking feed.

20. The method according to any one of the preceding claims, wherein, The prehydroconversion includes a prehydrogenation treatment, wherein the prehydrogenation treatment is carried out in the presence of a prehydrogenation catalyst under the following conditions: a temperature in the range of 300°C to 420°C, preferably 320°C to 380°C; a pressure in the range of 3 MPa to 15 MPa, preferably 4 MPa to 10 MPa; an H2 partial pressure at the inlet of the prehydroconversion reactor in the range of 3 MPa to 15 MPa, preferably 4 MPa to 10 MPa; a weight hourly space velocity in the range of 0.1 to 10, preferably 0.2 to 8 kg prehydroconversion feed / kg catalyst / hour; and an H2 to prehydroconversion feed ratio in the range of 50 to 2000, preferably 100 to 1500 standard liters of H2 / liter of prehydroconversion feed; and / or The prehydroconversion includes prehydrocracking, wherein the prehydrocracking is carried out under the following conditions: temperature in the range of 280°C to 450°C, preferably 300°C to 420°C; pressure in the range of 8 MPa to 20 MPa, preferably 12 MPa to 18 MPa; H2 partial pressure at the inlet of the prehydroconversion reactor in the range of 8 MPa to 20 MPa, preferably 12 MPa to 18 MPa; weight hourly space velocity in the range of 0.1 to 10, preferably 0.2 to 8 kg prehydroconversion feed / kg catalyst / hour; and H2 to prehydroconversion feed ratio in the range of 50 to 2000, preferably 500 to 1500 standard liters of H2 / liter of prehydroconversion feed.

21. A naphtha fraction having a boiling point range of 1 bp to 230°C, preferably 20°C to 220°C (ASTM D7096-2019), and a difference between T90 and T10 temperatures in the range of 30°C to 150°C, preferably 50°C to 120°C (ASTM D7096-2019), and optionally, based on the total weight (TC) of carbon in the fraction, having a biogenic carbon content in the range of 1 to 50 wt.-%, preferably 3 to 40 wt.-%, (EN 16640:2017), wherein, The naphtha fraction has at least one or more additional properties as defined in claim 10, and is preferably obtained by the method according to any one of claims 1 to 20.

22. An aviation fuel boiling range fraction having a boiling point range in the range of 120°C to 310°C, preferably 130°C to 300°C (EN ISO 3405-2019); a difference between T90 and T10 temperatures in the range of 40°C to 200°C, preferably 60°C to 180°C (EN ISO 3405-2019); and optionally, a biogenic carbon content in the range of 5 to 50 wt.-%, preferably 10 to 40 wt.-%, based on the total weight (TC) of carbon in the fraction (EN 16640:2017), wherein, The aviation fuel boiling range fraction has at least one or more additional properties as defined in claim 11, and is preferably obtained by the method according to any one of claims 1 to 20.

23. A light gas oil fraction having a boiling point range of 120°C to 330°C, preferably 130°C to 320°C (EN ISO 3405-2019); a difference between T90 and T10 temperatures in the range of 50°C to 200°C, preferably 80°C to 190°C (EN ISO 3405-2019); and optionally, a biogenic carbon content in the range of 5 to 60 wt.-%, preferably 10 to 40 wt.-%, based on the total weight (TC) of carbon in the fraction (EN 16640:2017), wherein, The light gas oil fraction has at least one or more additional properties as defined in claim 12, and is preferably obtained by the method according to any one of claims 1 to 20.

24. An intermediate gas oil fraction having a boiling point range of 190°C to 390°C, preferably 200°C to 380°C (EN ISO 3405-2019); a difference between T90 and T10 temperatures in the range of 50°C to 200°C, preferably 80°C to 200°C (EN ISO 3405-2019); and optionally, a biogenic carbon content in the range of 5 to 80 wt.-%, preferably 10 to 70 wt.-%, based on the total weight (TC) of carbon in the fraction (EN 16640:2017), wherein, The intermediate gas oil fraction has at least one or more additional properties as defined in claim 13, and is preferably obtained by the method according to any one of claims 1 to 20.

25. A heavy gas oil fraction having a boiling point range of 270°C to 430°C, preferably 280°C to 410°C (EN ISO 3405-2019); a difference between T90 and T10 temperatures in the range of 5°C to 140°C, preferably 10°C to 100°C (EN ISO 3405-2019); and optionally, a biogenic carbon content in the range of 5 to 80 wt.-%, preferably 10 to 70 wt.-%, based on the total weight (TC) of carbon in the fraction (EN 16640:2017), wherein, The heavy gas oil fraction has at least one or more additional properties as defined in claim 14, and is preferably obtained by the method according to any one of claims 1 to 20.

26. A residual marine fuel component having an initial boiling point of at least 300°C, such as in the range of 300°C to 420°C, preferably at least 320°C, such as in the range of 320°C to 410°C, more preferably at least 340°C, such as in the range of 340°C to 400°C (EN ISO 3405-2019); and optionally, a bio-based carbon content in the range of 5 to 50 wt.-%, preferably 8 to 40 wt.-%, based on the total weight (TC) of carbon in the fraction (EN 16640:2017), wherein, The residual marine fuel component has at least one or more additional properties as defined in claim 15, and is preferably obtained by the method according to any one of claims 1 to 20.

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