Stable hydrocarbon composition comprising a renewable base

Abstract

The invention relates to a stable hydrocarbon composition comprising: (a) 10% to 30% by weight of a renewable base comprising at least one component selected from a biomass pyrolysis oil and a residue of the vacuum distillation of a biomass pyrolysis oil, (b) 70% to 90% by weight of a fossil base containing at least 1% by weight of asphaltenes and having an aromatics content of at most 54% by weight.

Description

[0001] DESCRIPTION

[0002] TITLE: STABLE HYDROCARBON COMPOSITION COMPRISING A RENEWABLE BASE

[0003] Field of invention

[0004] The invention relates to a stable hydrocarbon composition comprising a renewable base, in particular based on biomass pyrolysis oil. The composition according to the invention can in particular be used as a base for marine fuel, as marine fuel or as a feedstock for a refining unit.

[0005] Prior art

[0006] Marine fuels are usually manufactured by mixing a residue (atmospheric residue, vacuum residue or visbreaking residue) with one or more fluxes usually of petroleum origin.

[0007] To reduce the environmental impact of marine fuels, producers are increasingly seeking to incorporate renewable components into their manufacturing processes. In particular, producers are seeking to produce fuels with a reduced overall greenhouse gas emissions balance, such as carbon dioxide, and a low sulfur content to limit emissions, particularly in Arctic regions.

[0008] Marine fuels containing renewable bases have been developed. For example, hydrotreated vegetable oils (HVO) or fatty acid methyl esters (FAME) can be incorporated into marine fuels. However, these renewable bases are too high in added value for marine applications.

[0009] Biomass pyrolysis oils could prove to be economically viable renewable bases when blended with fossil bases for marine applications or as feedstock for a refining unit. However, these pyrolysis oils are not miscible with fossil bases: a more or less rapid phase separation is observed after mixing, which results in a two-phase system that is not usable for marine applications or as feedstock for a refining unit. One way to improve the compatibility between biomass pyrolysis oils and fossil bases is to chemically transform them. A second approach is to add co-solvents to obtain a single phase. A third approach is to use block copolymers, which are expensive to synthesize, to stabilize oil-in-oil emulsions. These approaches, used separately or together, have a significant cost.

[0010] There is therefore a need to improve the compatibility between biomass pyrolysis oils and fossil fuel bases that is simpler to implement and less expensive.

[0011] Definitions

[0012] By "asphaltenes" we mean compounds insoluble in n-heptane and soluble in toluene, contained in particular in crude oils, bitumens, and coal. In general, asphaltenes include carbon, hydrogen, nitrogen, sulfur, vanadium, and nickel. The asphaltene content can be measured according to standard NF T60-115 (January 2000).

[0013] “Fluxant” means a hydrocarbon stream that allows one or more physical characteristics of another hydrocarbon stream to be modified so that they comply with specifications. The physical characteristic(s) that may be modified by the addition of a fluxant are chosen from: viscosity, density, sulfur content, pour point or carbon residue.

[0014] Crude oil refers to oil from a natural deposit, which is extracted in liquid form at atmospheric pressure. This term therefore refers to a natural product before refining, but which has already lost part of its deposit composition, the light hydrocarbon fraction leaving the liquid phase at the very place of its extraction.

[0015] "Petroleum product" means an effluent from a crude oil or effluent processing unit, or an effluent from a crude oil or effluent separation unit, or non-recoverable petroleum products such as slops. Heavy petroleum products are mixtures with a boiling point greater than or equal to 350°C, noted 350°C+. These include petroleum distillation residues, effluents from thermal conversion processes, catalytic cracking processes, hydrocracking processes, deep hydroconversion processes, atmospheric or vacuum residue hydrotreatment processes (ARDS or VRDS), or fuel oils from mixtures of heavy products.

[0016] The composition of a petroleum product in aromatic, saturates and resin compounds can be determined by the analytical method known as SARA, which allows the classification of the multiple hydrocarbon components into one of four categories based on their polarizability and polarity: saturates (S), aromatics (A), resin (R) or asphaltenes (As).

[0017] In petroleum products or crude oil, saturated (S) components (also referred to herein as "saturates") are generally non-polar molecules and include saturated hydrocarbons that may be linear, branched, or cyclic. For example, crude oils may contain from 15% by mass to about 85% by mass of saturated (S) components. These components are also generally known as paraffins, iso-paraffins, and naphthenes.

[0018] Aromatic components (A) (also referred to herein as "aromatics") contain one or more aromatic rings and are slightly more polarizable than saturated components (S). For example, crude oils may contain from about 10% by mass to about 45% by mass of aromatic components (A).

[0019] Resins (R) (also referred to herein as "resin components") and asphaltenes (As) in petroleum products typically have many cyclic moieties and / or aromatic rings but also contain polar substituents such as carboxylate groups. The molecular weights of the resin components (R) and asphaltene components (As) can vary, but asphaltenes are generally the largest components of crude oil in terms of molecular weight, with individual asphaltene molecules having mass distributions generally ranging from 400 to 1500 daltons. Asphaltenes can also form aggregates having molecular weights up to 20,000 daltons or can precipitate as particles.

[0020] By definition, resinous (R) components are distinguished from asphaltene (As) components by their solubility in various solvents. In particular, resinous (R) components are defined as the fraction soluble in light alkanes such as n-pentane, n-hexane, or n-heptane, but insoluble in liquid propane. Resins (R) have also been defined as the fraction that is strongly adsorbed in materials such as fuller's clay, alumina, or silica, so that they can only be desorbed by a solvent such as pyridine or a mixture of toluene and methanol. For example, crude oils can contain from about 5% by mass to about 40% by mass of resinous (R) components. Asphaltene (As) components are by definition insoluble even in excess n-heptane, but are usually soluble in benzene or toluene.Crude oils worldwide typically contain from 0% by mass to about 35% by mass of asphaltene (As) components.

[0021] Many analytical protocols for the SARA method are known, allowing the determination of the relative amounts of saturates (S), aromatics (A), resins (R) and asphaltenes (As) in a given crude oil or hydrocarbon sample. In general, the asphaltenes present are first separated by precipitation in n-heptane, and then, the resins, aromatics and saturates are separated and quantified by HPLC (High Performance Liquid Chromatography). In the present invention, the aromatic content of the fossil base can be performed by SARA analysis in accordance with ASTM D4124-09(2018).

[0022] Bleed: heavy fraction (very paraffinic) resulting from the hydrocracking of a distillate-type feedstock, usually corresponding to a unit bottom.

[0023] Kerosene cut from atmospheric distillation, usually having an initial distillation point of 150 to 180°C and a final distillation point of 225 to 250°C.

[0024] Diesel (gas oil in English): distillate cut from atmospheric, vacuum or visbreaker distillation, usually having an initial distillation point of 220°C to 240°C and a final distillation point of 350 to 380°C.

[0025] VGO (Vacuum gasoil): heavy vaporizable fraction resulting from vacuum distillation of an atmospheric residue. The boiling temperature range of this fraction is usually 360-380 to 540-600°C.

[0026] The characteristic called "S value" or "S-value" or "intrinsic stability" is measured according to the ASTM D7157-18 standard (2018 Revision). The S-value is the result of the combination of two parameters, the So parameter characteristic of the aromaticity of the oil matrix and the Sa parameter characteristic of the intrinsic stability of asphaltenes. These parameters are defined in the aforementioned standard and can be measured according to this standard.

[0027] Density at 15°C is measured according to ISO 12185:1996.

[0028] Kinematic viscosity at 50°C is measured according to ISO 3104:2020.

[0029] Pour point is measured according to ISO 3016:2019.

[0030] Sulfur content can be measured according to ISO 8754 or ASTM D4294.

[0031] Summary of the invention

[0032] A first subject of the invention relates to a stable hydrocarbon composition characterized in that it comprises:

[0033] (a) 10 to 30% by mass of a renewable base comprising at least one component selected from a biomass pyrolysis oil and a residue from the vacuum distillation of a biomass pyrolysis oil,

[0034] (b) 70 to 90% by mass of a fossil base containing at least 1% by mass of asphaltenes and having an aromatics content of not more than 54% by mass.

[0035] The composition according to the invention has the advantage of forming an emulsion that is stable over time, without phase separation. Without wishing to be bound by a theory, it is the combination of the specific maximum content of the fossil base in aromatics and its asphaltene content that makes it possible to obtain a stable composition.

[0036] Advantageously, the fossil base may contain at least 2% by mass of asphaltenes.

[0037] In one embodiment, the fossil base may contain from 2% to 10% by mass of asphaltenes, preferably from 2 to 8% by mass of asphaltenes, more preferably from 2 to 5% by mass of asphaltenes.

[0038] Advantageously, the fossil base may have a Sa parameter of 0.2 to 0.9, preferably 0.2 to 0.6, measured according to ASTM D7157-18 (2018 Revision) standard. Advantageously, at least one component of the fossil base may have a Sa parameter of 0.4 to 0.9 measured according to ASTM D7157-18 (2018 Revision) standard. Preferably, the component(s) having a Sa parameter of 0.4 to 0.9 advantageously represent(s) 10 to 65% of the total mass of the fossil base.

[0039] Advantageously, the fossil base may comprise at least one petroleum product containing asphaltenes and at least one flux, and optionally the fossil base having a flux content of 2 to 45% by mass, preferably 10 to 35% by mass relative to the total mass of the fossil base.

[0040] The fossil base may in particular comprise at least one flux chosen from (i) a diesel fuel from the direct distillation of petroleum, (ii) the products of vacuum distillation of an atmospheric residue, (iii) the products of atmospheric or vacuum distillation of effluents from conversion units, (iv) the products from catalytic cracking units and desulfurization and hydrodesulfurization units, (v) the products from steam cracking units.

[0041] Advantageously, the fossil base may comprise at least one component containing asphaltenes chosen from:

[0042] (i) atmospheric residues or vacuum residues from the distillation of crude oil, (ii) effluents, in particular residues, from thermal conversion processes, such as the visbreaking process,

[0043] (iii) effluents, in particular residues or slurry, from catalytic cracking processes, such as the FCC process (“Fluid Catalytic Cracking”),

[0044] (iv) effluents, in particular residues, from hydrotreatment, hydrocracking, deep hydroconversion, ARDS and VRDS processes,

[0045] (v) pitches resulting from physical separation processes, such as deasphalting, and mixtures of two or more of the petroleum products listed above.

[0046] Advantageously, the biomass pyrolysis oil may be obtained from a process of pyrolysis of a biomass chosen from (i) lignocellulosic biomass, (ii) herbaceous biomass, (iii) biomass from plants growing in or under water, (iv) algal biomass, (v) agricultural residues from livestock farming,

[0047] (vi) organic waste, (vii) paper, (viii) cardboard, and their mixtures.

[0048] Advantageously, the renewable base can contain from 20 to 60% by mass of oxygen.

[0049] The invention also relates to a composition for marine fuel consisting of, or comprising, the stable hydrocarbon combustion according to the invention.

[0050] The invention also relates to a method for preparing a stable hydrocarbon composition, comprising: a) providing a renewable base comprising at least one component chosen from a biomass pyrolysis oil and a residue from the vacuum distillation of a biomass pyrolysis oil, b) providing a fossil base containing at least 1% by mass of asphaltenes and having an aromatic content of at most 54% by mass, c) mixing from 10 to 30% by mass of oil of the renewable base with 70 to 90% by mass of the fossil base with sufficient stirring to obtain a stable emulsion forming the stable hydrocarbon composition.

[0051] In particular, the renewable base and the fossil base provided in steps a) and b) may be as previously defined.

[0052] In one embodiment, the stable hydrocarbon composition thus prepared forms a marine fuel composition usable as a marine fuel or as a base for marine fuel. The invention also relates to the use of a fossil base for preparing a stable emulsion in admixture with a renewable base, in which: the fossil base contains at least 1% by mass of asphaltenes and has an aromatic content of at most 54% by mass, the renewable base comprises at least one component selected from a biomass pyrolysis oil and a residue from the vacuum distillation of a biomass pyrolysis oil, and a stable emulsion is formed by mixing 10 to 30% by mass of the renewable base and 70 to 90% by mass of the fossil base.

[0053] It has in fact been discovered that the use of a fossil base containing asphaltenes in a sufficient quantity of at least 1% by mass, preferably at least 2% by mass, makes it possible to form a stable emulsion in a mixture with a renewable residue as defined when the fossil base contains at most 54% by mass of aromatics.

[0054] This effect is more marked when the fossil base has a Sa parameter of 0.2 to 0.9, preferably 0.2 to 0.6, measured according to ASTM D7157-18 (2018 Revision), and in particular when at least one component of the fossil base has a Sa parameter of 0.4 to 0.9.

[0055] The renewable base and the fossil base may be as previously defined with reference to the stable hydrocarbon composition.

[0056] It will thus be noted that the invention also relates to the use of asphaltenes and aromatics present in a fossil base for stabilizing a hydrocarbon composition comprising (i) 10 to 30% by mass of a renewable base comprising at least one component chosen from a biomass pyrolysis oil and a residue from the vacuum distillation of a biomass pyrolysis oil, and (ii) 70 to 90% by mass of the fossil base, the fossil base containing at least 1% by mass of asphaltenes and having an aromatics content of at most 54% by mass.

[0057] The renewable base and the fossil base may be as previously defined with reference to the stable hydrocarbon composition.

[0058] The invention also relates to the use of the stable hydrocarbon composition of the present invention as (i) a base for manufacturing a marine fuel, (ii) a marine fuel, or (iii) a feedstock for a refining unit chosen from a fluid catalytic cracking (FCC) unit, a hydrotreatment unit, a hydrocracking unit, or a partial oxidation unit. In other words, in one embodiment, the invention also relates to a refining process in which the stable hydrocarbon composition of the present invention is introduced into a refining unit as previously described. Detailed description of the invention

[0059] Renewable base

[0060] By "renewable base" we mean a mixture of hydrocarbon compounds derived exclusively from biological material such as biomass.

[0061] The renewable base used in the present invention comprises, or consists of, at least one component selected from a biomass pyrolysis oil and a residue from the vacuum distillation of a biomass pyrolysis oil. Such a renewable base typically comprises from 20 to 60% by mass of oxygen and from 0.1 to 35% by mass of water or from 5 to 35% by mass of water.

[0062] Preferably, the renewable base comprises, or consists of, at least one residue from the vacuum distillation of a biomass pyrolysis oil.

[0063] Pyrolysis oil is an oil resulting from a pyrolysis process of a hydrocarbon feedstock.

[0064] The residue from vacuum distillation of biomass pyrolysis oil, also called RSV of biomass pyrolysis oil, typically corresponds to the residue from distillation under reduced pressure (80-90 mbar) of pyrolysis oil at 70°C.

[0065] The biomass pyrolysis oil used can contain up to 25% water by mass.

[0066] Biomass pyrolysis oil RSV may contain up to 7% by mass of water, typically 0.1 to 7% by mass of water^advantageously up to 3% by mass of water, or even less than 1% by mass of water. Low water content may result from a dehydration treatment of the RSV.

[0067] Advantageously, the biomass pyrolysis oil or biomass pyrolysis oil RSV may contain at least 5% by mass of water, in particular to facilitate handling of the oil or RSV.

[0068] In one embodiment, the renewable base may contain from 5% by mass to 25% by mass of water.

[0069] The water content can be determined by the Karl Fischer method (ISO- 12937- January 2001).

[0070] The pyrolysis process should be understood as a thermal cracking process, typically carried out at a temperature of 300 to 1000 °C or 400 to 700 °C, carried out in the presence or absence of a catalyst and / or a gas (fast pyrolysis, flash pyrolysis, catalytic pyrolysis, hydropyrolysis, steam pyrolysis, etc.). The pyrolysis process produces a hydrocarbon effluent comprising a gaseous phase, a liquid phase and a solid phase. The effluent is then subjected to a separation step which eliminates the gaseous phase, essentially C1-C4 hydrocarbons, and the solid phase (typically char), to recover only the liquid organic phase forming a pyrolysis oil.

[0071] Biomass can be defined as an organic plant or animal product, namely a product composed of agricultural or forestry plant material or composed of animal material, including vegetable or animal oils or fats.

[0072] The biomass may be selected from lignocellulosic biomass, herbaceous biomass (biomass of plants having a non-woody stem), biomass from plants growing in or under water, algal biomass, agricultural residues from livestock farming, organic waste, paper and / or cardboard, preferably lignocellulosic biomass.

[0073] Biomass can be in the form of waste. Biomass can include (i) biomass produced from surplus agricultural land, particularly land not used for human or animal food: dedicated crops, called energy crops; (ii) biomass produced by deforestation (forest maintenance) or the clearing of agricultural land; (iii) agricultural residues from cereal crops, vines, orchards, olive trees, fruit and vegetables, agri-food residues, etc.; (iv) forest residues from forestry and wood processing; (v) agricultural residues from livestock farming (manure, slurry, bedding, droppings, etc.); (vi) household organic waste (paper, cardboard, green waste, etc.); (vii) ordinary industrial organic waste (paper, cardboard, wood, putrescible waste, etc.)); (viii) algal biomass, namely biomass formed from algae, for example microalgae (the algal biomass may be an algal suspension obtained by harvesting algae from, for example, a bioreactor, or an algal residue obtained by dehydrating an algal suspension) or macroalgae; (ix) herbaceous biomass.

[0074] Biomass pyrolysis oils, also called "bio-oils", have a qualitative and quantitative composition which varies depending on the biomass from which they are produced as well as the pyrolysis and condensation conditions of the pyrolysis vapors from which they are derived.

[0075] However, they have in common the fact that they contain a significant water content, typically in the order of 5 to 35% by mass, numerous oxygenated organic compounds (carboxylic acids, ketones, aldehydes, phenols and phenolic derivatives) and an acidic pH, typically in the order of 2.0 to 3.7.

[0076] A bio-oil or bio-oil vacuum residue typically contains 20 to 60% by mass of oxygen. This oxygen is present in oxygenated compounds containing at least one hydroxyl group (-OH) and / or at least one carbonyl group (>C=O).

[0077] A biomass pyrolysis oil, in particular lignocellulosic biomass, also typically has one or more of the following characteristics:

[0078] - a dynamic viscosity at 50°C of 10-100 mPa.s, and / or

[0079] - an acid index of 50 to 250 mgKOH per gbio-oil, and / or

[0080] - a density at 15°C of 1110 to 1300 kg / m3, and / or

[0081] - a viscosity at 20°C of 15 to 130 mm2 / s, and / or

[0082] - a viscosity at 40°C of 12 to 35°C.

[0083] Fossil base

[0084] By "fossil base" we mean a mixture of hydrocarbons of fossil origin.

[0085] The fossil base used in the present invention is thus of petroleum origin. It comprises, or is made up of, one or more petroleum products.

[0086] In order to enable the preparation of a stable hydrocarbon composition, the fossil base according to the invention must contain asphaltenes and have an aromatic content of at most 54% by mass.

[0087] This aromatic content can be 25 to 54% by mass relative to the total mass of the fossil base.

[0088] The asphaltene content of the fossil base must be at least 1% by mass, preferably at least 2% by mass relative to the total mass of the fossil base. The fossil base typically contains from 2% to 10% by mass of asphaltenes, preferably from 2 to 8% by mass of asphaltenes, more preferably from 2 to 5% by mass of asphaltenes.

[0089] The fossil base may in particular include, or consist of, at least one petroleum product containing asphaltenes.

[0090] Petroleum products containing asphaltenes can be:

[0091] • atmospheric residues noted RAT or vacuum residues noted RSV from the distillation of crude oil which typically contain from 0.01% by mass to 25% by mass of asphaltenes, most often from 0.01% by mass to 10% by mass of asphaltenes, typically of the order of 5% by mass, and which have a parameter value Sa of 0.75 to 0.9. • effluents, in particular residues, from thermal conversion processes such as the visbreaking process whose residue is noted RVR, which typically contain from 5% by mass to 30% by mass of asphaltenes, most often from 5% by mass to 15% by mass of asphaltenes, and which have a parameter value Sa of 0.45 to 0.75.

[0092] • effluents, in particular residues or slurry cut, from catalytic cracking processes, such as the FCC process (“Fluid Catalytic Cracking”), and whose slurry cut (350°C+ cut) typically contains from 0.1% by mass to 8% by mass of asphaltenes, and has a Sa parameter value of 0.1 to 0.3.

[0093] • effluents, in particular residues, from hydrotreatment, hydrocracking, deep hydroconversion processes (fixed bed, moving bed, ebullated bed, entrained bed, or in a slurry phase reactor (where the catalyst is in suspension)), or from the ARDS (“Atmospheric Residue DeSulfurization” or VRDS (“Vacuum Residue DeSulfurization” or Vacuum Residue Desulfurization) process and which typically contain up to 20% by mass of asphaltenes.

[0094] • pitches from physical separation processes, such as deasphalting, which typically contain 4 to 50% by mass of asphaltenes, most often 4 to 25% by mass of asphaltenes, and which have Sa parameter values ​​of 0.6 to 0.9.

[0095] • mixtures of the petroleum products listed above for the formulation of heavy fuels which typically contain from 0.20% by mass to 20% by mass of asphaltenes.

[0096] The person skilled in the art will thus be able to choose one or more petroleum products according to their asphaltene content in order to obtain a fossil base having an asphaltene content of at least 1% by mass, preferably at least 2%, and mix them with the renewable base in the proportions of the invention. Preferably, the petroleum products used are chosen from RSV, RAT, RVR, slurry cuts and pitches.

[0097] In one embodiment, the fossil base may in particular comprise, or consist of, at least one petroleum product containing asphaltenes and at least one fluxing agent.

[0098] The proportions of asphaltene-containing component(s) and fluxing agent(s) may be chosen so that the total asphaltene content of the fossil base is at least 1% by mass, preferably at least 2% by mass. Advantageously, the fossil base may then have a fluxing agent(s) content of 2 to 45% by mass, preferably 10 to 35% by mass.

[0099] The flux can also be a petroleum product. It can then be chosen from: gas oils from the direct distillation of petroleum: kerosene, kerosene, light gas oil, medium gas oil, heavy gas oil, vacuum distillation products from atmospheric residue: light vacuum gas oil (VGO: Vacuum Gasoil), medium vacuum gas oil, heavy vacuum gas oil, distillate, atmospheric or vacuum distillation products from conversion unit effluents: visbreaking gas oil, visbreaking distillate, products from catalytic cracking units and desulfurization and hydrodesulfurization units: catalytic cracker gas oil (LCO: Light cycle oil), heavy catalytic cracker gas oil (HCO: Heavy cycle oil), desulfurized gas oil, gas oil and bleed (residue) from hydrodesulfurization units, products from steam cracking units: pyrolysis oil or gasoline, and mixtures of one or more of the products listed above.

[0100] In a preferred embodiment, the fossil base comprises, or consists of, at least one petroleum product selected from an RSV, a RAT, an RVR, a slurry cut and a pitch, and at least one diesel-type flux.

[0101] In a particularly preferred embodiment, the fossil base comprises, or consists of, at least one petroleum product chosen from an RSV, a RAT, an RVR, a slurry cut and a pitch, including at least one component having an Sa parameter of 0.4 to 0.9, such a component advantageously representing 10 to 65% by mass of the fossil base, and at least one diesel-type fluxing agent.

[0102] Preferably, the fossil base has a Sa parameter of 0.2 to 0.9, preferably 0.2 to 0.6, measured according to ASTM D7157-18 (2018 Revision). It would appear that the asphaltenes present when the Sa parameter is in this range promote the formation of a stable emulsion, in particular when at least one component of the fossil base has a Sa parameter of 0.4 to 0.9. The component(s) having a Sa parameter of 0.4 to 0.9 advantageously represent 10 to 65% of the total mass of the fossil base.

[0103] Preferably, the component(s) having a Sa parameter of 0.4 to 0.9 is (are) chosen from RSV, RVR, slurry cuts and pitches.

[0104] The fossil base used in the present invention advantageously has one or more of the following characteristics: an aromatic content of 25 to 54% by mass, preferably 40 to 54% by mass, a saturates content of 30 to 48% by mass, preferably 30 to 45% by mass, a resins content of 7 to 11% by mass.

[0105] The content of aromatic, saturate and resin compounds in the fossil base can be determined by the analytical method known as SARA.

[0106] Composition according to the invention

[0107] The stable hydrocarbon composition according to the invention comprises, or consists of:

[0108] (a) 10 to 30% by mass of a renewable base comprising at least one component selected from a biomass pyrolysis oil and a residue from the vacuum distillation of a biomass pyrolysis oil,

[0109] (b) 70 to 90% by mass of a fossil base, said fossil base containing at least 1% by mass of asphaltenes and having an aromatics content of at most 54% by mass.

[0110] According to the invention, in order for the composition to form a stable emulsion, the fossil base must have an aromatic content of at most 54% by mass and contain at least 1% by mass, preferably at least 2% by mass of asphaltenes.

[0111] Without wishing to be bound by theory, an asphaltene content of the fossil base of at least 1% by mass and the use of a fossil base concerning at most 54% by mass of aromatics, favors the stabilization of the emulsion probably by favoring the placement of asphaltenes at the interfaces between the polar oil droplets and the apolar oil, which leads to the formation of rigid interfaces which prevent the coalescence of the droplets and allow the persistence of the emulsion.

[0112] By "stable composition" we mean a composition which forms an emulsion without demixing over time, and in particular during long storage periods of at least one month.

[0113] In one embodiment, the stable hydrocarbon composition according to the invention comprises, or consists of:

[0114] (a) 10 to 30% by mass of a renewable base comprising at least one component selected from a biomass pyrolysis oil and a residue from the vacuum distillation of a biomass pyrolysis oil, (b) 70 to 90% by mass of a fossil base, said fossil base containing 2% to 10% by mass of asphaltenes and having an aromatics content of 25 to 54% by mass or 40 to 54% by mass, and an Sa parameter of 0.2 to 0.9, preferably 0.2 to 0.6, measured according to ASTM D7157-18 (2018 Revision), and at least one component of the fossil base has an Sa parameter of 0.4 to 0.9 measured according to ASTM D7157-18 (2018 Revision).

[0115] Preferably, the component(s) having a Sa parameter of 0.4 to 0.9 advantageously represent(s) 10 to 65% of the total mass of the fossil base. In a preferred embodiment, the stable hydrocarbon composition according to the invention comprises, or consists of:

[0116] (a) 10 to 30% by mass of a renewable base comprising at least one component selected from a biomass pyrolysis oil and a residue from the vacuum distillation of a biomass pyrolysis oil,

[0117] (b) 70 to 90% by mass of a fossil base, said fossil base containing 2% to 8% by mass, preferably 2 to 5% by mass, of asphaltenes and having an aromatics content of 25 to 54% by mass or 40 to 54% by mass, and an Sa parameter of 0.2 to 0.9, preferably 0.2 to 0.6, measured according to ASTM D7157-18 (2018 Revision), and at least one component of the fossil base has an Sa parameter of 0.4 to 0.9 measured according to ASTM D7157-18 (2018 Revision).

[0118] Preferably, the component(s) having a Sa parameter of 0.4 to 0.9 advantageously represent(s) 10 to 65% of the total mass of the fossil base.

[0119] In one embodiment, the stable hydrocarbon composition according to the invention is a marine fuel composition and can be used as a base for manufacturing a marine fuel or forming a marine fuel. Marine fuel means a fuel having specifications suitable for use in diesel engines and boilers of ships, before any conventional on-board treatment (decantation, centrifugation, filtration) prior to their use. This type of fuel can also be used in stationary diesel engines, of the same or similar type as those used for marine applications.

[0120] The composition for marine fuel according to the invention can in particular comply with all the specifications for marine fuels presented in standard ISO 8217: 2017 or NF ISO 8217: 2018, or NF ISO 8217: 2024.

[0121] Marine fuel may in particular comply with the specifications of fuels of type RMD, RME, RMG, RMK of the ISO 8217: 2017 or NF ISO 8217: 2018 standard, or the specifications of fuels of the type appearing in tables 2 and 4 of the NF ISO 8217: 2024 standard.

[0122] The stable hydrocarbon composition according to the invention, in particular when it forms a composition for marine fuel, may in particular have one or more of the following characteristics:

[0123] - a sulfur content of less than or equal to 3.5% by mass, preferably less than or equal to 1.5% by mass, more preferably less than or equal to 0.5% by mass, for example from 0.05 to 0.5% by mass or in any interval defined by two of these limits,

[0124] - a density at 15°C of not more than 1010 kg / m 3 , of not more than 991 kg / m 3 , of not more than 975 kg / m 3 , of not more than 960 kg / m 3, of not more than 920 kg / m 3 , of not more than 900 kg / m 3 or not more than 890 kg / m 3 , especially greater than 900 kg / m 3 , or in any interval defined by two of these limits,

[0125] - a pour point of not more than 30°C, not more than 6°C, not more than 0°C or not more than -6°C, in particular greater than -42°C, or in any interval defined by two of these limits,

[0126] - a kinematic viscosity at 50°C of at most 700 mm 2 / s, of at most 500 mm 2 / s, of at most 380 mm 2 / s, of at most 180 mm 2 / s, of at most 80 mm 2 / s, of at most 30 mm 2 / s or at most 10 mm 2 / s, especially greater than 2 mm 2 / s, or in any interval defined by two of these limits.

[0127] The invention makes it possible in particular to formulate a marine fuel with a very low sulfur content (less than 0.50% by mass of sulfur), comprising a renewable component.

[0128] When the stable hydrocarbon composition according to the invention is used as a base for manufacturing a marine fuel, it can be added in any proportions to a base for fossil-based marine fuel, in particular so as to formulate a marine fuel meeting all the specifications for marine fuels presented in the ISO 8217: 2017 or NF ISO 8217: 2018 or NF ISO 8217: 2024 standard, and in particular the specifications for RMD, RME, RMG, RMK type fuels of the ISO 8217: 2017 or NF ISO 8217: 2018 standard, or fuels of the type appearing in tables 2 and 4 of the NF ISO 8217: 2024 standard. A person skilled in the art will be able to determine the appropriate proportions by measuring the properties appearing in the standards and / or specifications.

[0129] In another embodiment, the stable hydrocarbon composition can be used as feedstock for a refining unit selected from a fluid catalytic cracking (FCC) unit, a hydrotreating unit, a hydrocracking unit, a partial oxidation (PCX) unit.

[0130] In one embodiment, the stable hydrocarbon composition may be processed in an FCC unit, for example in at least one reactor in which it is contacted with at least one fluidized catalyst.

[0131] The catalytic cracking reaction is typically carried out at a temperature of 300 to 700°C or 400 to 650°C. In general, the reaction is carried out at moderate pressure, for example at atmospheric pressure.

[0132] In some embodiments, the mass ratio of stable hydrocarbon composition to the amount of catalyst used that contacts the catalyst ("catalyst-to-oil ratio") may be from 4:1 to 15:1. For example, the catalyst-to-oil ratio may be from 4:1 to 13:1, including from 5:1 to 10:1, from 5:1 to 9:1, from 6:1 to 8:1, from 4:1 to 7:1, or from 6:1 to 7:1.

[0133] The contact time of the stable hydrocarbon composition with the catalyst may be 0.1 to 7 seconds, preferably 0.1 to 5 seconds, 0.1 to 4 seconds or 0.1 to 3 seconds or even 0.1 to 1 second.

[0134] The catalyst may be a conventional FCC catalyst. FCC catalysts typically comprise a zeolite, such as USY zeolite, a matrix, such as alumina, and a kaolin clay. The catalyst may further comprise additives for trapping metal contaminants, for converting sulfur compounds and others, well known to those skilled in the art.

[0135] Alternatively, the catalyst may comprise a basic catalyst. Examples of suitable basic catalysts include layered materials and materials obtained by heat treatment of the layered materials. Preferably, the layered materials are selected from the group consisting of smectites, anionic clays, layered hydroxy salts, and mixtures thereof. Hydrotalcite-type materials, particularly Mg-Al and Ca-Al anionic clays, are particularly preferred.

[0136] Basic catalysts can be used as is or blended with a conventional FCC cracking catalyst.

[0137] In one embodiment, the stable hydrocarbon composition may be treated in a hydrotreatment unit, for example in at least one reactor in which it is contacted with at least one hydrotreatment catalyst.

[0138] Usable hydrotreatment conditions include a pressure of 15 to 130 bars, preferably 15 to 50 bars, a temperature of 250 to 380°C, preferably 280 to 340°C, in the presence of a hydrotreatment catalyst and dihydrogen. Typically, a liquid hourly space velocity (LHSV) of 0.2 to 9 hr can be provided. 1 , preferably 0.5 to 7, and more preferably 0.8 to 1.8 or 1 to 1.6 h' 1 , and a dihydrogen ratio: 50 to 1500 Nm 3 / m 3load, preferably 120 to 250 Nm 3 / m 3 or from 120 to 180 Nm 3 / m 3 and more preferably 120 to 200 Nm 3 / m 3 dump.

[0139] The hydrotreatment catalyst is a conventional hydrotreatment catalyst. Conventional hydrotreatment catalysts include, in particular, an active metal compound such as nickel, platinum, palladium, rhenium, rhodium, nickel tungstate, nickel molybdenate, molybdenum, cobalt molybdenate, nickel molybdenate, this metal compound may or may not be deposited on a support. This support may generally include oxides such as silicas, aluminas, aluminosilicates (in particular zeolites), titanium oxides, or carbon oxides, molecular sieves, salts or alkaline earth metals. When a support is present, it advantageously has a specific surface area ranging from 100 to 250 m 2 / g, preferably 150 to 200 m 2 / g.

[0140] Advantageously, the catalyst comprises at least two metals from groups 6, 9, 10, 11 of the periodic table of elements, preferably at least two metals such as NiMo, CoMo, or CoNiMo, preferably on an alumina support.

[0141] When supported, conventional hydrotreating catalysts typically comprise a metal content of 0.01 to 25% by mass relative to the total mass of the catalyst, preferably 15 to 20% by mass, for example 20% by mass relative to the total mass of the catalyst.

[0142] In a preferred embodiment, the catalyst used does not have an isomerizing function or has negligible isomerizing activity under the reaction conditions. In other words, the catalyst does not promote the isomerization of the hydrocarbon compounds present in the feedstock. When a support is present, it is preferably slightly acidic or not at all.

[0143] Thus, a catalyst not having an isomerizing function may comprise at least one metal from groups 6, 9, 10, 11 of the periodic table of elements, optionally on a support chosen from alumina, silica alumina, phosphated alumina, borated alumina, phosphated silica alumina, alone or as a mixture.

[0144] In one embodiment, the stable hydrocarbon composition may be processed in a hydrocracking unit. The hydrocracking unit may include at least one hydrocracking reactor in which the feedstock is contacted with at least one hydrocracking catalyst.

[0145] Typically, hydrocracking conditions include a temperature of 250 to 480°C, a hydrogen partial pressure of 1.5 to 25 MPa abs., and an hourly volumetric flow rate of 0.1 to 10 h'. 1 .

[0146] A usable hydrocracking catalyst comprises, for example, a support chosen from halogenated aluminas, combinations of boron and aluminum oxides, amorphous silica-aluminas and zeolites and a hydro-dehydrogenating function comprising at least one metal from group 6 chosen from chromium, molybdenum and tungsten, alone or as a mixture, and / or at least one metal from groups 8-10 chosen from iron, cobalt, nickel, ruthenium, rhodium, palladium and platinum.

[0147] In one embodiment, the stable hydrocarbon composition may be processed in a partial oxidation gasification (POX) unit to produce, in the presence of an oxidizing agent comprising molecular oxygen (O2), a synthesis gas comprising at least dihydrogen, carbon monoxide and carbon dioxide.

[0148] The POX gasification unit comprises at least one reactor or at least one POX gasification gasifier.

[0149] Alternatively or in combination with any other variation of this embodiment, the oxidizing agent comprises an oxidizing gas which may include air, oxygen-enriched air, or molecular oxygen (O2), or steam.

[0150] Partial oxidation gasification can be carried out in the presence or absence of a catalyst. Suitable catalysts include one or more metal components from groups 8 to 10 of the periodic table, such as platinum, palladium, rhodium, iridium, osmium, ruthenium, and optionally, one or more elements from groups 5 to 7, 11, such as iron, cobalt, nickel, copper, vanadium and chromium, these elements typically being supported on a support such as zirconia, alumina, CeCh, Y2O3 or TiO2.

[0151] Alternatively or in combination with any other variation of this embodiment, the gasification zone, and optionally all reaction zones in the gasifier / gasification reactor, may operate at a temperature of at least 1000°C, at least 1100°C, at least 1200°C, at least 1250°C, or at least 1300°C and / or not more than 2500°C, not more than 2000°C, not more than 1800°C, or not more than 1600°C. The reaction temperature may be autogenous. Alternatively or in combination with any other variation of this embodiment, the gasifier may operate at a pressure within the gasification zone (or combustion chamber) of at least 1.3 MPa to 9 MPa, examples of suitable pressure ranges include 2 to 7 MPa, 2 to 6 MPa, 2.5 to 7 MPa, 2 to 5.5 MPa, 3 to 5 MPa or any range defined by any of the limits of these ranges.

[0152] In general, the average residence time of the gases in the gasification reactor may be very short to increase the throughput. Since the gasifier may operate at a high temperature and pressure, substantially complete conversion of the feedstock to gas may occur in a very short time. In one embodiment or in combination with any embodiment mentioned herein, the average residence time of the gases in the gasifier may be no more than 30, no more than 25, no more than 20, no more than 15, no more than 10, or no more than 7 seconds.

[0153] The stable hydrocarbon composition according to the invention can be prepared by mixing the two components (a) and (b) in the proportions indicated with sufficient stirring to obtain an emulsion.

[0154] The agitation conditions for obtaining an emulsion are the usual conditions used by those skilled in the art and are therefore not described in further detail. Adequate agitation can typically be achieved using a turbine or a rotor / stator.

[0155] The emulsion can also be produced by heating components (a) and (b) to a temperature that facilitates their handling depending on their viscosity, for example to a temperature of 30 to 60°C.

[0156] Description of figures

[0157] [Fig. 1] Figure 1 represents a curve of the half-life times of the emulsions of Example 2 subjected to centrifugation of 2325 g at 50°C, as a function of the aromatic content of the fossil base.

[0158] Examples

[0159] Different emulsions were formulated from a fossil base and a renewable base. In all examples, the emulsions were prepared by stirring with a rotor-stator (30,000 rpm, 2 minutes) at 50°C. In the examples, a vacuum residue of pine pyrolysis oil containing 6.3% by mass of water was used as the renewable base.

[0160] Example 1: Impact of asphaltene content on the stability of a composition comprising a fossil base and a vacuum residue of a biomass pyrolysis oil

[0161] Asphaltenes extracted from a fossil vacuum residue (fossil VSR) by n-heptane precipitation were reincorporated at different contents into the same vacuum residue.

[0162] Emulsions containing 30% by mass of a vacuum residue of pine pyrolysis oil (renewable RSV) in fossil RSV were prepared, observed by optical microscopy and their stability was evaluated for 2 h under centrifugation (2000 rpm, or 581 g) at 50°C. Stability monitoring is done by measuring the intensity of light transmitted along the sample over time (wavelength 870 nm and at 50°C) using a LumiSizer® device from LUM. The lifetime corresponds to the time after which 50% of the maximum intensity of transmitted light is reached in the lower half of the tested sample.

[0163] Table 1 lists the characteristics of the emulsions formed.

[0164] Table 1

[0165] Observation by optical microscopy shows that fossil RSV does not transmit light, nor does the emulsion. Only renewable RSV transmits light and allows the emulsion separation to be monitored. For samples a) to c), the emulsion breaks during the analysis, with a maximum transmission at the bottom of the sample after 2 h, which means that all the renewable RSV is separated. For sample d), the sample begins to destabilize after 2 h of analysis, while sample e) is stable throughout the 2 h of analysis.

[0166] For these 5 emulsions, a half-life can be calculated, i.e. the time after which 50% of the dispersed phase is separated. These times are shown in Table 1. It is clear that an increase in the asphaltene content increases the half-life, and therefore the stability of the emulsion. This example shows the impact of the asphaltene content on the stability of the emulsion.

[0167] Example 2: impact of the nature of the dispersing phase at the same asphaltene content

[0168] Different emulsions containing 30% by mass of pine pyrolysis oil RSV (renewable RSV) in a fossil base were prepared. The composition of the fossil base was modified to maintain an asphaltene content of around 2% in the emulsions.

[0169] The fossil base contains a RSV (vacuum residue), a RAT (atmospheric residue), a slurry and a diesel fuel (GO).

[0170] Asphaltenes are contained in RSV (4.4% by mass) and in slurry (0.86% by mass). These asphaltenes are of different natures, RSV having a Sa parameter of 0.87 and slurry a Sa parameter of 0.20.

[0171] The compositions are detailed in Table 2, as well as the half-life of the emulsions measured under centrifugation (4000 revolutions per minute, or 2325 g) at 50°C, as in Example 1.

[0172] Table 2

[0173] These results show that the stability of the emulsion can be multiplied by a factor of around 4 when the composition of the dispersing phase is modified, at a constant asphaltene content. The half-life of the emulsion is relatively well correlated with the RAT base and slurry contents: the higher the amount of RAT, the more stable the emulsion, and vice versa for the RSV content.

[0174] The SAR composition (Saturates, Aromatics, Resins) of the different constituents of the fossil base is gathered in table 3 and table 4 gathers the SAR composition calculated for emulsions A to L.

[0175] Table 3

[0176] Table 4

[0177] Figure 1 shows that the half-life of emulsions A-L is well correlated with the aromatic content of the mixture (emulsion G was excluded from the correlation). The most stable emulsions are obtained for fuels with the lowest aromatic contents. Considering that an emulsion is stable when its half-life is greater than 1 hour under the analysis conditions, a stable emulsion can be obtained when the fossil base has an aromatic content of at most 54% by mass, regardless of the nature of the components of the fossil base.

[0178] Example 3 - Emulsions from a fossil base containing 2.8% by mass of asphaltenes

[0179] Different emulsions were prepared containing 10 or 30 wt% pine pyrolysis oil RSV (renewable RSV) in different fossil bases each with an asphaltene content of 2.8 wt%.

[0180] The fossil base is a mixture of fossil petroleum products such as a VSR (Vacuum Residual), a TSR (Atmospheric Residual), a VSR (Visbreaking Residual), a slurry, a pitch and a diesel fuel (DO).

[0181] The characteristics of the different constituents used to make the fossil bases are gathered in Table 5. The components RSV, RAT, Slurry, GO and the pyrolysis oil RSV are the same as those used in Examples 1 and 2.

[0182] Table 5

[0183] The compositions of the tested emulsions are listed in Table 6.

[0184] Fossil bases not containing pitch were prepared as follows. The components are weighed and preheated: GO (25°C), RAT (50°C), RSV or RVR (80°C), then mixed under magnetic stirring at 50°C until homogenized.

[0185] Fossil bases containing pitch were prepared as follows. GO was weighed with pitch previously ground into powder in a mortar and mixed until GO was colored, then heated at 80°C for 24 hours with stirring for 2 to 3 hours until homogenized. Then, RAT (heated to 50°C) was added and mixed under magnetic stirring at 50°C until homogenized.

[0186] Table 6

[0187] The emulsions were stored at 50°C, a sample was taken regularly and the stability was assessed using Lum's LumiSizer® under centrifugation (2000 rpm, or 581 g) at 50°C for 2 h. The transmitted light intensity (wavelength 870 nm) along the sample remained constant over time and during the measurement under centrifugation, which confirms the stability of the emulsion for 6 months, without observation of demixing.

[0188] Examples 1 to 3 demonstrate that specific asphaltenes characterized by a particular Sa parameter of the fossil base in which they are contained, and in particular by a particular Sa parameter of at least one component of the fossil base as described above, these asphaltenes being present in a particular content in the fossil base, in particular in a content of 2 to 10% by mass, preferably of 2 to 8% by mass, more preferably of 2 to 5% by mass, when they are combined with a maximum content of aromatics in the fossil base, make it possible to stabilize a composition resulting from the mixing of the fossil base with a renewable base comprising a biomass pyrolysis oil or a residue of such an oil. It is thus the use of specific asphaltenes in a particular content combined with a particular aromatic content which makes it possible to stabilize this type of composition.

[0189] In other words, the use of a fossil base as described in the present application makes it possible to stabilize a mixture of this fossil base with a renewable base comprising a biomass pyrolysis oil or a residue of such an oil.

Claims

CLAIMS 1. Stable hydrocarbon composition characterized in that it comprises: (a) 10 to 30% by mass of a renewable base comprising at least one component selected from a biomass pyrolysis oil and a residue from the vacuum distillation of a biomass pyrolysis oil, (b) 70 to 90% by mass of a fossil base, said fossil base containing at least 2% by mass of asphaltenes and having an aromatics content of at most 54% by mass and an Sa parameter of 0.2 to 0.9, preferably 0.2 to 0.6, measured according to ASTM D7157-18 (2018 Revision).

2. Composition according to claim 1, characterized in that the fossil base contains from 2% to 10% by mass of asphaltenes, preferably from 2 to 8% by mass of asphaltenes, more preferably from 2 to 5% by mass of asphaltenes.

3. Composition according to claim 1 or 2, characterized in that at least one component of the fossil base has a Sa parameter of 0.4 to 0.9 measured according to standard ASTM D7157-18 (Revision 2018), and optionally the component(s) having a Sa parameter of 0.4 to 0.9 represent 10 to 65% of the total mass of the fossil base.

4. Composition according to any one of claims 1 to 3, characterized in that the fossil base comprises at least one petroleum product containing asphaltenes and at least one fluxing agent, optionally the fossil base having a fluxing agent content of 2 to 45% by mass, preferably 10 to 35% by mass.

5. Composition according to claim 4, characterized in that the fossil base comprises at least one fluxing agent chosen from (i) a diesel oil from the direct distillation of petroleum, (ii) the products of vacuum distillation of an atmospheric residue, (iii) the products of atmospheric or vacuum distillation of the effluents from the conversion units, (iv) the products from the catalytic cracking units and the desulfurization and hydrodesulfurization units, (v) the products from the steam cracking units.

6. Composition according to any one of claims 1 to 5, characterized in that the fossil base comprises at least one component containing asphaltenes chosen from: Tl (i) atmospheric residues or vacuum residues from the distillation of crude oil, (ii) effluents, in particular residues, from thermal conversion processes, such as the visbreaking process, (iii) effluents, in particular residues or slurry, from catalytic cracking processes, such as the FCC process, (iv) effluents, in particular residues, from hydrotreatment, hydrocracking, deep hydroconversion, ARDS and VRDS processes, (v) pitches from physical separation processes, such as deasphalting.

7. Composition according to any one of claims 1 to 6, characterized in that the biomass pyrolysis oil is obtained from a process of pyrolysis of a biomass chosen from (i) lignocellulosic biomass, (ii) herbaceous biomass, (iii) biomass from plants growing in or under water, (iv) algal biomass, (v) agricultural residues from livestock farming, (vi) organic waste, (vii) paper, (viii) cardboard, and mixtures thereof.

8. Composition according to any one of claims 1 to 7, characterized in that the renewable base contains from 20 to 60% by mass of oxygen.

9. A marine fuel composition consisting of or comprising the stable hydrocarbon combustion according to any one of claims 1 to 8.

10. A method for preparing a stable hydrocarbon composition, comprising: a) providing a renewable base comprising at least one component selected from a biomass pyrolysis oil and a residue from the vacuum distillation of a biomass pyrolysis oil, b) providing a fossil base containing at least 2% by mass of asphaltenes and having an aromatics content of at most 54% by mass and an Sa parameter of 0.2 to 0.9, preferably 0.2 to 0.6 measured according to ASTM D7157-18 (2018 Revision), c) mixing from 10 to 30% by mass of oil of the renewable base with 70 to 90% by mass of the fossil base with sufficient agitation to obtain a stable emulsion forming the stable hydrocarbon composition.

11. Preparation method according to claim 10, characterized in that the fossil base comprises from 2% to 10% by mass of asphaltenes, preferably from 2 to 8% by mass of asphaltenes, more preferably from 2 to 5% by mass of asphaltenes.

12. Preparation method according to claim 10 or 11, characterized in that at least one component of the fossil base has a Sa parameter of 0.4 to 0.9 measured according to standard ASTM D7157-18 (Revision 2018), and optionally the component(s) having a Sa parameter of 0.4 to 0.9 represent 10 to 65% of the total mass of the fossil base.

13. Use of asphaltenes and aromatics present in a fossil base for stabilizing a hydrocarbon composition comprising (i) 10 to 30% by mass of a renewable base comprising at least one component selected from a biomass pyrolysis oil and a residue from the vacuum distillation of a biomass pyrolysis oil, and (ii) 70 to 90% by mass of the fossil base, the fossil base containing at least 2% by mass of asphaltenes and having an aromatics content of at most 54% by mass and an Sa parameter of 0.2 to 0.9, preferably 0.2 to 0.6, measured according to ASTM D7157-18 (2018 Revision).

14. Use according to claim 13, wherein the fossil base has: at least one component having a Sa parameter of 0.4 to 0.9 measured according to the ASTM D7157-18 standard (2018 Revision), and optionally the component(s) having a Sa parameter of 0.4 to 0.9 represent 10 to 65% of the total mass of the fossil base, and / or 2% to 10% by mass of asphaltenes, preferably 2 to 8% by mass of asphaltenes, more preferably 2 to 5% by mass of asphaltenes.

15. Use of the hydrocarbon composition according to any one of claims 1 to 8 as (i) base for manufacturing a marine fuel, (ii) marine fuel, or (iii) feedstock for a refining unit chosen from a fluid catalytic cracking unit, a hydrotreatment unit, a hydrocracking unit, a partial oxidation unit.

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