STABLE HYDROCARBONATE COMPOSITION COMPRISING A RENEWABLE BASE

Abstract

The invention relates to a stable hydrocarbon composition comprising: (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 containing at least 1% by mass of asphaltenes and having an aromatics content of not more than 54% by mass. Figure for the abstract: without

Description

Title of the invention: STABLE HYDROCARBON COMPOSITION COMPRISING A RENEWABLE BASE Field of invention

[0001] 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. Prior art

[0002] 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.

[0003] In order to reduce the impact of marine fuels on the environment, producers are seeking to integrate more and more components of renewable origin into their production. In particular, producers are seeking to manufacture fuels with a reduced overall balance of greenhouse gas emissions such as carbon dioxide, and a low sulfur content to limit emissions, particularly in Arctic regions.

[0004] 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, economically, these renewable bases are too high in added value for marine applications.

[0005] Biomass pyrolysis oils could prove to be economically viable renewable bases in mixture 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 a marine application or as feedstock for a refining unit. One way to improve the compatibility between biomass pyrolysis oils and fossil bases is to transform them chemically. A second way is to add co-solvents to obtain a single phase. A third way consists of using block copolymers that are expensive to synthesize to stabilize oil-in-oil emulsions. These methods, used separately or together, have a significant cost.

[0006] There is therefore a need to improve the compatibility between biomass pyrolysis oils and fossil bases which is simpler to implement and less expensive. Definitions

[0007] By "asphaltenes" is meant compounds insoluble in n-heptane, and soluble in toluene, contained in particular in crude oils, bitumens, coal. In general, asphaltenes comprise carbon, hydrogen, nitrogen, sulfur, vanadium and nickel. The asphaltene content can be measured according to standard NF T60-115 (January 2000).

[0008] “Fluxant” means a hydrocarbon stream which makes it possible to modify one or more physical characteristics of another hydrocarbon stream so that they comply with specifications. The physical characteristic(s) likely to be modified by the addition of a flux are chosen from: viscosity, density, sulfur content, pour point or carbon residue.

[0009] "Crude oil" (or "crude", crude oil in English) means oil from a natural deposit, and which is exploited in liquid form at atmospheric pressure. This name therefore designates a natural product before refining, but which has already lost part of its deposit composition, the fraction of light hydrocarbons leaving the liquid phase at the very place of its exploitation.

[0010] “Petroleum product” means an effluent from a crude oil processing unit or an effluent, or an effluent from a crude oil separation unit or effluent, 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.

[0011] The composition of a petroleum product in aromatic, saturates and resin compounds can be determined by the analytical method known as SARA, allowing the classification of the multiple hydrocarbon components into one of the following four categories according to their polarizability and polarity: saturates (S), aromatics (A), resin (R) or asphaltenes (As).

[0012] 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.

[0013] The aromatic components (A) (also referred to as “aromatics” in the present application) contain one or more aromatic rings and are slightly more polar- risables than the saturated components (S). For example, crude oils can contain from about 10% by mass to about 45% by mass of aromatic components (A).

[0014] 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.

[0015] 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 which 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 may contain from about 5% by mass to about 40% by mass of resinous (R) components. The asphaltene (As) components are by definition insoluble, even in excess n-heptane, but are generally soluble in benzene or toluene.Crude oils worldwide typically contain from 0% by mass to about 35% by mass of asphaltene (As) components.

[0016] Many analytical protocols for the SARA method are known, allowing the relative amounts of saturates (S), aromatics (A), resins (R) and asphaltenes (As) to be determined 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).

[0017] Bleed: heavy fraction (very paraffinic) resulting from the hydrocracking of a distillate-type feedstock, usually corresponding to a unit bottom.

[0018] Kerosene: cut resulting from atmospheric distillation, usually having an initial distillation point of 150 to 180°C and a final distillation point of 225 to 250°C.

[0019] 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.

[0020] VGO (Vacuum gasoil): heavy vaporizable cut resulting from the vacuum distillation of an atmospheric residue. The boiling temperature range of this cut is usually 360-380 to 540-600°C.

[0021] 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 oily 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.

[0022] The density at 15°C is measured according to ISO 12185:1996.

[0023] Kinematic viscosity at 50°C is measured according to ISO 3104:2020.

[0024] The pour point is measured according to ISO 3016:2019.

[0025] Sulfur content can be measured according to ISO 8754 or ASTM D4294. Summary of the invention

[0026] A first subject of the invention relates to a 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 containing at least 1% by mass of asphaltenes and having an aromatics content of not more than 54% by mass.

[0027] 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.

[0028] Advantageously, the fossil base can contain at least 2% by mass of asphaltenes.

[0029] Advantageously, the fossil base can have a parameter Sa of 0.2 to 0.9 measured according to the standard ASTM D7157-18 (Revision 2018).

[0030] 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.

[0031] The fossil base may in particular comprise at least one fluxing agent chosen from (i) a diesel fuel from the direct distillation of petroleum, (ii) vacuum distillation products of an atmospheric residue, (iii) atmospheric or vacuum distillation products of effluents from conversion units, (iv) products from catalytic cracking units and desulfurization and hydrodesulfurization units, (v) products from steam cracking units.

[0032] Advantageously, the fossil base may comprise at least one component containing asphaltenes chosen from:

[0033] (i) atmospheric residues or vacuum residues from the distillation of the crude oil,

[0034] (ii) effluents, in particular residues, from thermal conversion processes, such as the visbreaking process,

[0035] (iii) effluents, in particular residues or slurry cuts, from catalytic cracking processes, such as the FCC process (“Fluid Catalytic Cracking”),

[0036] (iv) effluents, in particular residues, from hydrotreatment, hydrocracking, deep hydroconversion, ARDS and VRDS processes,

[0037] (v) pitches from physical separation processes, such as deasphalting,

[0038] and mixtures of two or more of the petroleum products listed above.

[0039] 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, (vi) organic waste, (vii) paper, (viii) cardboard, and mixtures thereof.

[0040] The invention also relates to a composition for marine fuel consisting of, or comprising, the stable hydrocarbon combustion according to the invention.

[0041] The invention also relates to a method for preparing a stable hydrocarbon composition, comprising:

[0042] 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,

[0043] b) providing a fossil base containing at least 1% by mass of asphaltenes and having an aromatics content of at most 54% by mass,

[0044] 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.

[0045] In particular, the renewable base and the fossil base provided in steps a) and b) may be as previously defined.

[0046] 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.

[0047] The invention also relates to the use of a fossil base for preparing a stable emulsion mixed 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.

[0048] 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.

[0049] This effect is more marked when the fossil base has a Sa parameter of 0.2 to 0.9 measured according to the ASTM D7157-18 standard (2018 Revision).

[0050] The renewable base and the fossil base may be as previously defined with reference to the stable hydrocarbon composition.

[0051] 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.

[0052] The renewable base and the fossil base may be as previously defined with reference to the stable hydrocarbon composition.

[0053] 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, 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 Renewable base

[0054] By “renewable base” is meant a mixture of hydrocarbon compounds derived exclusively from biological material such as biomass.

[0055] 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.

[0056] Preferably, the renewable base comprises, or consists of, at least one residue from the vacuum distillation of a biomass pyrolysis oil.

[0057] A pyrolysis oil is an oil resulting from a pyrolysis process of a hydrocarbon feedstock.

[0058] The residue from the vacuum distillation of a biomass pyrolysis oil, also called RSV of biomass pyrolysis oil, typically corresponds to the residue from the distillation under reduced pressure (80-90 mbar) of a pyrolysis oil at 70°C.

[0059] The biomass pyrolysis oil used can contain up to 25% by mass of water.

[0060] The biomass pyrolysis oil RSV may contain up to 7% by mass of water, advantageously up to 3% by mass of water. Low water content may result from a dehydration treatment of the RSV.

[0061] Advantageously, the biomass pyrolysis oil or the biomass pyrolysis oil RSV may contain at least 5% by mass of water, in particular to facilitate the handling of the oil or the RSV.

[0062] In one embodiment, the renewable base may contain from 5% by mass to 25% by mass of water.

[0063] The water content can be determined by the Karl Fischer method (ISO-12937-January 2001).

[0064] The pyrolysis process must 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, steampyrolysis, etc.).

[0065] 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 makes it possible to eliminate the gaseous phase, essentially the C1-C4 hydrocarbons, and the solid phase (typically char), to recover only the liquid organic phase forming a pyrolysis oil.

[0066] 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.

[0067] The biomass may be chosen 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.

[0068] Biomass can in particular be in the form of waste. Biomass can thus include (i) biomass produced by surplus agricultural land, in particular 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, fruits 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 (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. Fossil base.

[0069] By “fossil base” we mean a mixture of hydrocarbons of fossil origin.

[0070] 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.

[0071] In order to allow 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.

[0072] The asphaltene content of the fossil base must be at least 1% by mass, preferably at least 2% by mass.

[0073] The fossil base may in particular comprise, or consist of, at least one petroleum product containing asphaltenes.

[0074] Petroleum products containing asphaltenes can be: • atmospheric residues or vacuum residues from the distillation of crude oil which typically contain from 0.01% by mass to 25% by mass of asphaltenes. • effluents, in particular residues, from thermal conversion processes such as the visbreaking process, which typically contain from 5% by mass to 30% by mass of asphaltenes. • effluents, in particular residues or slurry cuts, from processes of catalytic cracking, 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. • 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. • pitches from physical separation processes, such as deasphalting, which typically contain 4 to 50% by mass of asphaltenes. • 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.

[0075] A 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.

[0076] 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.

[0077] The proportions of component(s) containing asphaltenes 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.

[0078] Advantageously, the fossil base can then have a fluxing agent(s) content of 2 to 45% by mass.

[0079] The flux can also be a petroleum product. It can then be chosen from:

[0080] - diesel fuels from the direct distillation of petroleum: kerosene, kerosene, light diesel, medium diesel, heavy diesel,

[0081] - vacuum distillation products of the atmospheric residue: light diesel under vacuum (VGO: Vacuum Gasoil), medium vacuum diesel, heavy vacuum diesel, distillate,

[0082] - atmospheric or vacuum distillation products of effluents from units of conversion: visbreaking diesel, visbreaking distillate,

[0083] - products from catalytic cracking units and desulfurization units and hydrodesulfurization: catalytic cracker diesel (LCO: Light cycle oil), heavy catalytic cracker diesel (HCO: Heavy cycle oil), desulfurized diesel, diesel and bleed (residue) from hydrodesulfurization units,

[0084] - products from steam cracking units: pyrolysis oil or gasoline,

[0085] - and mixtures of one or more of the products listed above.

[0086] Preferably, the fossil base has a parameter Sa of 0.2 to 0.9 measured according to the ASTM D7157-18 (2018 Revision) standard. It appears that asphaltenes present when the Sa parameter is in this range promote the formation of a stable emulsion.

[0087] The fossil base used in the present invention advantageously has one or more of the following characteristics: - an aromatic content of 40 to 54% by mass, - a saturates content of 30 to 45% by mass, - a resin content of 7 to 11% by mass.

[0088] The content of aromatic, saturate and resin compounds in the fossil base can be determined by the analytical method known as SARA. Composition according to the invention

[0089] The stable hydrocarbon composition according to the invention comprises:

[0090] (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,

[0091] (b) 70 to 90% by mass of a fossil base containing at least 1% by mass asphaltenes and having an aromatic content of not more than 54% by mass.

[0092] 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.

[0093] 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, promotes the stabilization of the emulsion probably by promoting 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.

[0094] 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. By marine fuel is meant 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.

[0095] The composition for marine fuel according to the invention can in particular comply with all the specifications of marine fuels presented in standard NF ISO 8217: 2017 or NF ISO 8217: 2018.

[0096] Marine fuel may in particular comply with the specifications of RMD, RME, RMG, RMK type fuels of the standard.

[0097] 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: - 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, - a density at 15°C of not more than 1010 kg / m3, not more than 991 kg / m3, not more than 975 kg / m3, not more than 960 kg / m3, not more than 920 kg / m3, not more than 900 kg / m3 or not more than 890 kg / m3, in particular greater than 900 kg / m3, or in any interval defined by two of these limits, - 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, - a kinematic viscosity at 50°C of not more than 700 mm2 / s, not more than 500 mm2 / s, not more than 380 mm2 / s, not more than 180 mm2 / s, not more than 80 mm2 / s, not more than 30 mm2 / s or not more than 10 mm2 / s, in particular greater than 2 mm2 / s, or in any interval defined by two of these limits.

[0098] 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.

[0099] 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 proportion to a base for fossil-based marine fuel, in particular so as to formulate a marine fuel complying with all the specifications for marine fuels presented in the NF ISO 8217: 2017 or NF ISO 8217: 2018 standard, and in particular the specifications for RMD, RME, RMG, RMK type fuels. 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.

[0100] In another embodiment, the stable hydrocarbon composition can be used as a feedstock for a refining unit selected from a fluid catalytic cracking (FCC) unit, a hydrotreatment unit, a hydrocracking unit, a partial oxidation (POX) unit.

[0101] In one embodiment, the stable hydrocarbon composition may be treated in an FCC unit, for example in at least one reactor in which it is brought into contact with at least one fluidized catalyst.

[0102] 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.

[0103] 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.

[0104] The contact time of the stable hydrocarbon composition with the catalyst may be from 0.1 to 7 seconds, preferably from 0.1 to 5 seconds, from 0.1 to 4 seconds or from 0.1 to 3 seconds or even from 0.1 to 1 second.

[0105] The catalyst may be a conventional FCC catalyst. FCC catalysts generally 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.

[0106] 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 hydroxyl salts, and mixtures thereof. Hydrotalcite-type materials, particularly Mg-Al and Ca-Al anionic clays, are particularly preferred.

[0107] The basic catalysts can be used as such or mixed with a conventional FCC cracking catalyst.

[0108] 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 brought into contact with at least one hydrotreatment catalyst.

[0109] 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 hr1, preferably 0.5 to 7, and more preferably 0.8 to 1.8 or 1 to 1.6 h1, and a dihydrogen ratio of 50 to 1500 Nm3 / m3 of feed, preferably 120 to 250 Nm3 / m3 or 120 to 180 Nm3 / m3 and more preferably 120 to 200 Nm3 / m3 of load.

[0110] The hydrotreatment catalyst is a conventional hydrotreatment catalyst. Conventional hydrotreatment catalysts comprise 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 being able to be deposited or not on a support. This support can generally comprise oxides such as silicas, aluminas, alumino-silicates (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 varying from 100 to 250 m2 / g, preferably from 150 to 200 m2 / g.

[0111] 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.

[0112] 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.

[0113] 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 acidic.

[0114] 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.

[0115] In one embodiment, the stable hydrocarbon composition may be processed in a hydrocracking unit. The hydrocracking unit may comprise at least one hydrocracking reactor in which the feedstock is contacted with at least one hydrocracking catalyst.

[0116] 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 *.

[0117] 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 in mixture, and / or at least one metal from groups 8-10 chosen from iron, cobalt, nickel, ruthenium, rhodium, palladium and platinum.

[0118] 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.

[0119] The POX gasification unit comprises at least one reactor or at least one POX gasification gasifier.

[0120] In one variation 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.

[0121] Partial oxidation gasification may 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, CeO2, Y2O3 or TiO2.

[0122] In a variant or in combination with any other variant 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] The stirring 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 stirring can typically be achieved using a turbine or a rotor / stator.

[0127] The emulsion can also be produced by heating components (a) and (b) to a temperature which facilitates their handling depending on their viscosity, for example at a temperature of 30 to 60°C. Description of figures

[0128] [Fig-1] [Fig.l] represents a curve of the half-life times of the emulsions of Example 2 subjected to centrifugation of 2325 g at 50°C, depending on the aromatic content of the fossil base. Examples

[0129] 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.

[0130] In the examples, a vacuum residue of pine pyrolysis oil containing 6.3% by mass of water was used as the renewable base.

[0131] 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

[0132] Asphaltenes extracted from a fossil vacuum residue (fossil RSV) by n-heptane precipitation were reincorporated at different contents into the same vacuum residue.

[0133] 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).

[0134] Table 1 lists the characteristics of the emulsions formed.

[0135] [Table 1] Table 1 Emulsion Asphaltene content of fossil RSV (% by mass) Emulsion life (h) a) 0 0.39 b) 0.05 0.57 c) 0.1 0.69 d) 0.5 Start of destabilization at 2h e) 1 Stable for 2h

[0136] Observation by optical microscopy shows that the fossil RSV does not transmit light, nor does the emulsion. Only the renewable RSV transmits light and allows the separation of the emulsion to be followed. 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 beginning of destabilization of the sample is observed after 2 h of analysis, while sample e) is stable throughout the 2 h of analysis.

[0137] For these 5 emulsions, a V2 life time 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 makes it possible to increase the half-life time, and therefore the stability of the emulsion. This example shows the impact of the asphaltene content on the stability of the emulsion.

[0138] Example 2: impact of the nature of the dispersing phase at the same asphaltene content

[0139] 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 in order to maintain an asphaltene level of around 2% in the emulsions.

[0140] The fossil base contains a RSV (atmospheric residue), a RAT (atmospheric residue), a slurry and a diesel (GO).

[0141] Asphaltenes are contained in the RSV (4.4% by mass) and in the slurry (0.86% by mass). These asphaltenes are of different natures, the RSV having a Sa parameter of 0.87 and the slurry a Sa parameter of 0.20.

[0142] 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.

[0143] [Table 2] Table 2 Emulsion (30% Renewable RSV in the fossil base) Composition of the fossil base (% by mass) % by mass Asphaltenes in the fossil base Time of x / 2 life of the emulsion (h) RSV RAT Slurry GO A 40 10 10 40 1.9 1.24 B 40 20 10 30 1.9 1.56 C 40 30 10 20 1.9 1.73 D 40 10 20 30 2.0 1.39 E 40 20 20 20 2.0 1.26 G 40 40 10 10 1.9 2.95 H 40 25 25 10 2.0 1.19 I 40 30 20 10 2.0 1.51 J 40 20 30 10 2.1 1.22 K 40 10 40 10 2.1 0.74 L 40 25 30 5 2.0 1.21

[0144] These results show that the stability of the emulsion can be multiplied by a factor close to 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 quantity of RAT, the more stable the emulsion, and vice versa for the RSV content.

[0145] 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.

[0146] [Table 3] Table 3 S (% by mass) A (% by mass) R (% by mass) RSV 27.1 54.0 15.8 RAT 52.8 39.4 7.4 Slurry 26.0 65.7 6.8 GO 56.3 43.0 0.7

[0147] [Table 4] Table 4 S (% by mass) A (% by mass) R (% by mass) A 41.2 49.3 8.0 B 40.9 49.0 8.7 c 40.5 48.6 9.4 D 38.2 51.6 8.6 E 37.9 51.2 9.3 G 40.2 48.2 10.0 H 36.2 52.2 9.9 I 37.5 50.9 10.0 J 34.8 53.5 9.9 K 32.2 56.1 9.9 L 34.7 53.3 10.2

[0148] [Fig. 1] shows that the half-life of the A-L emulsions 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.

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 containing at least 1% by mass of asphaltenes and having an aromatics content of at most 54% by mass.

2. Composition according to claim 1, characterized in that the fossil base contains at least 2% by mass of asphaltenes.

3. Composition according to claim 1 or 2, characterized in that the fossil base has a Sa parameter of 0.2 to 0.9 measured according to standard ASTM D7157-18 (Revision 2018).

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.

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 asphaltene-containing component chosen from: (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 cut, from catalytic cracking processes, such as the FCC process, (iv) effluents, in particular residues, from hydrotreatment, hydrocracking, deep hydroconversion, ARDS process, VRDS process, (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. A marine fuel composition consisting of or comprising the stable hydrocarbon combustion of any one of claims 1 to 7.

9. A method of 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 1% by mass of asphaltenes and having an aromatics 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 agitation to obtain a stable emulsion forming the stable hydrocarbon composition.

10. Preparation method according to claim 9, characterized in that the fossil base comprises at least 2% by mass of asphaltenes.

11. Preparation method according to claim 9 or 10, characterized in that the fossil base has a Sa parameter of 0.2 to 0.9 measured according to standard ASTM D7157-18 (Revision 2018).

12. 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 1% by mass of asphaltenes and having an aromatics content of at most 54% by mass.

13. Use according to claim 12, wherein the fossil base has a Sa parameter of 0.2 to 0.9 measured according to ASTM D7157-18 (2018 Revision).

14. Use of the hydrocarbon composition according to any one of claims 1 to 7 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 unit, a hydrotreatment unit, a hydrocracking unit, a partial oxidation unit.

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