Renewable composition of jet fuel with a high naphthenic compound content and associated preparation process

Abstract

Renewable jet fuel composition with high naphthenic compound content and associated preparation process The present invention relates to a jet fuel composition derived from renewable feedstocks comprising, relative to the total volume of the composition: a. 50 to 90% by volume of at least one paraffinic base derived from a hydrotreating of esters and fatty acids, a Fischer-Tropsch process or a process for producing jet fuel from alcohols, and comprising at least 90% by mass of paraffins relative to the total mass of the paraffinic base, b.of 10 to 50% by volume of at least one C8-C16 naphthenic base, said naphthenic base being obtained from the hydrogenation of a C8-C16 aromatic base, said aromatic base corresponding to the C8-C16 fraction of a biofuel produced by a process of converting at least one C1-C6 bioalcohol into fuel, and said aromatic base containing at least 60% by mass of aromatic compounds relative to the total mass of the aromatic base, said aromatic compounds comprising at least 50% by mass, preferably at least 80% by mass, of benzene substituted by at least m methyl groups, m being an integer from 1 to 3, and optionally n C2-C5 alkyl groups, n being an integer from 1 to 3, wherein said jet fuel composition comprises from 10 to 49% by mass of naphthenic compounds relative to the total mass of the composition. Figure for the abbreviation : None.

Description

Title of the invention: Renewable jet fuel composition with a high naphthenic compound content and associated preparation process technical field

[0001] The present invention relates to the field of jet fuels and in particular to a jet fuel derived from renewable feedstocks with a high content of naphthenic compounds.

[0002] CONTEXT OF THE INVENTION

[0003] Conventional jet fuel is produced from crude oil and contains a complex mixture of hydrocarbons that typically have 6 to 18 carbon atoms. These hydrocarbons include linear and branched alkanes, cycloalkanes, and aromatic hydrocarbons. Due to the petroleum feedstock and production processes, conventional jet fuel typically contains up to 25% by volume of aromatic hydrocarbons, more specifically typically from 10% to 25% by volume. A significant proportion, usually less than 5% of the aromatic hydrocarbons, are polycyclic (i.e., they contain two or more aromatic rings) and generally of the naphthalene type. Such compounds are harmful to health (e.g., carcinogenic) and have poor combustion properties.

[0004] Environmental, economic and energy constraints have encouraged the diversification of energy resources and the development of new fuels, particularly in the field of aviation.

[0005] Renewable fuels derived from biological matter are an alternative to conventional fossil fuels. Conventional jet fuels can be blended with paraffinic base fuels derived from renewable feedstocks as defined by standard D7566-21, thus enabling the production of alternative aviation fuels. Aviation fuel base fuels derived from renewable feedstocks that can be blended with fossil jet fuels are:

[0006] - synthetic paraffinic kerosenes [SPK], from processes such as the Fischer-Tropsch process, hydrotreating of esters and fatty acids [HEFA-SPK] or produced by the Alcohol-to-jet process (transformation of alcohol into kerosene) [ATJ-SPK], - synthetic isoparaffins produced by hydrotreatment from fermented sugars [SIP-HFS], - synthetic aromatic kerosenes obtained by alkylation of aromatics light non-petroleum source [SPK / A], - synthetic kerosenes obtained from the hydrothermal conversion of fatty acid esters and fatty acids, and - synthetic paraffinic kerosenes [SPK] obtained from hydrocarbons, esters and hydrotreated fatty acids.

[0007] In the short term, renewable fuels are introduced in blends with fossil fuels, but it will soon be necessary to use pure renewable fuels, without blending them with fossil fuel jet fuel. It is therefore necessary to develop renewable fuel formulations that meet current specifications and / or are compatible with current and future aircraft.

[0008] Currently, most renewable aviation fuel bases cannot be used on their own due to their composition being very different from that of fossil fuels, which poses problems, in particular, with the compatibility of the materials of the components with which the fuel comes into contact. This stems from the fact that these bases are primarily composed of paraffins. They therefore exhibit good combustion properties, but present problems for use in current aircraft, including issues of material compatibility, low density, low lubricity, and excessively low auto-ignition temperature. One possibility for resolving this problem is to add an aromatic base to the paraffinic base. (Article - Kramer S, Andac G, Heyne J, Ellsworth J, Herzig P and Lewis KC (2022) Perspectives on Fully Synthesized Sustainable Aviation Fuels: Direction and Opportunities. Front. Energy Res. 9:782823. doi: 10.3389 / fenrg.)202L782823 - thus presents the probable production routes of so-called 100% drop-in S AF, by mixing paraffinic bases and aromatic bases. However, even if aromatic compounds improve lubrication and seal strength, they have a negative impact on combustion emissions, mainly on the formation of fine particles and the presence of trails. STATE OF THE ART

[0009] US patent 8,629,310 describes a production process for converting oxygenated raw materials derived from biomass into various fuels, including hydrocarbons in the gas range, jet fuels, and diesel fuels. The resulting compositions comprise more than 50% by mass of naphthenic compounds.

[0010] Application WO 2021 / 237030 describes a kerosene composition produced from crude oil and shale oil, and comprising a substantial amount of aromatic compounds of between 4 and 10% by mass.

[0011] US application 2019 / 0002778 describes a kerosene composition produced by mixture of an a) aviation range fuel component and a b) renewable source diesel range fuel component.

[0012] US application 2009 / 0253947 describes a production process, in particular an integrated production process, of a fuel blend from a paraffin-rich component and a cyclic compound-rich component, each of the components being generated from a renewable feedstock.

[0013] US patent 10,087,374 describes a process for converting triacylglycerides into crude oil precursors and / or distilled hydrocarbon fuels.

[0014] None of these compositions allows for the optimization of their combustion quality while preserving, or even improving, their properties, such as their compatibility with materials, in particular with seals, their density, their lubricating power, their viscosity and / or their auto-ignition temperature.

[0015] There is therefore a need for new jet fuel compositions made exclusively from renewable feedstocks, exhibiting improved combustion quality compared to existing jet fuel compositions, while preserving, or even improving at least one of their properties chosen from among their compatibility with materials, in particular with seals, their density, their energy density, their lubricating power and / or their auto-ignition temperature.

[0016] There is also a need for a process enabling the preparation of jet fuel compositions derived exclusively from renewable feedstocks and exhibiting improved combustion quality compared to existing jet fuel compositions, while preserving, or even improving at least one of their properties chosen from among their compatibility with materials, in particular with seals, their density, their lubricating power, their viscosity, their auto-ignition temperature, and / or by improving their environmental impact.

[0017] DESCRIPTION OF THE INVENTION

[0018] To this end, the invention relates to a jet fuel composition derived from renewable feedstocks comprising, relative to the total volume of the composition:

[0019] a. 50 to 90% by volume of at least one paraffinic base obtained from a hydrotreating of esters and fatty acids, a Fischer-Tropsch process or a process for producing jet fuel from alcohols, and comprising at least 90% by mass of paraffins relative to the total mass of the paraffinic base,

[0020] b. 10 to 50% by volume of at least one C8-C16 naphthenic base, said naphthenic base being obtained from the hydrogenation of a C8-C16 aromatic base, said aromatic base corresponding to the C8-C16 fraction of a biofuel produced by a process converting at least one C1-C6 bioalcohol into fuel, and said aromatic base containing at least 60% by mass of aromatic compounds relative to the total mass of the aromatic base, said aromatic compounds comprising at less than 50% by mass, preferably at least 80% by mass, of benzene substituted by at least m methyl groups, m being an integer from 1 to 3, and optionally n alkyl groups in the C2-C5 range, n being an integer from 1 to 3,

[0021] wherein said jet fuel composition comprises from 10 to 49% by mass of naphthenic compounds relative to the total mass of the composition.

[0022] The inventors have discovered that such a composition, comprising in particular 10 to 50% by volume of at least one C8-C16 naphthenic base, makes it possible to solve the aforementioned technical problems. It exhibits improved combustion quality compared to existing jet fuel compositions, while preserving, or even improving, at least one of their properties selected from among their compatibility with materials, in particular with seals, their density, their lubricating power and / or their auto-ignition temperature.

[0023] Preferably, the composition comprises an amount less than or equal to 15% by volume, preferably less than 8% by volume, preferably less than or equal to 5% by volume of aromatic compounds, relative to the total volume of the composition.

[0024] Preferably, the naphthenic base comprises aromatic compounds and naphthenic compounds, and has a mass ratio between naphthenic compounds and aromatic compounds greater than or equal to 1, preferably greater than or equal to 2, preferably greater than or equal to 5.

[0025] Preferably, the composition further comprises from 1 to 18% by volume, preferably from 1 to 10% by volume, relative to the total volume of the composition, of at least one C8-C16 aromatic base, said aromatic base corresponding to the C8-C16 fraction of a biofuel produced by a process of converting at least one C1-C6 bioalcohol into fuel and characterized in that said aromatic base contains at least 60% by mass of aromatic compounds, said aromatic compounds comprising at least 50% by mass of benzene substituted by at least m methyl, m being an integer from 1 to 3, and optionally n alkyl in C2-C5, n being an integer from 1 to 3.

[0026] Preferably, the biofuel comprises at least 90% by volume of C4-C40 compounds, preferably of C4-C20 compounds, relative to the total volume of the biofuel.

[0027] The invention also relates to a first method for producing a jet fuel composition from renewable feedstocks, comprising at least the following steps:

[0028] a) the production of at least one paraffinic base from a hydrotreating of esters and fatty acids, a Fischer-Tropsch process or a process for producing jet fuel from alcohols (known as jet alcohols), said paraffinic base comprising at least 90% by mass of paraffins,

[0029] b) the production of at least one C8-C16 naphthenic base comprising at least the following steps:

[0030] i) the production of a biofuel by a process of converting at least one C1-C6 bioalcohol into fuel,

[0031] ii) the hydrogenation of the biofuel obtained at the end of step i) and the obtaining of a hydrogenated biofuel,

[0032] iii) the recovery of said C8-C16 naphthenic base by fractionation of said hydrogenated biofuel obtained in step ii), and

[0033] c) mixing 50% to 90% by volume of at least one paraffinic base produced in step a) with 10% to 50% by volume of the naphthenic base produced in step b), and obtaining a jet fuel composition comprising a paraffinic base and a naphthenic base.

[0034] The invention also relates to a second method for producing a jet fuel composition from renewable feedstocks, comprising at least the following steps:

[0035] a) the production of at least one paraffinic base from a hydrotreating of esters and fatty acids, a Fischer-Tropsch process or a process for producing jet fuel from alcohols (known as jet alcohols), said paraffinic base comprising at least 90% by mass of paraffins,

[0036] b) the production of a biofuel by a process of converting at least one C1-C6 bioalcohol into fuel,

[0037] c) i) the mixture of 50% to 90% by volume of at least one paraffinic base produced in step a) with 10% to 50% by volume of the biofuel produced in step b),

[0038] c) ii) hydrogenation of the mixture obtained in step c) i) to obtain a hydrogenated mixture, and

[0039] c) iii) the fractionation of the hydrogenated mixture and the obtaining of a jet fuel composition comprising a paraffinic base and a naphthenic base.

[0040] The production of the biofuel, the hydrogenation of the mixture and the fractionation of the hydrogenated mixture are as defined for the first process.

[0041] The invention also relates to a third method for producing a jet fuel composition from renewable feedstocks, comprising at least the following steps:

[0042] a) the production of at least one paraffinic base from a hydrotreating of esters and fatty acids, a Fischer-Tropsch process or a process for producing jet fuel from alcohols (known as jet alcohols), said paraffinic base comprising at least 90% by mass of paraffins,

[0043] b) the production of a biofuel by a process of converting into fuel from minus a C1-C6 bioalcohol,

[0044] c) i) hydrogenation of the biofuel obtained in step b) to obtain a hydrogenated biofuel

[0045] c) ii) the mixture of 50% to 90% by volume of at least one paraffinic base produced in step a) with 10% to 50% by volume of the hydrogenated biofuel produced in step c) i),

[0046] c) iii) the fractionation of the mixture obtained in step c) ii) and the obtaining of a jet fuel composition comprising a paraffinic base and a naphthenic base.

[0047] The production of the biofuel, the hydrogenation of the biofuel and the fractionation of the mixture are as defined for the first process.

[0048] According to one embodiment, in the processes according to the invention, hydrogenation is total.

[0049] According to another embodiment, in the processes according to the invention, hydrogenation is partial.

[0050] Preferably, in the processes according to the invention, at least one paraffinic base from step a) is produced from one or more oils selected from vegetable oils, animal fats, preferably highly saturated non-edible oils, used oils, by-products of refining vegetable or animal oil(s) containing free fatty acids, tallols, and oils produced by bacteria, yeasts, algae, prokaryotes or eukaryotes.

[0051] Preferably, the methods according to the invention further comprise:

[0052] - a step d) of producing at least one C8-C16 aromatic base comprising at least the following steps:

[0053] i) the production of a biofuel by a process of converting at least one C1-C6 bioalcohol into fuel,

[0054] ii) the recovery of said C8-C16 aromatic base by fractionation of said biofuel obtained in step i), said C8-C16 aromatic base comprising at least 60% by mass of aromatic compounds, said aromatic compounds comprising at least 50% by mass, preferably at least 80% by mass, of benzene substituted by at least m methyls, m being an integer from 1 to 3, and optionally n C2-C5 alkyls, n being an integer from 1 to 3, and

[0055] - a step e) of adding 1% to 18% by volume relative to the total volume of the communication position, preferably from 1% to 10% by volume, of the aromatic base produced in step b) in the jet fuel composition comprising a paraffinic base and a naphthenic base obtained at the end of step c).

[0056] Preferably, in the processes according to the invention, steps a), b), c), and possibly d) and e) when present, are carried out in separate processes. DETAILED DESCRIPTION OF THE INVENTION

[0057] The terms "including" and "includes" as used herein are synonymous with "including", "includes" or "contains", "containing", and are inclusive or boundless and do not exclude additional features, elements or unspecified method steps.

[0058] The expressions % by weight and % by mass have an equivalent meaning and refer to the proportion of the mass of a product relative to 100g of a composition comprising it.

[0059] The expression % by volume refers to the proportion of the volume of a product relative to 100 L of a composition comprising it.

[0060] By "naphthenic compounds" we mean C8-C16 cycloalkanes or polycycloalkanes, possibly substituted by C1-C5 alkyls. Paraffinic base according to the invention

[0061] Paraffin base means a synthetic paraffin fuel produced from non-petroleum-derived raw material.

[0062] Said synthetic paraffinic fuel is advantageously a renewable synthetic paraffinic kerosene (SPK) from a hydrotreating of esters and fatty acids (SPK-HEFA) or from a Fischer Tropsch process (SPK-FT) or from a process of transforming alcohol into isoparaffinic kerosene (SPK-ATJ).

[0063] The synthetic paraffinic fuel of the present invention is thus a renewable fuel obtained exclusively from compounds of non-fossil origin.

[0064] The renewable synthetic paraffinic fuel SPK-HEFA can be produced from naturally sourced oil(s) by a process of hydrogenation and deoxygenation of fatty acid esters and free fatty acids and subsequent processing of the product including hydrocracking, or hydroisomerization, or isomerization, or a combination thereof, and may include other conventional refining processes. In other words, the renewable synthetic paraffinic fuel SPK-HEFA is produced from the hydrotreating of esters and fatty acids from a naturally sourced oil. It is preferably compliant with ASTM D7566:21 Annex 2.

[0065] A naturally sourced oil is defined as an oil of biomass origin and containing no mineral oil. In the description, "naturally sourced oil(s)" refers indiscriminately to oils, fats, and mixtures thereof. Said naturally sourced oil(s) may contain one or more oils selected from among vegetable oils, animal fats, preferably highly saturated non-edible oils, used oils, by-products of the refining of vegetable or animal oil(s) containing free fatty acids, tallols, and produced oils. by bacteria, yeasts, algae, prokaryotes, or eukaryotes. Suitable vegetable oils include, for example, palm oil, palm kernel oil, soybean oil, rapeseed (canola) oil, sunflower oil, linseed oil, bran oil, rice bran oil, corn oil, olive oil, castor oil, sesame oil, pine oil, peanut oil, mustard oil, carinata oil, hemp oil, coconut oil, babassu oil, cottonseed oil, linola oil, and jatropha oil. Animal fats include tallow, lard, fat (yellow and brown), fish oil / fat, fat, and milk fats.

[0066] By-products of vegetable or animal oil refining are by-products containing free fatty acids that are removed from crude fats and oils by neutralization or vacuum or steam distillation. A typical example is PF AD (Palm Fatty Acid Distillate). Used oils include used cooking oils (waste food oils) and oils recovered from wastewater, such as motor oil / grease, gutter oil, sewage oil, for example from wastewater treatment plants, and used fats from the food industry. Tall oil, including crude tall oil, distilled tall oil (DTO), and tall oil fatty acids (TOFA), preferably DTO and TOFA, can also be used in the present invention.Tall oil, also known as tallol, is a liquid by-product of the Kraft wood processing method, used to isolate wood pulp, which is valuable for the paper industry. Tall oil is primarily obtained when conifers are used in the Kraft process. After treating wood chips with aqueous sodium sulfide solution, the isolated tall oil is alkaline. This is then acidified with sulfuric acid to produce crude tall oil. The natural oils used in the present invention also include oils produced by microorganisms, whether natural or genetically modified, such as bacteria, yeasts, algae, prokaryotes, or eukaryotes. In particular, such oils can be recovered by well-known mechanical or chemical extraction methods.

[0067] The renewable paraffinic synthetic fuel SPK-FT is produced using a Fischer-Tropsch process and can be produced from solid biomass. It is preferably compliant with ASTM D7566:21 Annex 1. The thermochemical conversion of biomass (gasification and Fischer-Tropsch synthesis), also known as BtL (Biomass to Liquid), comprises the following steps: conditioning of the biomass (preparation, crushing, torrefaction), gasification of the biomass (obtaining a synthesis gas), purification of the synthesis gas, and Fischer-Tropsch synthesis to transform the gas into synthetic biofuel.

[0068] Regardless of the aforementioned process used, the synthetic paraffinic fuel can having undergone an isomerization and / or distillation step before its incorporation into the composition of the invention, in order to eliminate the heaviest linear paraffins that would prevent compliance with the cold-weather properties of the jet, in particular the disappearance point of the crystals, which must be below -47°C for the Al Jet. The lighter compounds can also be separated by distillation, in order to comply, in particular, with the volatility and flash point properties of the Al Jet. Regardless of the aforementioned process used, the renewable synthetic paraffinic fuel may exhibit one or more of the following characteristics:

[0069] - a paraffin content exceeding 90% by mass,

[0070] - a cycloparaffin content of less than 10% by mass,

[0071] - a freezing point below -30°C, preferably below -40°C, by example below -47 °C

[0072] - a density at 15°C between 730 and 780 kg / m³,

[0073] - a distillation range of 145°C to 315°C,

[0074] - an isoparaffins content of 70% by mass or more.

[0075] The renewable synthetic paraffinic fuel SPK-ATJ can conform to ASTM D7566:21 Annex 5 but can also be produced from any alcohol with 1 to 6 carbon atoms. The renewable fuel SPK-ATJ is obtained by dehydrating alcohols to produce olefins, then oligomerizing the olefins to obtain unsaturated hydrocarbon molecules within the boiling range of SAF. These unsaturated hydrocarbon molecules are then hydrogenated to produce the paraffinic base.

[0076] For the implementation of the first process according to the invention, the paraffin base preferably conforms to the specification ASTM D7566:21.

[0077] The second and third methods according to the invention can be implemented whether or not the paraffinic base conforms to the ASTM D7566:21 specification. Naphthenic base according to the invention

[0078] The C8-C16 naphthenic base is produced by hydrogenation of a biofuel obtained by a process of converting at least one C1-C6 bioalcohol into fuel, followed by fractionation of the hydrogenated biofuel.

[0079] Step i): production of a biofuel

[0080] The production of the biofuel can be carried out by converting at least one C1-C6 bioalcohol in a catalytic process. The catalytic process can be carried out on an aluminosilicate bed, preferably of the zeolite type.

[0081] The C1-C6 bioalcohol mainly contains alcohols such as methanol, ethanol, propanols (n-propanol, i-propanol), butanols (n-butanol, i-butanol), pentanols (n-pentanols, i-pentanol), and hexanols. The C1-C6 bioalcohol preferably contains more than 80% by mass of C1-C6 alcohols, preferably more than 90%. in mass of alcohols in Cl to C6.

[0082] The C1-C6 bioalcohol can be:

[0083] - Methanol obtained from biomass:

[0084] Biomass may include, in particular, woody fuels from natural forests and woodlands (e.g., sawdust), agricultural residues (e.g., rice husks, straw manure), energy crops grown exclusively for energy production (e.g., maize and oil palm), urban waste (e.g., wood waste, rice, straw manure), energy crops grown exclusively for energy production (e.g., maize and oil palm), urban waste (e.g., municipal solid waste and wastewater), and biomass fuel derived from waste (e.g., wood pellets). Methanol from renewable sources may, in particular, be obtained by converting a synthetic gas rich in CO / H2, this synthetic gas being derived from biomass.Biomass can, for example, be gasified to produce a synthetic gas (or "syngas") rich in CO / H2, which is then converted into methanol in the presence of a catalyst. A process of this type is described, for example, in document WO2018134853A1. A synthetic gas suitable for subsequent conversion into methanol can also be obtained by partial oxidation in the presence of dioxygen of a biogas containing methane and CO2, this biogas resulting, for example, from the anaerobic digestion of biomass in the presence of one or more microorganisms. A process of this type is described, for example, in document WO2019060988A1.

[0085] - Methanol obtained from carbon dioxide:

[0086] Several transformation routes exist. One example is the catalytic conversion of carbon dioxide to methanol in the presence of hydrogen. Another route involves converting carbon dioxide to carbon monoxide by electroconversion or by reverse gas-water reaction in the presence of hydrogen. The carbon monoxide is then converted by catalytic conversion to methanol in the presence of hydrogen. The hydrogen used for the various operations described above is obtained, in particular, by steam reforming of methane, by gas-water reaction, or is produced by electrolysis from renewable energy sources such as solar energy, wind, geothermal energy, waves, or currents.

[0087] - Bioethanol produced from ethanolic fermentation by the action of iron- ment of microorganisms, yeasts and / or bacteria from at least one raw material of plant origin:

[0088] Bioethanol can advantageously be obtained by:

[0089] - anaerobic fermentation of a sugar-rich substrate derived from biomass, or

[0090] - anaerobic fermentation of a gas comprising CO, which may originate from biomass or not.

[0091] For the anaerobic fermentation of a sugar-rich substrate, the sugars are composed of chains of 6 or 5 carbons, such as glucose, sucrose (dimer of glucose and fructose), xylose and arabinose.

[0092] This substrate may, for example, comprise or be derived directly from agri-food plants, sugar cane, sugar beet, sweet sorghum, or by depolymerization of starch from maize, wheat, barley, rye, sorghum, triticale, potato, sweet potato, cassava, and / or cellulose and hemicellulose from lignocellulosic biomass.

[0093] The sugar-rich substrate can also be obtained from lignocellulosic biomass by a process comprising (i) a step of separating the lignin, cellulose, and hemicellulose contained in the lignocellulosic biomass, followed by (ii) a step of converting the cellulose and / or hemicellulose into sugars. Obtaining this type of substrate from lignocellulosic biomass is well known to those skilled in the art. The sugar-rich substrate is then subjected to fermentation, for example, using microorganisms.

[0094] Ethanol can also be produced by anaerobic fermentation of a gas containing CO. The substrate is then a gaseous substrate (a gas) containing CO. This gaseous substrate can be a by-product of an industrial process, such as the manufacture of ferrous metal products, in particular steel mills, the manufacture of non-ferrous products, petroleum refining processes, the gasification of coal and / or biomass or biochar, the production of electrical energy, the production of carbon black, the production of ammonia, the production of methanol, the manufacture of coke, catalytic cracking (in particular during the regeneration of the catalyst carbon monoxide is produced) and the reforming of methane.

[0095] In other embodiments, the gaseous substrate may originate from the gasification of biomass, such as biomass by-products obtained during the extraction and processing of food products. The gasification process involves the partial combustion of biomass in a restricted supply of air or oxygen. The resulting gas generally comprises mainly CO and H2, with minimal volumes of CO2, methane, ethylene, and ethane. The CO content of the gaseous substrate is typically 15% to 100% by volume, 15% to 95% by volume, 40% to 95% by volume, 40% to 60% by volume, and 45% to 55% by volume, or is within any range defined by two of these limits.

[0096] Any microorganism capable of fermenting a gaseous substrate including CO to produce ethanol may be used.

[0097] - Bioethanol produced from biomass by conversion of a gas CO / H2 rich synthesis, this synthetic gas being derived from biomass.

[0098] Biomass can, for example, be gasified to produce a synthesis gas (or "syngas") rich in CO / H2, this synthetic gas then being converted into methanol in the presence of a catalyst. A process of this type is described, for example, in document WO2012003901.

[0099] - Any other alcohol comprising 3 to 6 carbon atoms obtained, for example, by:

[0100] - catalytic reaction of hydrogen with carbon dioxide or monoxide carbon;

[0101] - catalytic reaction of hydrogen with carbohydrates;

[0102] - ABE fermentation, a bacterial fermentation producing a mixture of ethanol, acetone and butanol from carbohydrates such as glucose or starch;

[0103] - anaerobic fermentation of sugars from biomass, in particular to obtain propanol (iso or n), butanol (iso or n) or isoamyl alcohol;

[0104] - anaerobic fermentation of a mixture containing at least monoxide carbon, carbon dioxide and hydrogen to obtain in particular propanol (iso or n), butanol (iso or n) or isoamyl alcohol.

[0105] Step ii): hydrogenation of the biofuel

[0106] Hydrogenation of biofuel partially or totally hydrogenates unsaturated compounds included in the biofuel, in particular partially or totally hydrogenates aromatic compounds included in the biofuel.

[0107] Hydrogenation is carried out for example in one or more fixed bed reactors (falling or rising) and in mixed phase, the fraction to be hydrogenated being mainly in liquid phase.

[0108] Hydrogenation is carried out, for example, at a temperature between 50°C and 350°C, in particular between 100°C and 300°C. It is carried out under a pressure preferably greater than 10 bara and in particular between 20 bara and 80 bara.

[0109] A hydrogen stream is fed into the reactor(s) mixed with the aromatic base stream to be hydrogenated. The ratio of the volumetric flow rate of the hydrogen stream to the volumetric flow rate of the aromatic base (excluding the recycled stream) to be hydrogenated is advantageously between 50 NL / L and 3000 NL / L, in particular between 100 NL / L and 500 NL / L. The hydrogen can be added to the biofuel stream in several stages along the catalytic bed. The hourly spatial velocity is advantageously between 0.5 and 3, and in particular between 1 and 2 h'. Excess hydrogen can be recycled to the reaction zone after separation and compression.

[0110] The reaction is carried out in the presence of at least one catalyst comprising one or more metals of Group VIII (typically Pt, Pd, Ni) supported on a support such as silica, alumina, or any mixture of these two compounds or carbon. The reaction can also be carried out in the presence of a sulfide-type catalyst containing an element of Group VIB (Cr, Mo, W) and an element of Group VIIIB (Fe, Ru, Co, Os, Co, Rh, Ir, Pd, Ni, Pt) or mixtures of these two groups of metals.

[0111] The hydrogenation step is preferably followed by a separation step of the light compounds, generally carried out by stripping or distillation. This separation step makes it possible to produce a hydrogenated C8-C16 type fraction, suitable for incorporation into aviation fuel.

[0112] According to one variant, the hydrogenation of the biofuel is total. This means that the aromatic compounds contained in the biofuel are hydrogenated to more than 99%.

[0113] According to another embodiment, the hydrogenation of the biofuel is partial. Preferably, between 10% and 99%, preferably between 10% and 90% by mass of the aromatic compounds contained in the biofuel to be hydrogenated, preferably between 30% by mass and 80% by mass of the aromatic compounds contained in the biofuel to be hydrogenated, are hydrogenated into naphthenic compounds.

[0114] All the above characteristics and variants concerning the hydrogenation of the biofuel of the first process also apply to the hydrogenation of the mixture of the second process according to the invention, and to the hydrogenation of the biofuel of the third process according to the invention.

[0115] Step iii): recovery of the naphthenic base at C8-C16

[0116] The hydrogenated biofuel obtained in step ii) is fractionated to recover the C8-C16 naphthenic fraction.

[0117] According to the variant of the process in which the biofuel is partially hydrogenated, the naphthenic base recovered by fractionation of the partially hydrogenated biofuel comprises a mixture of aromatic compounds and naphthenic compounds.

[0118] According to this variant, the naphthenic base preferably comprises at least 60% by mass of naphthenic compounds, preferably from 70% to 95% by mass of naphthenic compounds, preferably from 75% to 95% by mass of naphthenic compounds.

[0119] According to this variant, the naphthenic base preferably has a mass ratio between naphthenic compounds and aromatic compounds greater than or equal to 1, preferably greater than or equal to 2, preferably greater than or equal to 5, preferably between 1 and 99, preferably between 5 and 24, preferably between 5 and 10.

[0120] In particular, the production of the paraffinic and naphthenic bases according to the invention can be carried out from different renewable sources, and in particular by separate processes.

[0121] All the above features and variants concerning the hydrogenated biofuel fractionation step of the first process also apply to the hydrogenated mixture fractionation step of the second process according to the invention and to the mixture fractionation step of the third process according to the invention. Aromatic base according to the invention

[0122] The composition according to the invention may further comprise a C8-C16 aromatic base.

[0123] The C8-C16 aromatic base can be produced according to the following steps:

[0124] i) production of a biofuel by submitting at least one C1-C6 bioalcohol derived of at least one renewable feedstock to a process for converting alcohol into fuel,

[0125] ii) recovery by fractionation of said aromatic base in C8-C16 from said biofuel obtained in step i).

[0126] Step i) of biofuel production is identical to that described above for naphthenic base production.

[0127] Step ii): recovery of the C8-C16 aromatic base

[0128] The biofuel obtained in step i) is fractionated to recover the C8-C16 fraction in order to meet the volatility properties of aviation fuels.

[0129] The C8-C16 aromatic base according to the invention may have one or more of the following characteristics:

[0130] - at least 60% by mass of C8-C16 aromatic compounds, in particular monoaromatic compounds, said aromatic compounds comprising at least 50% by mass, preferably at least 80% by mass, of benzene substituted by at least m methyl groups, m being an integer from 1 to 3, and optionally n alkyl groups in the C2-C5 range, n being an integer from 1 to 3,

[0131] - from 8% by mass to 15% by mass of naphthenic compounds,

[0132] - from 5% by mass to 15% by mass of isoparaffins,

[0133] - less than 5% by mass of n-paraffins.

[0134] It should be noted that said aromatic compounds, present in a content of at least 60% by mass, comprise benzene substituted by at least m methyl and optionally n alkyl groups in C2-C5. These aromatic compounds may thus comprise a mixture of benzene molecules substituted by at least m methyl groups, m being an integer from 1 to 3, and optionally benzene molecules substituted by at least m methyl groups, m being an integer from 1 to 3, and / or n alkyl groups in C2-C5, n being an integer from 1 to 3.

[0135] In particular, the production of paraffinic and naphthenic bases according to the invention can be carried out from different renewable sources, and in particular by separate processes. Jet fuel composition according to the invention

[0136] Preferably, the composition according to the invention comprises from 50% to 85% by volume, preferably from 55% to 80% by volume, preferably from 55% to 75% by volume of at least one paraffin base.

[0137] Preferably, the composition according to the invention comprises 15% to 50% by volume, preferably 20% to 45% by volume, preferably 25% to 45% by volume of at least one naphthenic base.

[0138] Preferably, the composition according to the invention comprises less than 18% by volume, preferably less than 10% by volume, preferably less than 8% by volume, preferably less than 5% by volume, preferably from 1% to 18% by volume, preferably from 1% to 10% by volume of at least one aromatic base.

[0139] Preferably, the composition according to the invention has a mass ratio of naphthenic compounds / aromatic compounds greater than or equal to 1, preferably greater than or equal to 2, preferably greater than or equal to 3, preferably between 3 and 5.

[0140] Preferably, the composition according to the invention comprises from 15% to 48% by mass of naphthenic compounds, preferably from 25% to 45% by mass of naphthenic compounds.

[0141] Preferably, the composition according to the invention comprises an amount of aromatic compounds less than or equal to 15% by volume, preferably less than or equal to 8% by volume, preferably less than or equal to 5% by volume, relative to the total volume of the composition. Preferably, the composition according to the invention comprises an amount of aromatic compounds between 1 and 15% by volume, preferably between 1 and 8% by volume, relative to the total volume of the composition.

[0142] The quantity of aromatic compounds included in the composition according to the invention is defined by volume in accordance with the specifications of ASTM D7566:21.

[0143] Advantageously, the jet fuel composition according to the invention can comply with Jet A or Jet Al requirements as defined in ASTM D7566:21 of July 2021 or in DefStan 91-091 Issue which refers to ASTM D7566:21.

[0144] For example, the composition according to the invention has a density between 755 kg / m3 and 840 kg / m3, preferably between 775 kg / m3 and 840 kg / m3.

[0145] In particular, the levels of paraffinic base, naphthenic base, and aromatic base when present, in the jet fuel composition according to the invention can be chosen so that the jet fuel composition according to the invention complies with these requirements.

[0146] In an advantageous embodiment, at least one paraffinic base and at least one naphthenic base are obtained from separate processing of renewable feedstocks (from distinct processes), in particular from distinct renewable feedstocks. In a preferred embodiment, the jet fuel composition according to the invention consists of the paraffinic, naphthenic, and aromatic bases, when present, obtained from renewable feedstocks.

[0147] According to one embodiment, the jet fuel composition according to the invention is free of petroleum-derived components.

[0148] The example below illustrates the invention without limiting its scope. EXAMPLES

[0149] Two compositions Cl and C2 according to the invention are prepared.

[0150] Cl comprises 68% by volume of HEFA conforming to the paraffinic base a) according to the invention and 32% by volume of the naphthenic base b).

[0151] C2 comprises 61% by volume of HEFA conforming to the paraffinic base a) according to the invention and 39% by volume of the naphthenic base b).

[0152] Compositions Cl and C2, as well as HEFA conforming to paraffinic base a) have the characteristics detailed in the following table (these characteristics were determined according to the standards specified in each column):

[0153] [Tables 1] Auto-ignition point (°C) Density (kg / m³) Viscosity @ -20°C (mm² / s) Viscosity @ -40°C (mm² / s) LOOP (mm) ASTM E659-15 ASTM D1298-06 ASTM D445-21 ASTM D5001 (19 units) HEFA 198 760.9 5.794 13.28 0.85 Cl 230 773.5 4.274 8.594 0.77 C2 249 776.3 4.024 7.897 0.77

[0154] The addition of the naphthenic base b) to a paraffinic base a) thus makes it possible to obtain compositions with improved properties. In particular, the addition of the naphthenic base b) surprisingly improves the viscosity at -40°C of the paraffinic base, as well as its lubricity (BOCLE). This shows that it is possible to replace at least part of the aromatic base, frequently used in combination with paraffinic bases, with a naphthenic base, and thus reduce the formation of fine particles and the presence of streaks.

Claims

Demands

1. Jet fuel composition from renewable feedstocks comprising, relative to the total volume of the composition: a. 50 to 90% by volume of at least one paraffinic base produced by hydrotreating esters and fatty acids, by a Fischer-Tropsch process or by a process for producing jet fuel from alcohols, and comprising at least 90% by mass of paraffins relative to the total mass of the paraffinic base, b.of 10 to 50% by volume of at least one C8-C16 naphthenic base, said naphthenic base being obtained from the hydrogenation of a C8-C16 aromatic base, said aromatic base corresponding to the C8-C16 fraction of a biofuel produced by a process of converting at least one C1-C6 bioalcohol into fuel, and said aromatic base containing at least 60% by mass of aromatic compounds relative to the total mass of the aromatic base, said aromatic compounds comprising at least 50% by mass, preferably at least 80% by mass, of benzene substituted by at least m methyls, m being an integer from 1 to 3, and optionally n C2-C5 alkyls, n being an integer from 1 to 3, in which said jet fuel composition comprises from 10 to 49% by mass of naphthenic compounds relative to the total mass of the composition.

2. Jet fuel composition according to claim 1, comprising an amount less than or equal to 15% by volume, preferably less than 8% by volume, preferably less than or equal to 5% by volume of aromatic compounds, relative to the total volume of the composition.

3. Jet fuel composition according to claim 1 or 2, wherein the naphthenic base comprises aromatic compounds and naphthenic compounds, and has a mass ratio of naphthenic compounds to aromatic compounds greater than or equal to 1, preferably greater than or equal to 2, preferably greater than or equal to 5

4. J. Jet fuel composition according to any one of the preceding claims, further comprising from 1 to 18% by volume, preferably from 1 to 10% by volume, relative to the total volume of the composition, of at least one C8-C16 aromatic base, said aromatic base corresponding to the C8-C16 fraction of a biofuel produced by a process of converting at least one C1-C6 bioalcohol into fuel and characterized in that said aromatic base contains at least 60% by mass of aromatic compounds, said aromatic compounds comprising at least 50% by mass of benzene substituted by at least m methyl, m being an integer from 1 to 3, and optionally n alkyl in C2-C5, n being an integer from 1 to 3.

5. A process for producing a jet fuel composition from renewable feedstocks, comprising at least the following steps: a) the production of at least one paraffinic base from a hydrotreating of esters and fatty acids, a Fischer-Tropsch process, or a process for producing jet fuel from alcohols, said at least one paraffinic base comprising at least 90% by mass of paraffins; b) the production of at least one C8-C16 naphthenic base comprising at least the following steps: i) the production of a biofuel by a process converting at least one C1-C6 bioalcohol into fuel; ii) the hydrogenation of the biofuel obtained in step i) and the production of a hydrogenated biofuel; iii) the recovery of said C8-C16 naphthenic base by fractionation of said hydrogenated biofuel obtained in step ii).and c) mixing 50% to 90% by volume of at least one paraffinic base produced in step a) with 10% to 50% by volume of the naphthenic base produced in step b), and obtaining a jet fuel composition comprising a paraffinic base and a naphthenic base.

6. A process for producing a jet fuel composition from renewable feedstocks according to claim 5, wherein hydrogenation is total.

7. A process for producing a jet fuel composition from renewable feedstocks according to claim 5, wherein hydrogenation is partial.

8. A method for producing a jet fuel composition from renewable feedstocks according to any one of claims 5 to 7, wherein at least one paraffinic base from step a) is produced from one or more oils selected from vegetable oils, animal fats, preferably non-edible highly saturated oils, used oils, by-products of refining of vegetable oils or animal oil(s) containing free fatty acids, tallols, and oils produced by bacteria, yeasts, algae, prokaryotes or eukaryotes.

9. A method for producing a jet fuel composition according to any one of claims 5 to 8, further comprising: - a step d) of producing at least one C8-C16 aromatic base comprising at least the following steps: (i) the production of a biofuel by a process of converting at least one C1-C6 bioalcohol into fuel, (ii) the recovery of said C8-C16 aromatic base by fractionation of said biofuel obtained in step (i), said C8-C16 aromatic base comprising at least 60% by mass of aromatic compounds, said aromatic compounds comprising at least 50% by mass, preferably at least 80% by mass, of benzene substituted by at least m methyl groups, m being an integer from 1 to 3, and optionally n C2-C5 alkyl groups, n being an integer from 1 to 3, and - a step e) of adding 1% to 18% by volume relative to the total volume of the composition, preferably 1% to 10% by volume, of the aromatic base produced in step b) into the jet fuel composition comprising a paraffinic base and a naphthenic base obtained at the end of step c).

10. A process for producing a jet fuel composition according to any one of claims 5 to 9, wherein steps a), b), c), and optionally d) and e) when present, are carried out in separate processes.