Renewable jet fuel composition with high content of naphthenic compounds

Abstract

The present invention relates to a jet fuel composition obtained from renewable feedstock comprising, relative to the total volume of the composition: a. 50-90% by volume of at least one paraffin matrix obtained from the hydrotreatment of esters and fatty acids, from the Fischer-Tropsch process or from the process for producing jet fuels from alcohols, and comprising, relative to the total weight of the paraffin matrix, a. 30-90% by volume of at least one paraffin matrix obtained from the hydrotreatment of esters and fatty acids, from the Fischer-Tropsch process or from the process for producing jet fuels from alcohols; the present invention relates to a composition comprising: a. At least 90% by weight of paraffin, b. 10% to 50% by volume of at least one C8-C16 cycloalkyl derived from the hydrogenation of a C8-C16 aromatic matrix corresponding to a C8-C16 fraction of a biofuel produced by a process for converting at least one C1-C6 bioalcohol into a fuel, and containing, relative to the total weight of the aromatic matrix, at least 90% by weight of paraffin, b. 10% to 50% by volume of at least one C8-C16 cycloalkyl derived from the hydrogenation of a C8-C16 aromatic matrix corresponding to a C8-C16 fraction of a biofuel produced by a process for converting at least one C1-C6 bioalcohol into a fuel, the invention relates to a jet fuel composition comprising at least 60% by weight of an aromatic compound comprising at least 50% by weight, preferably at least 80% by weight, of benzene substituted with at least m methyl groups, m being an integer of 1-3, and optionally with n C2-C5 alkyl groups, n being an integer of 1-3, where the jet fuel composition comprises at least 50% by weight, preferably at least 80% by weight, of at least 50% by weight, preferably at least 80% by weight, of benzene substituted with at least m methyl groups, and optionally with n C2-C5 alkyl groups, with respect to the total weight of the composition. 10 wt% to 49 wt% of a naphthenic compound.

Description

Technical Field

[0001] The present invention relates to the field of jet fuels, and in particular to jet fuels obtainable from renewable raw materials, which have a high content of cycloparaffinic compounds. Background Art

[0002] Conventional fuels of the jet fuel type are produced from crude oil and contain a complex mixture of hydrocarbons generally having 6-18 carbon atoms. These hydrocarbons include straight and branched alkanes, cycloalkanes and aromatic hydrocarbons. Considering their petroleum-derived raw materials and production methods, conventional fuels of the jet fuel type generally contain up to 25% by volume of aromatic hydrocarbons, more specifically, 10% to 25% by volume of aromatic hydrocarbons. A significant proportion of aromatic hydrocarbons (generally in the range of less than 5%) are polycyclic (i.e., they contain two or more aromatic rings) and are generally of the naphthalene type. Such compounds are harmful to health (e.g., carcinogenic) and have poor combustion properties.

[0003] Environmental, economic and energy constraints have prompted the diversification of energy sources and the development of new fuels, particularly in the aviation sector.

[0004] Renewable fuels derived from biomass are an alternative to conventional fossil fuels. Conventional jet fuel can be blended with a paraffinic matrix derived from renewable feedstocks (such as provided by the D7566-21 standard) to produce alternative aviation fuels. Aviation fuel matrices derived from renewable feedstocks that can be blended into fossil jet fuels are:

[0005] - synthetic paraffinic kerosene [SPK] obtained by processes such as the Fischer-Tropsch process, hydroprocessing of esters and fatty acids [HEFA-SPK] or produced by the Alcohol-to-Jet process (alcohol conversion to kerosene) [ATJ-SPK],

[0006] - Synthetic isoparaffins produced by hydroprocessing of fermented sugars [SIP-HFS],

[0007] - synthetic aromatic kerosenes obtained by alkylation of light aromatic compounds of non-petroleum origin [SPK / A],

[0008] - synthetic kerosenes obtained from the hydrothermal conversion of fatty acid esters and fatty acids, and

[0009] - Synthetic paraffinic kerosene [SPK] obtained from hydrotreated hydrocarbons, esters and fatty acids.

[0010] In the short term, renewable fuels are blended with fossil fuels, but soon it will be necessary to use pure renewable fuels without blending them with fossil jet fuels. Therefore, there is a need to develop renewable fuel formulations that meet current specifications and / or are compatible with current and future aircraft.

[0011] At present, the renewable bases of aviation fuels cannot be used alone for the most part, because their composition is very different from that of fossil jet fuels, especially giving rise to compatibility problems with the materials of the elements with which the fuel comes into contact. This is due to the fact that these bases consist mainly of paraffin wax. Therefore, they have good combustion properties, but problems arise when used in current aircraft, especially problems of material compatibility, low density, low lubricity, too low autoignition temperature. One possibility to solve this problem is to add an aromatic base to the paraffin wax base. The 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.2021.782823) proposes a possible direction to produce so-called 100% ready-to-use sustainable aviation fuels (SAF) by mixing a paraffin base with an aromatic base. However, although aromatic compounds improve the lubrication and durability of seals, they have a negative impact on combustion emissions, mainly on the formation of fine particles and the presence of condensation trails (condensation trails).

[0012] Prior art

[0013] Patent US 8,629,310 describes a production process that allows the conversion of oxygenated feedstocks originating from biomass into different fuels, in particular hydrocarbons in the range of gases, jet fuels and diesel fuels. The composition obtained contains more than 50% by weight of cycloparaffinic compounds.

[0014] Application WO 2021 / 237030 describes a kerosene composition produced from crude oil and shale oil, which contains a large amount of 4% to 10% by weight of aromatic compounds.

[0015] Application US 2019 / 0002778 describes a kerosene composition produced by mixing a) an aviation range fuel component and b) a diesel range fuel component from renewable resources.

[0016] Application US 2009 / 0253947 describes a production process, in particular an integrated production process for a fuel mixture produced from a component rich in paraffins and a component rich in cyclic compounds, each component being produced from renewable raw materials.

[0017] Patent US 10,087,374 describes a process for converting triacylglycerides into precursors for crude oil and / or distilled hydrocarbon fuels.

[0018] None of these compositions makes it possible to optimize their combustion properties while maintaining or even improving their properties, such as compatibility with materials (especially seals), their density, lubricity, viscosity and / or autoignition temperature.

[0019] Therefore, there is a need for a new jet fuel composition completely derived from renewable raw materials, which has improved combustion properties compared to existing jet fuel compositions, while retaining or even improving at least one property selected from its compatibility with materials (especially seals), its density, energy density, lubricity and / or autoignition temperature.

[0020] There is also a need for a process for preparing a jet fuel composition derived entirely from renewable raw materials, which has improved combustion properties over existing jet fuel compositions, while retaining or even improving at least one property selected from its compatibility with materials (particularly seals), its density, lubricity, viscosity and / or autoignition temperature, and / or improving its environmental impact. Summary of the invention

[0021] To this end, the present invention relates to a jet fuel composition obtainable from renewable raw materials, comprising: relative to the total volume of the composition:

[0022] a. 50% to 90% by volume of at least one paraffinic matrix obtained from the hydroprocessing of esters and fatty acids, from the Fischer-Tropsch process or from a process for producing jet fuel from alcohols and containing at least 90% by weight of paraffins relative to the total weight of the paraffinic matrix,

[0023] b. 10% to 50% by volume of at least one C8-C16 cycloalkyl substrate obtained from the hydrogenation of a C8-C16 aromatic substrate corresponding to the C8-C16 fraction of a biofuel produced by a process for converting at least one C1-C6 bioalcohol into a fuel, said aromatic substrate containing, relative to the total weight of said aromatic substrate, at least 60% by weight of aromatic compounds, said aromatic compounds comprising at least 50% by weight, preferably at least 80% by weight, of benzene substituted by at least m methyl groups, m being an integer from 1 to 3, and optionally substituted by n C2-C5 alkyl groups, n being an integer from 1 to 3,

[0024] The jet fuel composition comprises 10 wt% to 49 wt% of cycloalkane compounds relative to the total weight of the composition.

[0025] The inventors have found that the composition, in particular comprising 10% to 50% by volume of at least one C8-C16 cycloalkyl matrix, can solve the above technical problem and show improved combustion performance compared to existing jet fuel compositions, while retaining or even improving at least one property selected from its compatibility with materials (in particular seals), its density, lubricity and / or autoignition temperature.

[0026] Preferably, the composition comprises 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.

[0027] Preferably, the cycloalkane matrix comprises aromatic compounds and cycloalkane compounds, and has a mass ratio of cycloalkane compounds to aromatic compounds greater than or equal to 1, preferably greater than or equal to 2, preferably greater than or equal to 5.

[0028] Preferably, the composition further comprises, relative to the total volume of the composition, 1% to 18% by volume, preferably 1% to 10% by volume, of at least one C8-C16 aromatic substrate, the aromatic substrate corresponding to the C8-C16 fraction of a biofuel produced by a process for converting at least one C1-C6 bioalcohol into a fuel, and characterized in that the aromatic substrate contains at least 60% by weight of aromatic compounds, the aromatic compounds comprising at least 50% by weight of benzene, the benzene being substituted by at least m methyl groups, m being an integer from 1 to 3, and optionally substituted by n C2-C5 alkyl groups, n being an integer from 1 to 3.

[0029] Preferably, the biofuel comprises at least 90 volume % of C4-C40 compounds, preferably C4-C20 compounds, relative to the total volume of the biofuel.

[0030] The present invention also relates to a method for producing a jet fuel composition obtainable from renewable raw materials, comprising at least the following steps:

[0031] a) producing at least one paraffinic matrix by hydroprocessing of esters and fatty acids, by the Fischer-Tropsch process or by the process for producing jet fuel from alcohols (known as Alcohol-to-Jet), said paraffinic matrix comprising at least 90% by weight of paraffins,

[0032] b) producing at least one C8-C16 aromatic substrate, comprising at least the following steps:

[0033] i) producing a biofuel by a process for converting at least one C1-C6 bioalcohol into a fuel,

[0034] ii) recovering the C8-C16 aromatic matrix by fractional distillation of the biofuel obtained in step i), the C8-C16 aromatic matrix comprising at least 60% by weight of aromatic compounds, the aromatic compounds comprising at least 50% by weight, preferably at least 80% by weight of benzene, the benzene being substituted with at least m methyl groups, m being an integer from 1 to 3, and optionally substituted with n C2-C5 alkyl groups, n being an integer from 1 to 3,

[0035] c) Hydrogenation of C8-C16 aromatic substrates.

[0036] In one embodiment, step c) comprises hydrogenation of the C8-C16 aromatic substrate obtained after step b) to obtain a cycloalkyl substrate, and the process further comprises a step d) of mixing 50% to 90% by volume of at least one paraffinic substrate produced in step a) with 10% to 50% by volume of the cycloalkyl substrate produced in step c) to obtain a jet fuel composition comprising the paraffinic substrate and the cycloalkyl substrate, the volume % values ​​being relative to the total volume of the composition.

[0037] In another embodiment, between step b) and step c), the method comprises a step b'): mixing 50% to 90% by volume of at least one paraffinic base produced in step a) with 10% to 50% by volume of at least one aromatic base produced in step b) to obtain a mixture of a paraffinic base and an aromatic base, the volume % values ​​being relative to the total volume of the mixture, and the hydrogenation step c) of the C8-C16 aromatic base comprises hydrogenating the mixture of the paraffinic base and the aromatic base obtained in step b') to obtain a jet fuel composition comprising a paraffinic base and a cycloalkyl base.

[0038] Therefore, the present invention particularly relates to a method for producing a jet fuel composition derived from renewable raw materials, comprising at least the following steps:

[0039] a) producing at least one paraffinic matrix by hydroprocessing of esters and fatty acids, by a Fischer-Tropsch process or by a process for producing jet fuels from alcohols, said at least one paraffinic matrix comprising at least 90% by weight of paraffins,

[0040] b) producing at least one C8-C16 aromatic substrate, comprising at least the following steps:

[0041] i) producing a biofuel by a process for converting at least one C1-C6 bioalcohol into a fuel,

[0042] ii) recovering the C8-C16 aromatic matrix by fractionating the biofuel obtained in step i), the C8-C16 aromatic matrix comprising at least 60 wt% of aromatic compounds, the aromatic compounds comprising at least 50 wt%, preferably at least 80 wt% of benzene, the benzene being substituted with m methyl groups, m being an integer from 1 to 3, and optionally substituted with n C2-C5 alkyl groups, n being an integer from 1 to 3,

[0043] c) hydrogenating the C8-C16 aromatic substrate obtained after step b) to obtain a cycloalkyl substrate, and

[0044] d) 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 c) to obtain a jet fuel composition comprising the paraffinic base and the naphthenic base.

[0045] The present invention also relates in particular to a method for producing a jet fuel composition obtainable from renewable raw materials, comprising at least the following steps:

[0046] a) producing at least one paraffinic matrix by hydroprocessing of esters and fatty acids, by a Fischer-Tropsch process or by a process for producing jet fuels from alcohols, said at least one paraffinic matrix comprising at least 90% by weight of paraffins,

[0047] b) producing at least one C8-C16 aromatic substrate, comprising at least the following steps:

[0048] i) producing a biofuel by a process for converting at least one C1-C6 bioalcohol into a fuel,

[0049] ii) recovering the C8-C16 aromatic matrix by fractionating the biofuel obtained in step i), the C8-C16 aromatic matrix comprising at least 60% by weight of aromatic compounds, the aromatic compounds comprising at least 50% by weight, preferably at least 80% by weight of benzene, the benzene being substituted with at least m methyl groups, m being an integer from 1 to 3, and optionally substituted with n C2-C5 alkyl groups, n being an integer from 1 to 3,

[0050] c) mixing 50% to 90% by volume of at least one paraffin base produced in step a) with 10% to 50% by volume of at least one fragrance base produced in step b) to obtain a mixture of a paraffin base and a fragrance base, and

[0051] d) hydrogenating the mixture of the paraffinic base and the aromatic base obtained in step c) to obtain a jet fuel composition comprising a paraffinic base and a naphthenic base.

[0052] In one embodiment, the hydrogenation in the process of the present invention is a complete hydrogenation.

[0053] In another embodiment of the present invention, the hydrogenation in the process according to the invention is a partial hydrogenation.

[0054] Preferably, in the process of the present invention, the at least one paraffinic matrix obtained after step a) is produced from one or more oils selected from the group consisting of vegetable oils, animal fats, preferably non-edible highly saturated oils, waste oils, by-products from the refining of vegetable or animal oils containing free fatty acids, tall oil and oils produced by bacteria, yeasts, algae, prokaryotes or eukaryotes.

[0055] Preferably, the method of the present invention further comprises a step e): adding 1% to 18% by volume, preferably 1% to 10% by volume, of the aromatic base produced in step b) to the jet fuel composition comprising a paraffinic base and a naphthenic base, relative to the total volume of the composition.

[0056] Preferably, in the process of the present invention, steps a), b), c), d) and optionally e), if performed, are performed in separate processes. DETAILED DESCRIPTION

[0057] As used herein, the terms "comprising" and "comprises" are synonymous with "including", "includes" or "contains", "containing", and do not exclude additional features, elements or method steps that are not specified.

[0058] The expressions weight % and mass % have equivalent meanings and refer to the weight percentage of the product per 100 g of the composition comprising the product.

[0059] The expression of volume % refers to the volume percentage of the product per 100 L of the composition containing the product.

[0060] The "cycloalkane compound" refers to a C8-C16 cycloalkane or C8-C16 polycycloalkane optionally substituted with one or more C1-C5 alkyl groups.

[0061] The paraffin base of the present invention

[0062] Paraffin base refers to synthetic paraffin fuels that meet specification ASTM D7566:21 and are produced from feedstocks of non-petroleum origin and contain at least 95% by weight of paraffin compounds.

[0063] The synthetic paraffinic fuel is advantageously a renewable synthetic paraffinic kerosene (SPK) derived from the hydroprocessing of esters and fatty acids (SPK-HEFA), or from the Fischer-Tropsch (SPK-FT) process, or from a process for converting alcohols into isoparaffinic kerosenes (SPK-ATJ).

[0064] The synthetic paraffinic fuel of the present invention is therefore a renewable fuel obtained exclusively from compounds of non-fossil origin.

[0065] The renewable synthetic paraffin fuel SPK-HEFA complies with the requirements of ASTM D7566:21 Appendix 2.

[0066] Renewable synthetic paraffin fuel SPK-HEFA can be produced from oils of natural origin by hydrogenation and deoxygenation of fatty acid esters and free fatty acids, and subsequent processing of the products (including hydrocracking, hydroisomerization or isomerization or a combination of these steps), and may include other conventional refining methods. In other words, renewable synthetic paraffin fuel SPK-HEFA is produced by hydroprocessing of esters and fatty acids of oils derived from natural sources.

[0067] The oil of natural origin is defined as the oil from the biomass source that does not contain any mineral oil.In the specification, " oil (one or more) of natural origin " refers to oil, fat and its mixture.The described oil of natural origin can contain one or more oils selected from following: vegetable oil, animal fat, preferably inedible high saturated oil, waste oil, by-product, tall oil and the oil produced by bacterium, yeast, algae, prokaryotes or eukaryotes from the vegetable oil containing free fatty acids or the refining of animal oil.Suitable vegetable oil is for example palm oil, palm kernel oil, soybean oil, rapeseed oil (rapeseed oil or mustard oil), sunflower seed oil, linseed oil, rice oil, corn oil, olive oil, castor oil, sesame oil, pine oil, peanut oil, mustard oil, Carnata (carinata) oil, sesame oil, coconut oil, babassu oil, cottonseed oil, linseed oil, jatropha oil.Animal fat comprises tallow, lard, fat (brown and yellow fat), fish oil / fat, fatty substance, milk fat.

[0068] The byproduct of the refining of vegetable oil or animal oil is a byproduct containing free fatty acids, which are removed from crude fats and oils by neutralization or vacuum or steam distillation. A typical example is PFAD (palm fatty acid distillate). Waste oil includes used cooking oil (waste cooking oil) and oil recovered from wastewater (such as oil tank oil / fat, waste oil, sewage oil from water treatment plants) and waste fat from the food industry. Tall oil (Tall oil) includes crude tall oil, distilled tall oil (DTO), tall oil fatty acid (TOFA), preferably DTO and TOFA, which can also be used in the present invention. Tall oil (also known as tallol) is a liquid byproduct from the wood conversion kraft pulping process, which can separate the wood pulp used in the papermaking industry. Tall oil is mainly obtained when coniferous trees are used in the kraft pulping process. After treating wood chips with sodium sulfide in an aqueous solution, the separated tall oil is alkaline. Then acidify with sulfuric acid to produce crude tall oil. The oil of natural origin that is used for the present invention also comprises the oil produced by microorganism, no matter it is natural microorganism or genetic modification microorganism, as bacterium, yeast, algae, prokaryotic organism or eukaryotic organism.Particularly, this oil can be reclaimed using known mechanical or chemical extraction methods.

[0069] The renewable synthetic paraffin fuel SPK-FT is derived from the Fischer-Tropsch process and can be produced from solid biomass. It complies with the provisions of ASTM D7566:21 Appendix 1. Thermochemical conversion of biomass (gasification and Fischer-Tropsch synthesis), also known as BtL (biomass to liquid), includes the following steps: pretreatment of biomass (preparation, grinding, roasting), gasification of biomass (to obtain synthesis gas), purification of synthesis gas, Fischer-Tropsch synthesis to convert gas into synthetic biofuel.

[0070] Regardless of which of the above methods is used, the synthetic paraffin fuel may be subjected to an isomerization step and / or a distillation step before adding the composition of the present invention to remove heavier linear paraffins, which can impair the low temperature performance of the jet fuel properties, especially Jet A1, which must have a freezing point below -47°C. The lightest compounds can also be separated by distillation to meet the volatility and flash point requirements of Jet A1. Regardless of which of the above methods is used, the renewable synthetic paraffin fuel may have one or more of the following characteristics:

[0071] - a paraffin content of more than 90% by weight,

[0072] - a cycloparaffin content of less than 10% by weight,

[0073] - a freezing point below -30°C, preferably below -40°C, for example below -47°C,

[0074] -730kg / m at 15℃ 3 -780kg / m3 The density of

[0075] -145℃-315℃ distillation range,

[0076] - The isoparaffin content is 70% by weight or more.

[0077] The renewable synthetic paraffin fuel SPK-ATJ specifically complies with the specifications of ASTM D7566:21 Appendix 5, but can also be produced from any alcohol having 1 to 6 carbon atoms. The renewable fuel SPK-ATJ is obtained by dehydrating alcohols to produce olefins, which are then oligomerized to obtain unsaturated hydrocarbon molecules within the boiling temperature range of SAF. These unsaturated hydrocarbon molecules are then hydrogenated to produce a paraffin base.

[0078] The cycloalkyl matrix of the present invention

[0079] The C8-C18 cycloalkyl substrate is produced by hydrogenation of a C8-C16 aromatic substrate, the aromatic substrate being as defined below.

[0080] Hydrogenation of C8-C16 aromatic substrates fully or partially hydrogenates the aromatic compounds.

[0081] The hydrogenation of the C8-C16 aromatic substrate can be carried out on the basis of the aromatic substrate alone or in a mixture with other compounds, in particular in the presence of the paraffin substrate of the present invention. Thus, the hydrogenation of the C8-C16 aromatic substrate can be carried out when the aromatic substrate is mixed with the paraffin substrate of the present invention.

[0082] For example, the hydrogenation is carried out in one or more fixed-bed reactors (upward or downward flow) and in mixed phase, the fraction to be hydrogenated being predominantly in the liquid phase.

[0083] The hydrogenation is carried out, for example, at a temperature of 50° C. to 350° C., in particular at 100° C. to 300° C. It is carried out at a pressure preferably higher than 10 bara, in particular at a pressure of 20 bara to 80 bara.

[0084] A hydrogen stream is fed into the reactor or each reactor and mixed with the aromatic substrate stream to be hydrogenated. The ratio of the volume flow rate of hydrogen to the volume flow rate of the aromatic substrate to be hydrogenated (excluding the recycle stream) is advantageously in the range of 50 NL / L to 3000 NL / L, in particular 100 NL / L to 500 NL / L. Hydrogen may be added to the aromatic substrate stream in several stages along the catalytic bed. The hourly space velocity is advantageously in the range of 0.5 to 3 h / min. -1 , especially 1-2h -1 The excess hydrogen, after separation and compression, can be recycled back to the reaction zone.

[0085] The reaction is carried out in the presence of at least one catalyst comprising one or more Group VIII metals (usually Pt, Pd, Ni) supported on a matrix 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 a Group VIB element (Cr, Mo, W) and a Group VIIIB element (Fe, Ru, Co, Os, Co, Rh, Ir, Pd, Ni, Pt) or a mixture of these two groups of metals.

[0086] The hydrogenation step is preferably followed by a separation step of light compounds, generally by stripping or distillation. This separation step can produce a hydrogenated fraction of the C8-C16 type, suitable for addition to aviation fuel.

[0087] In one variant, there is complete hydrogenation of the aromatic substrate. This means that more than 99% of the aromatic compounds contained in the aromatic substrate are hydrogenated.

[0088] In another variant, there is a partial hydrogenation of the aromatic substrate. Preferably, 10% to 99% by weight, more preferably 10% to 90% by weight of the aromatic compounds contained in the aromatic substrate to be hydrogenated, preferably 30% to 80% by weight of the aromatic compounds contained in the aromatic substrate to be hydrogenated are hydrogenated to cycloparaffinic compounds. The partial hydrogenation can be obtained by selecting the operating conditions so that only part of the aromatic compounds are hydrogenated, or by subjecting only part of the aromatic substrate to the hydrogenation step, and then combining the unhydrogenated fraction with the fully hydrogenated fraction.

[0089] In this variation, the cycloalkane substrate comprises a mixture of aromatic and cycloalkane compounds.

[0090] In this variant, the cycloalkane matrix preferably comprises at least 60% by weight of cycloalkane compounds, preferably 70% to 95% by weight of cycloalkane compounds, more preferably 75% to 95% by weight of cycloalkane compounds.

[0091] In this variant, the cycloalkane matrix preferably has a mass ratio between cycloalkane 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 1-99, preferably 5-24, preferably 5-10.

[0092] Preferably, the cycloalkane matrix has a mass ratio between the mass of C9-C10 cycloalkane compounds in the cycloalkane matrix and the mass of C9-C14 cycloalkane compounds in the cycloalkane matrix greater than or equal to 0.10, preferably greater than or equal to 0.40, preferably greater than or equal to 0.50, preferably greater than or equal to 0.6, preferably 0.70-0.95.

[0093] Preferably, the cycloalkane matrix has a mass ratio between the mass of C9-C12 cycloalkane compounds in the cycloalkane matrix and the mass of C9-C14 cycloalkane compounds in the cycloalkane matrix greater than or equal to 0.60, preferably greater than or equal to 0.70, preferably greater than or equal to 0.80, preferably greater than or equal to 0.90, preferably in the range of 0.80-0.999.

[0094] The aromatic matrix of the present invention

[0095] The C8-C16 aromatic substrate is used to prepare the cycloalkyl substrate of the present invention. In some embodiments, an aromatic substrate is also added to the composition of the present invention to adjust the content of aromatic compounds in the composition to the desired specification.

[0096] The C8-C16 aromatic substrate can be produced by the following steps:

[0097] i) producing a biofuel by subjecting at least one C1-C6 bioalcohol derived from at least one renewable feedstock to an alcohol-to-fuel conversion,

[0098] ii) recovering said C8-C16 aromatic substrates derived from said biofuel obtained in step i) by fractionation.

[0099] Step i): Production of biofuels

[0100] The biofuel production according to step i) 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.

[0101] C1-C6 bioalcohol mainly comprises alcohols, such as methanol, ethanol, propanol (n-propanol, isopropanol), butanol (n-butanol, isobutanol), pentanol (n-pentanol, isopentanol) and hexanol. C1-C6 bioalcohol preferably contains more than 80% by weight of C1-C6 alcohol, preferably more than 90% by weight of C1-C6 alcohol.

[0102] C1-C6 bioalcohols can be:

[0103] -Methanol from biomass:

[0104] Biomass can particularly include wood fuels (e.g., sawdust) from forests and natural woodlands, agricultural waste (e.g., rice husks, straw manure), energy crops (e.g., corn, oil palm) specifically planted for energy production, urban waste (e.g., municipal solid waste and wastewater), and biomass fuels (e.g., wood pellets) derived from waste. Methanol from renewable sources can be obtained in particular by converting high CO / H2 synthesis gas, which is derived from biomass. Biomass can be gasified, for example, to produce high CO / H2 synthesis gas, which is then converted into methanol in the presence of a catalyst. This type of method is described, for example, in document WO2018134853A1. By partially oxidizing biogas containing methane and CO2 in the presence of oxygen, it is also possible to obtain synthesis gas suitable for subsequent conversion into methanol, which is produced, for example, by anaerobic digestion of biomass in the presence of one or more microorganisms. This type of method is described, for example, in document WO2019060988A1.

[0105] - Methanol from carbon dioxide:

[0106] There are several conversion pathways. Mention may be made, for example, of the catalytic conversion of carbon dioxide into methanol in the presence of hydrogen. Another approach is the conversion of carbon dioxide into carbon monoxide by electrochemical conversion or by reversing the water-gas shift in the presence of hydrogen. The carbon monoxide is then converted into methanol by catalytic conversion in the presence of hydrogen. The hydrogen used for the above-mentioned different operations is obtained in particular by steam-methane reforming, by water-gas shift, or by electrolysis of renewable energy sources such as solar energy, wind energy, geothermal energy, wave or electric current.

[0107] - Bioethanol produced by ethanol fermentation of at least one feedstock of plant origin by the action of microorganisms, yeasts and / or bacteria:

[0108] Bioethanol can be advantageously obtained by:

[0109] - anaerobic fermentation in high sugar substrates derived from biomass, or

[0110] - Anaerobic fermentation of gases including CO, which may or may not be derived from biomass.

[0111] For anaerobic fermentation of high sugar substrates, the sugars consist of chains of 6 or 5 carbons, such as glucose, sucrose (a dimer of glucose and fructose), xylose, and arabinose.

[0112] The substrate may, for example, comprise or be derived directly from agro-food plants, sugar cane, sugar beet, sweet sorghum, or depolymerization of starch from cellulose and hemicellulose of corn, wheat, barley, rye, sorghum, triticale, potato, sweet potato, cassava and / or lignocellulosic biomass.

[0113] High sugar substrates can also be obtained from lignocellulosic biomass by the following method, including the step of (i) separating lignin, cellulose and hemicellulose contained in the lignocellulosic biomass, followed by (ii) the step of converting cellulose and / or hemicellulose into sugars. It is well known to those skilled in the art to obtain substrates of this type from lignocellulosic biomass. The high sugar substrate is then fermented using, for example, a microorganism.

[0114] Ethanol can also be produced by anaerobic fermentation of gases comprising CO. The substrate is a gaseous substrate (gas) containing CO. The gaseous substrate can be a by-product from an industrial process, for example, the manufacture of ferrous metal products, the manufacture of non-ferrous metal products, petroleum refining processes, gasification of coal and / or biomass or biochar, production of electrical energy, production of carbon black, production of ammonia, production of methanol, manufacture of coke, catalytic cracking (especially regeneration of the catalyst to produce carbon monoxide) and methane reforming.

[0115] In other embodiments, the gaseous substrate can be derived from the gasification of biomass, such as the by-product of the biomass obtained when extracting and processing food. The gasification process involves the partial combustion of biomass under restricted air or oxygen addition. The resulting gas usually and mainly includes CO and H2, with a minimum volume of CO2, methane, ethylene and ethane. The CO content of the gaseous substrate is generally 15% by volume to 100% by volume, 15% by volume to 95% by volume, 40% by volume to 95% by volume, 40% by volume to 60% by volume and 45% by volume to 55% by volume, or is located in the range limited by two of these limits.

[0116] Any microorganism capable of fermenting a gaseous substrate comprising CO to produce ethanol may be used.

[0117] - Bioethanol produced from biomass by converting high CO / H2 synthesis gas derived from biomass.

[0118] For example, biomass can be gasified to produce a high CO / H2 synthesis gas, which is then converted to methanol in the presence of a catalyst. This type of process is described, for example, in document WO2012003901.

[0119] - any other alcohol having 3 to 6 carbon atoms, obtained, for example, by:

[0120] - Catalytic reaction of hydrogen with carbon dioxide or carbon monoxide;

[0121] - Catalytic reaction of hydrogen with carbohydrates;

[0122] - ABE fermentation, bacterial fermentation to produce a mixture of ethanol, acetone and butanol from carbohydrates such as glucose or starch;

[0123] - anaerobic fermentation of sugars derived from biomass, in particular to obtain propanol (iso- or n-propanol), butanol (iso- or n-butanol) or isopentanol;

[0124] - Anaerobic fermentation of a mixture containing at least carbon monoxide, carbon dioxide and hydrogen, in particular to obtain propanol (iso- or n-propanol), butanol (iso- or n-butanol) or isoamyl alcohol.

[0125] Step ii): Recovery of C8-C16 aromatic substrates

[0126] The biofuel obtained in step i) is fractionated to recover the C8-C16 fraction to meet the volatility performance requirements of aviation fuel.

[0127] The C8-C16 aromatic substrates of the present invention may have one or more of the following characteristics:

[0128] at least 60% by weight of C8-C16 aromatic compounds, in particular monoaromatic compounds, said aromatic compounds comprising at least 50% by weight, preferably at least 80% by weight, of benzene, said benzene being substituted by at least m methyl groups, m being an integer from 1 to 3, and optionally substituted by n C2-C5 alkyl groups, n being an integer from 1 to 3,

[0129] - 8% to 15% by weight of cycloalkane compounds,

[0130] - 5% to 15% by weight of isoparaffins,

[0131] - Less than 5% by weight of normal paraffins.

[0132] It should be noted that the aromatic compound content is at least 60% by weight, including benzene substituted by at least m methyl groups and optionally by n C2-C5 alkyl groups. Therefore, these aromatic compounds may include a mixture of benzene molecules substituted by at least m methyl groups, m being an integer from 1 to 3, and optionally substituted by at least m methyl groups (m being an integer from 1 to 3), and / or a mixture of benzene molecules substituted by n C2 to C5 alkyl groups (n being an integer from 1 to 3).

[0133] In particular, the production of paraffinic and naphthenic substrates according to the invention can use different renewable resources and in particular use separate processes.

[0134] The mixing step of the present invention

[0135] Preferably, the method of the invention comprises the step of mixing the paraffin base with another base.

[0136] In one embodiment, the mixing step is carried out after the hydrogenation step c) of the aromatic substrate and corresponds to step d) of mixing 50% to 90% by volume of at least one paraffinic substrate produced in step a) with 10% to 50% by volume of at least one naphthenic substrate produced in step c).

[0137] Preferably, in this embodiment, the mixing in step d) comprises mixing 50% to 85% by volume of the at least one paraffinic base produced in step a) with 15% to 50% by volume of the at least one cycloalkyl substrate produced in step c), preferably step d) comprises mixing 55% to 80% by volume of the at least one paraffinic base produced in step a) with 20% to 45% by volume of the at least one cycloalkyl substrate produced in step c), most preferably step d) comprises mixing 55% to 75% by volume of the at least one paraffinic base produced in step a) with 25% to 45% by volume of the at least one cycloalkyl substrate produced in step c).

[0138] In another embodiment, the mixing step is carried out between step b) and the hydrogenation step and corresponds to a step of mixing 50% to 90% by volume of at least one paraffin base produced in step a) with 10% to 50% by volume of at least one aromatic base produced in step b) to obtain a mixture of paraffin and aromatic base.

[0139] Preferably, in this embodiment, the mixing step comprises mixing 50% to 85% by volume of the at least one paraffin base produced in step a) with 15% to 50% by volume of the at least one fragrance base produced in step b), preferably the mixing step comprises mixing 55% to 80% by volume of the at least one paraffin base produced in step a) with 20% to 45% by volume of the at least one fragrance base produced in step b), more preferably the mixing step comprises mixing 55% to 75% by volume of the at least one paraffin base produced in step a) with 25% to 45% by volume of the at least one fragrance base produced in step b).

[0140] The jet fuel composition of the present invention

[0141] Preferably, the composition according to the invention comprises 50% to 85% by volume, preferably 55% to 80% by volume, more preferably 55% to 75% by volume of at least one paraffin base.

[0142] Preferably, the composition of the invention comprises from 15% to 50% by volume, preferably from 20% to 45% by volume, more preferably from 25% to 45% by volume of at least one cycloalkane substrate.

[0143] Preferably, the composition of 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 1% to 18% by volume, preferably 1% to 10% by volume of at least one aromatic substrate.

[0144] Preferably, the composition of the present invention has a mass ratio of cycloalkane compounds / aromatic compounds greater than 1, preferably greater than or equal to 2, preferably greater than or equal to 3, preferably 3-5.

[0145] Preferably, the composition of the present invention comprises 15% to 48% by weight of cycloalkane compounds, more preferably 25% to 45% by weight of cycloalkane compounds.

[0146] Preferably, the composition of the present invention comprises an amount of less than or equal to 15% by volume, preferably less than or equal to 8% by volume, more preferably less than or equal to 5% by volume of aromatic compounds relative to the total volume of the composition. Preferably, the composition of the present invention comprises an amount of 1% by volume to 15% by volume, preferably 1% by volume to 8% by volume of aromatic compounds relative to the total volume of the composition.

[0147] The amount of aromatic compound included in the composition of the invention is defined by volume according to the specifications of standard ASTM D7566:21.

[0148] Advantageously, the fuel composition of the present invention may comply with Jet A or Jet A1 requirements as defined by standard ASTM D7566:21 of July 2021 or DefSta 91-091 version referencing standard ASTM D7566:21.

[0149] For example, the density of the composition of the present invention is 755 kg / m 3 -840kg / m 3 , preferably 775kg / m 3 -840kg / m 3 .

[0150] Specifically, the contents of the paraffinic matrix, the naphthenic matrix, and the aromatic matrix (if any) in the jet fuel composition of the present invention can be selected so that the composition of the jet fuel of the present invention meets these requirements.

[0151] In an advantageous embodiment, the at least one paraffinic base and the at least one naphthenic base are obtained from separate processing of renewable raw materials (from separate processes), in particular from independent renewable raw materials. In a preferred embodiment, the jet fuel composition of the invention consists of a paraffinic base, a naphthenic base and, if present, an aromatic base obtained from renewable raw materials.

[0152] In one embodiment, the composition of the jet fuel of the present invention is free of petroleum-derived components.

[0153] The following examples illustrate the present invention without limiting the scope of the invention.

[0154] Example

[0155] Example 1

[0156] Two compositions C1 and C2 according to the invention were prepared.

[0157] C1 comprises a paraffin matrix a) according to the invention of 68% by volume of HEFA, and 32% by volume of a cycloalkane matrix b).

[0158] C2 comprises a paraffin matrix a) according to the invention, 61% by volume of HEFA, and 39% by volume of a naphthenic matrix b).

[0159] The composition of the cycloalkane substrate b) is given in Table 1 below and was determined by the GC2D method.

[0160] [Table 1] Composition of cycloalkyl matrix b)

[0161] C9-C10 content C11-C12 content C13-C14 content Isoparaffin content (weight %) 3.60 3.19 0.35 0.02 Normal paraffin content (weight %) 0.51 0.36 0.00 0.02 Cycloalkane content (weight %) 85.00 72.69 11.84 0.47 Saturated hydrocarbons < C9 (wt%) 4.84 - - - Polycycloalkanes (wt%) 6.05 - - - total 100 - - -

[0162] Compositions C1 and C2, HEFA bases corresponding to paraffin base a) and naphthenic bases b) have the properties detailed in the following table (these properties are determined according to the criteria specified in each column):

[0163] [Table 2]

[0164]

[0165] Thus, the addition of cycloalkyl substrates b) to the paraffinic base a) makes it possible to obtain compositions with improved properties. In particular, the addition of cycloalkyl substrates b) surprisingly improves the viscosity of the paraffinic base at -40°C and its lubricity (BOCLE). This indicates that it is possible to replace at least a portion of the aromatic bases usually used in combination with paraffinic bases with cycloalkyl substrates, thereby reducing the formation of fine particles and the presence of condensation trails.

[0166] Example 2 - Comparative composition comprising a naphthenic matrix of fossil origin

[0167] A comparative composition C3* was prepared comprising a paraffin matrix a) according to the invention (the matrix in Example 1), 61% by volume of HEFA and 39% by volume of a fossil naphthenic matrix b′).

[0168] The composition of the cycloalkane substrate b') was determined by GC2D and is given in the table below.

[0169] [Table 3] Composition of cycloalkyl matrix b')

[0170] C9-C10 content C11-C12 content C13-C14 content Isoparaffin content (weight %) 22.44 0.03 5.75 14.74 Normal paraffin content (weight %) 18.35 0.35 8.66 8.97 Cycloalkane content (weight %) 32.96 1.21 16.90 14.27 Saturated hydrocarbons < C9 (wt%) 0.02 - - - Polycycloalkanes (wt%) 26.21 - - - Monoaromatic 0.02 - - - total 100 - - -

[0171] The comparative composition C3*, HEFA matrix and cycloalkyl matrix b') have the properties detailed in the table below (these properties are determined according to the criteria specified in each column):

[0172] [Table 4]

[0173]

[0174] The cycloalkyl substrate b') of fossil origin comprises compounds with a higher average carbon number than the cycloalkyl substrate b) according to the invention used in Example 1. The viscosity of composition C3* is too high and does not comply with standard ASTM D7566.

Claims

1. A jet fuel composition obtained from a renewable feedstock, comprising: relative to the total volume of the composition: a. 50% to 90% by volume of at least one paraffinic matrix obtained from the hydroprocessing of esters and fatty acids, from the Fischer-Tropsch process or from a process for producing jet fuel from alcohols and containing at least 90% by weight of paraffins relative to the total weight of the paraffinic matrix, b. 10% to 50% by volume of at least one C8-C16 cycloalkyl substrate obtained from the hydrogenation of a C8-C16 aromatic substrate corresponding to the C8-C16 fraction of a biofuel produced by a process for converting at least one C1-C6 bioalcohol into a fuel, and containing, relative to the total weight of the aromatic substrate, at least 60% by weight of aromatic compounds, said aromatic compounds comprising at least 50% by weight, preferably at least 80% by weight, of benzene substituted by at least m methyl groups, m being an integer from 1 to 3, and optionally substituted by n C2-C5 alkyl groups, n being an integer from 1 to 3, in, The jet fuel composition comprises 10 wt% to 49 wt% of cycloparaffinic compounds, relative to the total weight of the composition.

2. The jet fuel composition according to claim 1, comprising an amount of 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. The jet fuel composition according to claim 1 or 2, wherein: The cycloalkane matrix comprises aromatic compounds and cycloalkane compounds, and has a mass ratio of the cycloalkane compounds to the aromatic compounds greater than or equal to 1, preferably greater than or equal to 2, preferably greater than or equal to 5.

4. A jet fuel composition according to any one of the preceding claims, wherein: The cycloalkane matrix has a mass ratio between the mass of C9-C10 cycloalkane compounds in the cycloalkane matrix and the mass of C9-C14 cycloalkane compounds in the cycloalkane matrix greater than or equal to 0.10, preferably greater than or equal to 0.40, preferably greater than or equal to 0.50, preferably greater than or equal to 0.6, preferably 0.70-0.

95.

5. A jet fuel composition according to any one of the preceding claims, further comprising, relative to the total volume of the composition, 1% to 18% by volume, preferably 1% to 10% by volume, of at least one C8-C16 aromatic substrate corresponding to the C8-C16 fraction of a biofuel produced by a process for converting at least one C1-C6 bioalcohol into a fuel, and characterized in that The aromatic matrix contains at least 60 wt% of aromatic compounds, the aromatic compounds contain at least 50 wt% of benzene, the benzene is substituted by at least m methyl groups, m is an integer of 1-3, and is optionally substituted by n C2-C5 alkyl groups, n is an integer of 1-3.

6. A method for producing a jet fuel composition obtained from a renewable feedstock, comprising at least the steps of: a) producing at least one paraffinic matrix by hydroprocessing of esters and fatty acids, by a Fischer-Tropsch process or by a process for producing jet fuels from alcohols, said at least one paraffinic matrix comprising at least 90% by weight of paraffins, b) producing at least one C8-C16 aromatic substrate, comprising at least the following steps: i) producing a biofuel by a process for converting at least one C1-C6 bioalcohol into a fuel, ii) recovering the C8-C16 aromatic matrix by fractionating the biofuel obtained in step i), the C8-C16 aromatic matrix comprising at least 60% by weight of aromatic compounds, the aromatic compounds comprising at least 50% by weight, preferably at least 80% by weight of benzene, the benzene being substituted with at least m methyl groups, m being an integer from 1 to 3, and optionally substituted with n C2-C5 alkyl groups, n being an integer from 1 to 3, c) hydrogenating the C8-C16 aromatic base obtained after step b) to obtain a paraffinic base, and d) 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 c) to obtain a jet fuel composition comprising the paraffinic base and the naphthenic base.

7. A method for producing a jet fuel composition obtained from a renewable feedstock, comprising at least the steps of: a) producing at least one paraffinic matrix by hydroprocessing of esters and fatty acids, by a Fischer-Tropsch process or by a process for producing jet fuels from alcohols, said at least one paraffinic matrix comprising at least 90% by weight of paraffins, b) producing at least one C8-C16 aromatic substrate, comprising the following steps: i) producing a biofuel by a process for converting at least one C1-C6 bioalcohol into a fuel, ii) recovering the C8-C16 aromatic matrix by fractionating the biofuel obtained in step i), the C8-C16 aromatic matrix comprising at least 60% by weight of aromatic compounds, the aromatic compounds comprising at least 50% by weight, preferably at least 80% by weight, of benzene, the benzene being substituted with at least m methyl groups, m being an integer from 1 to 3, and optionally substituted with n C2-C5 alkyl groups, n being an integer from 1 to 3, c) mixing 50% to 90% by volume of at least one paraffin base produced in step a) with 10% to 50% by volume of at least one fragrance base produced in step b) to obtain a mixture of a paraffin base and a fragrance base, and d) hydrogenating the mixture of the paraffinic base and the aromatic base obtained in step c) to obtain a jet fuel composition comprising a paraffinic base and a naphthenic base.

8. A process for producing a jet fuel composition obtained from renewable raw materials according to claim 6 or 7, wherein: The hydrogenation was complete.

9. A method for producing a jet fuel composition obtained from renewable raw materials according to claim 6 or 7, wherein: The hydrogenation is partial.

10. A method for producing a jet fuel composition obtained from renewable raw materials according to any one of claims 6 to 9, wherein: The at least one paraffinic matrix obtained after step a) is produced from one or more oils selected from the group consisting of vegetable oils, animal fats, preferably non-edible highly saturated oils, waste oils, by-products from the refining of vegetable or animal oils containing free fatty acids, tall oil and oils produced by bacteria, yeasts, algae, prokaryotes or eukaryotes.

11. The method for producing a jet fuel composition according to any one of claims 6 to 10, further comprising a step e): adding 1% to 18% by volume, preferably 1% to 10% by volume, of the aromatic base produced in step b) to the jet fuel composition, the jet fuel composition comprising a paraffinic base and a naphthenic base, relative to the total volume of the composition.

12. A method for producing a jet fuel composition according to any one of claims 6 to 11, wherein: Steps a), b), c), d) and optionally e), if performed, are carried out in separate processes.

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