Process for producing a jet fuel from a mixture comprising, in particular, a lignin oil

Abstract

The invention relates to a process for producing a jet fuel from a mixture to be treated, comprising, in particular, a mixture of phenolic compounds, preferably a lignin oil, the process comprising a step of hydrotreating the mixture to be treated, wherein the mixture to be treated has specific properties. The present invention also relates to a mixture of hydrocarbons and to a jet fuel obtained using this process.

Description

[0001] Process for preparing jet fuel from a mixture including a lignin oil

[0002] The present invention relates to a process for preparing jet fuel from a mixture to be treated comprising in particular a mixture of phenolic compounds, preferably a lignin oil, the process comprising a hydrotreating step of the mixture to be treated, the mixture to be treated having particular characteristics.

[0003] The present invention also relates to a mixture of hydrocarbons and a jet fuel obtained according to this process.

[0004] Decarbonizing the aviation sector requires the increasing use of renewable fuels (SAF) whose carbon footprint is greatly reduced compared to the fossil jet currently used.

[0005] SAFs are used alone, or in a mixture with a fossil fuel jet. They are obtained from renewable raw materials, such as used cooking oils, first-generation vegetable oils, bioethanol, or synthesis gas obtained by Fischer-Tropsch synthesis.

[0006] However, the quantities of raw materials currently used (used cooking oils, first-generation vegetable oils) to produce SAF are limited and will not be sufficient to meet the entire demand for SAF in the near future. These raw materials also require a cracking / isomerization step because the chain lengths of the resulting compounds are too long (C18) to meet the cold-weather properties of the fuel. Therefore, it is necessary to use other biomass sources to produce SAF.

[0007] More generally, it is necessary to continue to reduce the carbon footprint of jet fuels for aviation, while increasing the quantities produced of these jet fuels.

[0008] Therefore, there is a need for a process to produce a mixture of hydrocarbons or jet fuel with a reduced carbon footprint.

[0009] There is also a need for a process to produce larger quantities of hydrocarbon blends or jet fuel with a reduced carbon footprint. In particular, there is a need for a process to produce hydrocarbon blends or jet fuel from renewable raw materials other than used cooking oils or first-generation vegetable oils.

[0010] In particular, there is a need for a process capable of reducing by at least 60% by mass, preferably at least 70% by mass, the oxygen content of a mixture comprising a high oxygen content, typically at least 5% by mass.

[0011] The present invention therefore relates to a process for preparing a mixture of hydrocarbons, comprising a hydrotreatment step, in particular a hydrodeoxygenation step, of a mixture to be treated, the mixture to be treated comprising a) a mixture of phenolic compounds, and b) an effluent intended to be hydrotreated and optionally c) a diluent.

[0012] The inventors have discovered that it is possible to incorporate a mixture of phenolic compounds, such as lignin oil, into an effluent intended for hydrotreatment (for example, in a hydrotreating process for an oil fraction or a hydrodeoxygenation process for vegetable oils) in order to reduce the carbon footprint of the resulting hydrocarbon mixture and / or increase the quantity of low-carbon jet fuel produced. Surprisingly, adding the mixture of phenolic compounds to the effluent intended for hydrotreatment requires no modification of the hydrotreating process, making the process according to the invention particularly attractive from an economic standpoint.The inventors also discovered, surprisingly, that hydrotreating the mixture of phenolic compounds is more efficient, particularly in terms of conversion yield and / or percentage reduction of oxygen content, when said mixture of phenolic compounds is co-hydrotreated with an effluent intended for hydrotreating than when hydrotreated alone or in the presence of an inert diluent.

[0013] The present invention further relates to a mixture of hydrocarbons obtained by the process according to the invention, comprising from 50% to 90% by mass of C9-C18 compounds relative to the total mass of the hydrocarbon mixture and / or having an average number of carbon atoms between 7 and 18, preferably between 8 and 15, preferably between 9 and 12.

[0014] Process for preparing a hydrocarbon mixture: Hydrotreating step

[0015] The process according to the invention comprises a hydrotreatment step of a mixture to be treated, the mixture to be treated comprising (or consisting of) a) a mixture of phenolic compounds, b) an effluent intended for hydrotreatment, and optionally c) a diluent. This hydrotreatment step is, in particular, a co-hydrotreatment step of a mixture of phenolic compounds with an effluent intended for hydrotreatment, optionally in the presence of a diluent. The process according to the invention therefore comprises a co-hydrotreatment step of an effluent intended for hydrotreatment in the presence of a mixture of phenolic compounds and optionally in the presence of a diluent.

[0016] For the purposes of this invention, hydrotreating refers to a reaction carried out under hydrogen pressure and in the presence of a catalyst, which removes one or more chemical elements other than hydrogen and carbon from the mixture being treated. Examples include sulfur (in which case it is called hydrodesulfurization or HDS), nitrogen (in which case it is called hydrodeazotation or HDN), oxygen (in which case it is called hydrodeoxygenation or HDO), and / or a metal (in which case it is called hydrodemetallation or HDM).

[0017] Preferably, the hydrotreating step is carried out at a temperature less than or equal to 380°C, preferably less than or equal to 350°C, preferably less than or equal to 330°C, preferably less than or equal to 325°C, preferably less than or equal to 320°C, preferably less than or equal to 300°C, preferably less than or equal to 299°C, preferably less than or equal to 290°C, preferably between 200°C and 380°C.

[0018] The reaction temperature preferably corresponds to the average temperature of the adiabatic catalytic bed, or, as used by those skilled in the art, the WABT (weighted average bed temperature). The WABT per adiabatic catalytic bed is defined as WABT = (inlet temperature - 2 x outlet temperature) / 3.

[0019] Preferably, the hydrotreating step is carried out in the presence of a catalyst having an active phase selected from (i) metals, oxides, phosphides or sulfides of Ni, Mo, W, Co or mixtures of NiCo, NiW, NiMo, CoMo, NiCoW, NiCoMo, NiMoW and CoMoW, preferably comprising molybdenum or nickel, preferably molybdenum, preferably comprising nickel, cobalt, molybdenum, tungsten or mixtures thereof, preferably comprising oxides, sulfides or phosphides of nickel, cobalt, molybdenum, tungsten or mixtures thereof, preferably the catalyst being selected from NiMoS, CoMoS and Ni 3x P y , where the x / y ratio is between 0.3 and 3, advantageously from NiMoS and CoMoS, (ii) metals or mixtures of metal alloys from Group 10 and Group 11 of the periodic table. Alternatively, the catalyst is Ni-P.

[0020] The main drawback of using NiMo / CoMo sulfide catalysts is the need to introduce sulfide reagents to maintain catalyst activity and stability. Transition metal phosphide-based catalysts introduced for hydrotreating reactions can be attractive alternatives to expensive noble metal-based catalysts. One advantage of this class of catalysts is that the use of a sulfur-introducing reagent is not required to maintain activity.

[0021] According to one embodiment, the catalyst comprises molybdenum, preferably chosen from NiMoS and CoMoS.

[0022] According to another embodiment, the catalyst comprises nickel, preferably Ni-P.

[0023] A phosphide is a compound containing the P ion 3-Binary phosphides, composed solely of phosphorus and a less electronegative element, and polyphosphides, composed of anionic chains and / or phosphorus clusters, are two main types of phosphides. Used as catalytic materials, metal-rich phosphides exhibit excellent activity in hydrogenation, hydrodesulfurization (HDS), hydrodenitrogenation (HDN), and hydrodeoxygenation (HDO) reactions. Hydrogenation and hydrogenolysis (bond breaking) reactions are necessary for HDS, HDN, and HDO. Many metallic phosphides possess metallic properties and can therefore be used as HDS, HDN, and HDO catalysts. The composition of binary transition metal phosphides ranges from metal-rich M4P to phosphorus-rich MP15 (for example, nickel forms eight phosphides, from Ni3P to Ni5P2, Ni12P5, Ni2P, Ni5P4, NiP, NiP2 and NiP3).Many binary and ternary metal phosphides have metallic or semiconducting properties and are therefore potential catalysts for hydrogenation and hydrolysis.

[0024] The catalyst may have a supported or unsupported catalytic active phase.

[0025] Preferably, the catalyst is supported.

[0026] When the catalyst includes a support for the catalytic active phase, it is preferable for the support to have a high specific surface area. In one embodiment, the specific surface area should be at least 75 m². 2 / g, preferably at least 150 m 2 / g and more preferably at least 200 m 2 / g, this specific surface area can be measured by methods known in the art such as the BET method where the adsorption of nitrogen allows the specific surface area of ​​the solid material to be estimated.

[0027] Preferably, the catalyst is supported, for example on a refractory metal oxide, such as silica (SiO2, amorphous and / or mesoporous), alumina (Al2O3, crystalline, amorphous and / or mesoporous), cerium oxide (CeO2), titanium oxide (TiO2) and zirconium oxide (ZrO2), a carbon support (such as activated carbon, graphite, graphene, carbon black), silicon carbide, amorphous silica-aluminas, amorphous silica-aluminas-titaniums, phosphated alumina or phosphated silica alumina, sulfated zirconias, tungsten zirconias and zeolites, diatomite, hydroxyapatite, or a mixture of these, preferably chosen from silica (SiO2, amorphous and / or mesoporous), alumina (Al2O3, crystalline, amorphous and / or mesoporous), a carbon support (such as activated carbon, graphite, graphene, black carbon), or a mixture of these.Preferably, the support is chosen from silica, alumina, titanium oxide, zirconium oxide, carbon, cerium oxide, silicon carbide, silica-alumina, silica-alumina-titanium, phosphated alumina or phosphated silica alumina, sulfated zirconia, tungsten zirconia, a zeolite or mixtures thereof.

[0028] According to one embodiment, the active phase of the catalyst does not include molybdenum carbide (MoC or Mo2C), preferably does not include Ni, Mo, W, Co carbide, preferably does not include any metal carbide.

[0029] The hydrotreating step is carried out under a partial pressure of dihydrogen greater than or equal to 1.10 5 Pa, preferably between 1.10 5 and 200.10 5 Pa, preferably between 10 and 10 5 Pa and 150.10 5 Pa, preferably between 20.10 5 Pa and 120.10 5 Pa, preferably between 30.10 5 Pa and 100.105 Pa, preferably between 50.10 5 Pa and 90.10 5 Pa, preferably between 70.10 5 Pa and 90.10 5 Pa.

[0030] High hydrogen pressure allows for the advantageous adjustment of the ratio between aromatic and naphthenic compounds in the resulting hydrocarbon mixture, thereby optimizing the properties of the final jet fuel. Furthermore, varying the hydrogen pressure allows for the formation of naphthenic compounds in the hydrocarbon mixture, which have a less negative impact on combustion emissions than aromatic compounds, primarily on the formation of fine particles and the presence of contrails. Adding a mixture of phenolic compounds to an effluent intended for hydrotreatment therefore allows for the formation of naphthenic compounds in the hydrotreatment product. The presence of naphthenic compounds in the hydrocarbon mixture advantageously improves the cold-weather properties of the final jet fuel, particularly its freezing point.

[0031] Preferably, the hydrotreatment step is carried out under a total pressure greater than or equal to 1.10 5 Pa, preferably between 1.10 5 and 250.10 5 Pa, preferably between 10 and 10 5 Pa and 180.10 5 Pa, preferably between 30.10 5 Pa and 150.10 5 Pa, preferably between 50.10 5 Pa and 120.10 5 Pa, preferably between 70.10 5 Pa and 90.10 5 Pa.

[0032] If the process is implemented continuously, the hydrotreating step has a mass flow rate per hour (WHSV) defined by the ratio of the mass flow rate of liquid feed to the mass of catalyst loaded into the reactor, ranging from 0.1 to 10 h -1 preferably ranging from 0.2 to 5 hours -1 preferably ranging from 0.25 to 2.5 tr 1 .

[0033] Preferably, the hydrotreating step is carried out in a single stage. Therefore, the hydrotreating step is preferably carried out in a single reactor and / or with a single type of catalyst. According to the invention, it is therefore not necessary to use two or more reactors to transform the mixture to be treated into a hydrocarbon mixture.

[0034] In one embodiment, the hydrotreating step is implemented in a reactor operating in batch mode or in continuous mode, preferably in continuous mode.

[0035] In one embodiment, the hydrotreating step is implemented in a fixed bed reactor.

[0036] In one embodiment, the hydrodeoxygenation step is implemented in a continuously stirred tank reactor (CSTR).

[0037] In one embodiment, the hydrodeoxygenation step is carried out in a bubbling bed reactor or a slurry-type reactor.

[0038] According to one embodiment, the process according to the invention further includes a step of fractionating the hydrocarbon mixture, in order to produce in particular a jet fuel.

[0039] The fractionation stage can also produce a naphtha fraction and a diesel fraction.

[0040] In one embodiment, the process may further include a stripping step of the hydrocarbon mixture obtained at the end of the hydrotreating step, and before any fractionation step. This step removes light compounds, such as C1-C4 hydrocarbons, and gaseous components including H2, H2S, CO2, and possibly CO and NH3.

[0041] According to one embodiment, the process may further include a step of recycling the excess dihydrogen remaining at the end of the hydrotreatment step.

[0042] The process according to the invention may further include a step of mixing a) mixture of phenolic compounds, b) effluent intended to be hydrotreated, and optionally c) diluent.

[0043] Preferably, the hydrotreatment step is a hydrodeoxygenation step. All embodiments in this description apply.

[0044] Hydrodeoxygenation, as used in the present invention, refers to a hydrogenolysis reaction that eliminates oxygenated functional groups (e.g., hydroxyl, ether (methoxy, for example), carboxyl, etc.) from a compound or mixture of compounds. a) Mixture of phenolic compounds

[0045] A mixture of phenolic compounds is understood to be a mixture of at least two phenolic compounds.

[0046] A phenolic compound is defined as any compound containing at least one hydroxyl group directly bonded to an aromatic ring, preferably a phenyl group. Therefore, it is any compound containing at least one phenoxy group, that is, a phenyl group substituted by at least one -OR group, where R is H, or a C1-C4 alkyl group, preferably a methyl group. Preferably, phenolic compounds are either monomeric, that is to say they comprise one and only one phenoxy motif, that is to say one and only one aromatic ring bearing at least one -OR group, or dimeric, that is to say comprising two aromatic rings of which at least one phenoxy motif, or oligomeric, that is to say containing an assembly of at least two monomeric phenolic compounds assembled by covalent bonds typically having a molecular weight between 250 and 5000 g / mol and / or comprising at least three aromatic rings.Oligomeric phenolic compounds preferentially contain 3 or 4 monomeric phenolic compounds.

[0047] Preferably, monomeric phenolic compounds comprise between 6 and 12 carbon atoms, preferably between 8 and 12 carbon atoms, preferably between 8 and 11 carbon atoms. Preferably, dimeric phenolic compounds comprise between 14 and 24 carbon atoms, preferably between 18 and 22 carbon atoms.

[0048] Preferably, oligomeric phenolic compounds comprise at least 26 carbon atoms.

[0049] Preferably, the mixture of phenolic compounds comprises 9% to 80% by mass, preferably 20% to 80% by mass, preferably 11% to 60% by mass, preferably 25% to 60% by mass, preferably 13% to 50% by mass, preferably 30% to 50% by mass, preferably 13% to 40% by mass, preferably 25% to 40% by mass, preferably 30% to 40% by mass, of monomeric phenolic compounds, relative to the total mass of the mixture of phenolic compounds. Thus, preferably, the mixture of phenolic compounds comprises from 9% to 80% by mass, preferably from 20% to 80% by mass, preferably from 11% to 60% by mass, preferably from 25% to 60% by mass, preferably from 13% to 50% by mass, preferably from 30% to 50% by mass, preferably from 13% to 40% by mass, preferably from 25% to 40% by mass, preferably from 30% to 40% by mass, of monomeric phenolic compounds comprising between 8 and 12 carbon atoms, preferably between 8 and 11 carbon atoms.

[0050] Monomeric phenolic compounds are preferably phenolic compounds of formula (I) as defined below.

[0051] The mixture of phenolic compounds preferably comprises a mixture of compounds of the following formula (I): in which each and R2 is independently chosen from -O-CH3 and H, and each R3 is independently chosen from H, a methyl, an ethyl, a propyl, a propenyl, a 1-alkoxypropyl, a 2-hydroxyethyl and a 3-hydroxypropyl, preferably each RT and R2 is independently chosen from -O-CH3 and H, and each R3 is independently chosen from H, a methyl, an ethyl, a propyl, a propenyl, a 1-alkoxypropyl and a 3-hydroxypropyl.

[0052] In particular, in formula (I): - R2= -O-CH3 and / or

[0053] - R3 is independently chosen from a propyl and a 3-hydroxypropyl (-CH2-CH2-CH2-OH).

[0054] Preferably, the mixture of phenolic compounds comprises at least two, preferably at least three compounds selected from compounds (la), (lb), (lc), (ld),

[0055] Preferably, the mixture of phenolic compounds includes the four phenolic compounds (la), (lb), (lc), and (ld) described above.

[0056] Preferably, the mixture of phenolic compounds includes the eight phenolic compounds (la), (lb), (lc), (ld), (le), (lf), (lg) and (lh) described above.

[0057] Compounds (la) to (lg), particularly (la) to (ld), are especially advantageous for the process. Indeed, these are C8-C12 compounds, and their presence in the mixture to be treated allows the formation, during the hydrodeoxygenation step, of hydrocarbons with a carbon number corresponding to that expected in jet fuel (C8-C24 cut, preferably C9-C16), which are therefore directly usable as jet fuel. Furthermore, they are at least partially transformed into naphthenic derivatives, which improve the properties of the jet fuel, particularly its freezing point. The mixture of phenolic compounds contains oxygen primarily in hydroxyl, etheric (including alkoxys), carboxylic, and carbonyl forms (aldehyde or ketone, possibly conjugated with the aromatic ring or carbon-carbon double bonds).Preferably, the mass of oxygen atoms in carboxylic and carbonyl form in the mixture of phenolic compounds is less than or equal to 20% of the total mass of oxygen atoms present in the mixture of phenolic compounds, preferably less than or equal to 10%, preferably less than or equal to 5% and even more preferably less than or equal to 2%, preferably between 0.1% and 20% by mass.

[0058] Preferably, the mixture of phenolic compounds is a lignin oil, preferably a lignin oil obtained from a reductive catalytic fractionation process of a lignocellulosic biomass (RCF lignin oil) or an AAF lignin oil, i.e. obtained from an aldehyde-assisted fractionation process of a lignocellulosic biomass, or a DAF lignin oil, i.e. obtained from a diol-assisted fractionation process of a lignocellulosic biomass.

[0059] Preferably, the mixture of phenolic compounds is a lignin oil, preferably an RCF lignin oil, i.e., one obtained from a catalytic reduction fractionation process of a lignocellulosic biomass.

[0060] Lignin oil, preferably from one of the three processes listed above, preferably from a catalytic fractionation process, is more stable than other raw materials derived from lignin, for example from the paper industry, or pyrolysis oil from biomass, is more easily processable and allows a very high yield for the hydrotreating step.

[0061] Preferably, the lignin oil has an average molecular weight between 200 and 950 g / mol, preferably between 350 and 830 g / mol. The molecular weight distribution varies from 150 to 2000 g / mol. The molecular weight distribution (and therefore the average molecular weight) is determined by gel permeation-size chromatography (GPC-SEC), for example, according to the following procedure: a lignin sample is solubilized in THF (5 mg.mL) 1 ) then filtered with a 0.2 µm PTFE membrane to remove any particles and prevent column clogging. GPC-SEC analyses are performed at 40 °C on a Waters E2695 equipped with a 300 mm long PL-Gel 3 µm Mixed-E column, using THF as the solvent at a flow rate of 1 mL / min 1 Detection is based on UV at a wavelength of 280 nm. Calibrations are performed with commercial polystyrene standards from Agilent.

[0062] Lignin oil with such a high molecular weight is more fluid than other lignin-derived raw materials, for example those from the paper industry, or pyrolysis oil from biomass. As a result, it is more easily processed.

[0063] Lignin oil typically contains between 6 and more than 100 oxygenated hydrocarbons and an average number of carbon atoms between 20 and 60, preferably between 25 and 50, preferably between 30 and 45, and preferably between 35 and 40. The average number of carbon atoms represents the average number of carbon atoms per molecule. It can be calculated by dividing the molecular mass of the lignin oil by the carbon content of the lignin oil, as determined by elemental analysis.

[0064] Preferably, the lignin oil comprises, relative to the total mass of the lignin oil, an amount greater than or equal to 95% by mass, preferably between 97% and 100% by mass, and preferably between 99% and 99.99% by mass, of carbon, hydrogen, and oxygen atoms. Preferably, the lignin oil comprises an undetectable amount of heteroatoms other than oxygen. By heteroatoms other than oxygen, we mean atoms other than carbon, hydrogen, and oxygen. The lignin oil will therefore be less likely to deactivate catalysts, particularly the hydrotreating catalyst.

[0065] According to one embodiment, the lignin oil comprises, relative to the total mass of the lignin oil, less than 10% by mass, preferably less than 3% by mass, of sugars. Sugars are understood to mean carbohydrates and their derivatives composed of carbon (C), hydrogen (H), and oxygen (O) atoms without aromatic groups, generally with a hydrogen-oxygen ratio of about 2:1 and an oxygen-carbon ratio of about 1:1. This is then referred to as refined lignin oil.

[0066] According to another embodiment, lignin oil can also be crude lignin oil, that is, lignin oil obtained before the separation of water-soluble compounds, in particular sugars. According to this embodiment, the lignin oil is crude lignin oil and then comprises between 15 and 60% by mass of water-soluble compounds, relative to the total mass of crude lignin oil, preferably between 20 and 50% by mass, preferably between 30 and 40% by mass, and in particular between 10 and 50% by mass of sugars, preferably between 15% and 30% by mass.

[0067] Preferably, the lignin oil comprises from 9% to 80% by mass, preferably from 11% to 60% by mass, preferably from 13% to 50% by mass, preferably from 13% to 40% by mass, preferably from 25% to 40% by mass, of monomeric phenolic compounds, relative to the total mass of the lignin oil.

[0068] Preferably, the lignin oil comprises 0.4% to 25% by mass, preferably 1% to 20% by mass, preferably 2% to 18% by mass, preferably 5% to 18% by mass, preferably 8% to 15% by mass, of phenolic dimers, relative to the total mass of the lignin oil.

[0069] Preferably, the lignin oil comprises 9% to 80% by mass, preferably 13% to 70% by mass, preferably 18% to 60% by mass, of lignin oligomers, relative to the total mass of the lignin oil.

[0070] Indeed, lignin oil is preferably obtained by a catalytic reduction fractionation process of a lignocellulosic biomass, and comprises, at the end of this catalytic reduction fractionation process, a mixture of monomeric phenolic compounds (lignin monomers having a single aromatic ring, therefore a single phenolic motif), phenolic dimers and lignin oligomers, as defined above for the mixture of phenolic compounds.

[0071] A high content of monomeric phenolic compounds, such as that of the lignin oil defined in this application, improves the processability of the oil because these compounds are more soluble than dimers or oligomers. Consequently, a greater proportion of the lignin oil can be utilized, thereby increasing the carbon yield of the process. A high content of dimeric phenolic compounds also improves the processability of the lignin oil because they are more soluble than oligomeric phenolic compounds.

[0072] Furthermore, C8-C12 monomers, preferably C8-C11, are particularly advantageous for the process because they allow the formation, during the hydrodeoxygenation step, of compounds with a carbon number corresponding to that expected in jet fuel (C8-C24 cut, preferably C9-C16), which can therefore be directly used as jet fuel. Their presence in large quantities thus increases the jet fuel yield.

[0073] Preferably, the lignin oil comprises 1% to 20% by mass, preferably 3% to 15% by mass, preferably 5% to 10% by mass, of phenolic dimers, relative to the total mass of the lignin oil.

[0074] Preferably, the lignin oil comprises 20% to 80% by mass, preferably 30% to 70% by mass, preferably 40% to 60% by mass, of lignin oligomers, relative to the total mass of the lignin oil. According to one embodiment, the lignin oil is a refined lignin oil and comprises, relative to the total mass of the refined lignin oil, 20% to 80% by mass, preferably 25% to 60% by mass, preferably 30% to 50% by mass, preferably 30% to 40% by mass, of monomeric phenolic compounds and / or 1% to 25% by mass, preferably 3% to 20% by mass, preferably 5% to 18% by mass, of phenolic dimers and / or 20% to 80% by mass, preferably 30% to 70% by mass, preferably 40% to 60% by mass, of lignin oligomers.

[0075] According to one embodiment, the lignin oil is crude lignin oil and comprises, relative to the total mass of crude lignin oil, 9% to 36% by mass, preferably 11% to 27% by mass, preferably 13% to 23% by mass, preferably 13% to 18% by mass, of monomeric phenolic compounds and / or 0.4% to 12% by mass, preferably 1% to 9% by mass, preferably 2% to 9% by mass, of phenolic dimers and / or 9% to 36% by mass, preferably 13% to 32% by mass, preferably 18% to 27% by mass, of lignin oligomers.

[0076] Monomeric phenolic compounds are preferably phenolic compounds of formula (I) as defined above.

[0077] Thus, preferably, the lignin oil (preferably the monomeric phenolic compounds of lignin oil) comprises a mixture of compounds of the following formula (I): in which each and R2 is independently chosen from -O-CH3 and H, and each R3 is independently chosen from H, a methyl, an ethyl, a propyl, a propenyl, a 1-alkoxypropyl, a 2-hydroxyethyl and a 3-hydroxypropyl, preferably each RT and R2 is independently chosen from -O-CH3 and H, and each R3 is independently chosen from H, a methyl, an ethyl, a propyl, a propylene, a 1-alkoxypropyl and a 3-hydroxypropyl.

[0078] In particular, in formula (I):

[0079] - R2= - O- CH3 and / or - R3 is independently chosen from a propyl and a 3-hydroxypropyl (-CH2-CH2-CH2-OH).

[0080] Preferably, the lignin oil (preferably the monomeric phenolic compounds of lignin oil) comprises a mixture of at least two, preferably at least three compounds of formula (I), preferably selected from the following compounds (la), (I-b), (lc), (ld), (le), (lf), (lg) and (lh):

[0081] Preferably, the lignin oil comprises, relative to the total mass of the lignin oil, 20% to 80% by mass, preferably 25% to 60% by mass, preferably 30% to 50% by mass, preferably 30% to 40% by mass, of compounds of formula (I).

[0082] Preferably, the lignin oil comprises, relative to the total mass of the lignin oil, 0.5% to 20% by mass, preferably 2% to 15% by mass, preferably 3% to 11% by mass, of a compound of formula (la).

[0083] Preferably, the lignin oil comprises, relative to the total mass of the lignin oil, 2% to 25% by mass, preferably 3% to 20% by mass, preferably 5% to 18% by mass, of a compound with formula (lb). Preferably, the lignin oil comprises, relative to the total mass of the lignin oil, 0% to 8% by mass, preferably 0.2% to 5% by mass, preferably 0.4% to 3% by mass, of a compound with formula (lc).

[0084] Preferably, the lignin oil comprises, relative to the total mass of the lignin oil, 0.2% to 12% by mass, preferably 0.4% to 8% by mass, preferably 2% to 7% by mass, of a compound of formula (ld).

[0085] According to one embodiment, lignin oil is refined lignin oil, and it comprises, relative to the total mass of refined lignin oil:

[0086] - from 2% to 20% by mass, preferably from 5% to 15% by mass, preferably from 7% to 11% by mass, of a compound of formula (la), and / or

[0087] - from 5% to 25% by mass, preferably from 8% to 20% by mass, preferably from 12% to 18% by mass, of compound of formula (lb), and / or

[0088] - from 0.1% to 8% by mass, preferably from 0.5% to 5% by mass, preferably from 1% to 3% by mass, of a compound of formula (lc), and / or

[0089] - from 0.5% to 12% by mass, preferably from 1% to 8% by mass, preferably from 3% to 7% by mass, of compound of formula (ld).

[0090] According to another embodiment, lignin oil is crude lignin oil and comprises, relative to the total mass of crude lignin oil:

[0091] - from 0.5% to 9% by mass, preferably from 2% to 7% by mass, preferably from 3% to 5% by mass, of a compound of formula (la), and / or

[0092] - from 2% to 12% by mass, preferably from 3% to 9% by mass, preferably from 5% to 9% by mass, of compound of formula (lb), and / or

[0093] - from 0% to 4% by mass, preferably from 0.2% to 3% by mass, preferably from 0.4% to 2% by mass, of a compound of formula (lc), and / or

[0094] - from 0.2% to 6% by mass, preferably from 0.4% to 4% by mass, preferably from 2% to 4% by mass, of compound of formula (ld).

[0095] Preferably, the lignin oil (preferably the phenolic dimers of lignin oil) comprises a mixture of compounds of formulas selected from the following formulas (I la), (ll-b), (I lc), (I ld), (ll-e) and (ll-f):

[0096] in which each R^ R2, R4 and R5 is independently chosen from -O-CH3 and H, each R3 and R6 is independently chosen from H, a methyl, an ethyl, a propyl, a propenyl, a 1-alkoxypropyl, a 2-hydroxyethyl and a 3-hydroxypropyl, and each R7 is independently chosen from H, a methyl, and -CH2-OH, preferably each R R2, R4 and R5 is independently chosen from -O-CH3 and H, each R3 and R6 is independently chosen from H, a methyl, an ethyl, a propyl, a propenyl, a 1-alkoxypropyl, and a 3-hydroxypropyl, and each R7 is independently chosen from H, and -CH2-OH.

[0097] Preferably, the lignin oil contains oxygen, and the mass of oxygen atoms in carboxylic (carboxyl function) and carbonyl (carbonyl function) form is less than or equal to 20% of the total mass of oxygen atoms present in the lignin oil, preferably less than or equal to 10%, preferably less than or equal to 5%, and even more preferably less than or equal to 2%, preferably between 0.1 and 20% by mass.

[0098] This explains at least in part the high chemical stability of RCF lignin oil compared to other lignin oils.

[0099] Preferably, the lignin oil has a viscosity at 25 °C less than or equal to 25 Pa.s, preferably between 0.010 and 20 Pa.s, preferably between 0.5 and 15 Pa.s, preferably between 1 and 10 Pa.s, preferably between 2.0 and 5.0 Pa.s, preferably between 3.0 and 4.0 Pa.s.

[0100] The viscosity at 25 °C can be determined according to the following protocol:

[0101] Viscosity measurements were performed on a controlled-stress rheometer (Anton Paar MCR501). The sample temperature was controlled using a Peltier system (P-PTD200) with a solvent plate and an evaporation blocker, with an accuracy of approximately 0.1°C. For viscosities above 0.1 Pa·s, a PP25 geometry was used, while for viscosities below 0.1 Pa·s, a PP50 geometry was used. Viscosity was determined as a function of the shear rate at a rate of 5 measurement points per decade. The shear rate range was adjusted according to the temperature and the sample so that measurements were performed in the Newtonian regime and above the instrument's minimum torque level. In the Newtonian regime, the average was calculated over 5 measurement points (1 decade). The RheoPlus software (Anton Paar GmbH, Austria) was used for data acquisition and analysis.

[0102] Preferably, the lignin oil is soluble in organic solvents or oily compounds, such as vegetable oils. Solubility is defined as having at least 85% of the lignin oil in a mixture of lignin oil and an organic solvent consisting of 30% lignin oil by mass relative to the total mass of the mixture, forming a homogeneous mixture at a temperature of 200°C or higher. Preferably, the mass content of the mixture of phenolic compounds (preferably lignin oil) in the mixture to be treated ranges from 1% to 30%, preferably from 2% to 25%, preferably from 3% to 20%, preferably from 4% to 15%, and preferably from 5% to 10% by mass relative to the total mass of the mixture to be treated.

[0103] Stage of catalytic reduction fractionation of a lignocellulosic biomass

[0104] The lignin oil which is preferably used in the process according to the invention is preferably obtained by catalytic reduction fractionation of a lignocellulosic biomass.

[0105] The term "lignocellulosic biomass" refers to biomass derived from plants or their by-products. Lignocellulosic biomass is composed of carbohydrate polymers (cellulose, hemicellulose) and an aromatic polymer (lignin).

[0106] The term "reductive catalytic fractionation" refers to a process that separates the different components of lignocellulose, as described above, into a solid pulp of carbohydrates and a lignin oil, by cleaving the ester and ether bonds following high-temperature tandem solvolysis, hydrogenation, and hydrogenolysis, either in batch mode or in (semi-)continuous mode on a metallic catalyst in the presence of a reducing agent, such as hydrogen.

[0107] Almost complete delignification of hardwoods, such as birch and poplar, can be achieved without significant degradation of carbohydrates and without condensation of lignin (formation of C-C bonds making lignin processing difficult because it is insoluble and very viscous or solid).

[0108] Preferably, catalytic reduction fractionation is carried out at a temperature between 180°C and 400°C, preferably between 200°C and 280°C.

[0109] Preferably, the catalytic reduction fractionation is carried out in the presence of a metallic catalyst, preferably supported, preferably comprising a platinum group metal (ruthenium Ru, rhodium Rh, palladium Pd, osmium Os, iridium Ir, platinum Pt) or nickel or cobalt, or mixtures of these metals, preferably comprising ruthenium, preferably ruthenium supported on carbon.

[0110] Preferably, catalytic reduction fractionation is carried out under hydrogen pressure. Preferably, catalytic reduction fractionation is carried out at a hydrogen pressure between 5 and 150 bar, preferably between 10 and 80 bar, preferably between 25 and 50 bar (1 bar = 1 x 10⁻³). 5 Pa). Preferably, the reductive catalytic fractionation is carried out for a duration of 1 hour to 8 hours, preferably from 2 hours to 4 hours.

[0111] Preferably, the catalytic reduction fractionation is carried out in the presence of a solvent, preferably an organic solvent, preferably selected from (1) linear or branched alcohols, preferably linear alcohols, advantageously methanol or ethanol, (2) acids, preferably acetic acid or propionic acid, and (3) esters, preferably methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, or mixtures thereof. Optionally, the catalytic reduction fractionation is carried out in the presence of water or mixtures of water and the alcohols, acids, and / or esters mentioned above.

[0112] Preferably, the process according to the invention comprises a catalytic reduction fractionation step of a lignocellulosic biomass to obtain the mixture of phenolic compounds, preferably lignin oil. The catalytic reduction fractionation step of a lignocellulosic biomass is as described above.

[0113] The process according to the invention may further include a step of separating the solid pulp fractions from carbohydrates and lignin oil, produced at the end of the catalytic reduction fractionation step of a lignocellulosic biomass. The separation step is preferably a filtration or hydrocyclone separation of the solid pulp (the lignin oil being located in the liquid fraction), optionally followed by washing the solid residue and combining the different liquid fractions.

[0114] The catalytic reduction fractionation of lignocellulosic biomass (and the separation of the solid pulp fractions of carbohydrates and lignin oil) is for example as described in application WO 2022 / 090364.

[0115] An example of a general procedure for the catalytic reduction fractionation of lignocellulosic biomass, followed by the separation of the solid pulp fractions from carbohydrates and lignin oil, is as described below:

[0116] A 2 L stirred batch reactor is loaded with 150 g of lignocellulosic biomass (particle size <10 mm), 800 mL of organic solvent, and 15 g of catalyst. The reaction vessel is sealed and flushed three times with N2 (8 bar) to remove residual oxygen. High-pressure H2 is applied to the reaction mixture before heating, and the reactor is stirred at 720 rpm. The reaction proceeds at 235 °C. After several hours, the reaction is stopped by rapid cooling with a stream of compressed air and water. The reactor contents are filtered to separate the solid fraction, containing carbohydrate pulp and catalyst, from the liquid fraction, containing lignin oil and some soluble sugar products. To collect all the liquid fraction, the solid residue is washed with ethanol.Next, the organic solvent used in the reaction and ethanol are removed from the liquid phase by rotary evaporation to give a brownish crude lignin oil of phenolic compounds, lignin oligomers and some soluble sugars.

[0117] According to a first embodiment, a triple liquid-liquid extraction with water and ethyl acetate at a mass ratio of 1 / 3 / 3 (crude lignin oil / ethyl acetate / water) can be carried out to separate water-soluble compounds, particularly soluble sugars. Evaporation of the ethyl acetate yields a lignin oil substantially free of sugars, composed of monomeric phenolic compounds, phenolic dimers, and phenolic oligomers.

[0118] According to another embodiment, the process for preparing a hydrocarbon mixture of the invention can also be carried out on a "crude" lignin oil, that is to say, the lignin oil obtained before the triple liquid-liquid extraction. b) Effluent intended for hydrotreatment

[0119] The mixture to be treated in the process of the invention includes, in particular, an effluent intended for hydrotreatment. Throughout this text, the effluent intended for hydrotreatment may also be referred to as "effluent b)".

[0120] The term "effluent intended for hydrotreatment" refers to any effluent intended to undergo a hydrotreatment step, preferably as part of a hydrocarbon preparation process, and more preferably of a jet fuel preparation process. An effluent intended for hydrotreatment is therefore an effluent intended to be a reagent in a hydrotreatment step, and not simply a solvent. During hydrotreatment, the effluent will be chemically modified (specifically, the removal of one or more chemical elements other than hydrogen and carbon, such as sulfur and / or nitrogen and / or oxygen and / or a metal). If the hydrotreatment is hydrodeoxygenation, the effluent loses oxygen atoms, which is not the case for the diluent.Preferably, the effluent intended for hydrotreatment comprises oxygen and / or sulfur and / or nitrogen atoms and / or a metal; preferably, the effluent intended for hydrodeoxygenation comprises oxygen atoms.

[0121] According to the invention, the effluent intended to be hydrotreated is hydrotreated in the presence of a mixture of phenolic compounds.

[0122] According to the invention, the effluent intended for hydrotreatment comprises at least one compound other than a phenolic compound. In particular, an effluent intended for hydrotreatment according to the invention comprises, relative to the mass of the effluent intended for hydrotreatment, 1% by mass or less of phenolic compounds, in particular phenolic compounds as described above. Preferably, an effluent intended for hydrotreatment according to the invention does not comprise any phenolic compounds, in particular phenolic compounds as described above.

[0123] Preferably, the effluent intended for hydrotreatment is either selected from a petroleum cut from a step of a petroleum refining process, or comprises one or more C12-C24 fatty acid esters, preferably C14-C20, preferably C16-C18 and / or one or more C12-C24 fatty acids, preferably C14-C20, preferably C16-C18. These two types of effluent are preferably as defined below.

[0124] According to a first embodiment, the effluent intended to be hydrotreated is a petroleum cut from a step of a petroleum refining process, preferably from a distillation step, preferably a petroleum cut from a petroleum refining process intended to be hydrotreated.

[0125] Preferably, the petroleum cut is obtained by atmospheric distillation and is preferably chosen from:

[0126] - a naphtha cup,

[0127] - a kerosene cup,

[0128] - a diesel fuel blend.

[0129] Preferably, the petroleum cut is obtained from catalytic cracking, from fractions obtained by vacuum distillation, from the C25-C50 fraction obtained by atmospheric distillation and is preferably chosen from a kerosene cut and a diesel cut (LCO, light cycle oil according to English terminology), advantageously a kerosene cut.

[0130] A fossil-derived naphtha cut typically has boiling points ranging from 15°C to 220°C. According to ASTM D86-12, it typically has an initial boiling point of 15°C to 42°C and a final boiling point of 220°C or lower. Such a naphtha cut generally originates from the direct distillation of crude oil or from fractionation after hydrotreating, hydroisomerization, and / or hydrocracking, and typically comprises C5-C12 compounds.

[0131] A fossil-based diesel fraction typically has boiling points ranging from 80°C to 360°C. According to ASTM D86-12, it typically has an initial boiling point of 180 to 240°C and a final boiling point of 360°C or lower. Such a diesel fraction generally originates from the direct distillation of crude oil or from fractionation after hydrotreating, hydroisomerization, and / or hydrocracking, and typically comprises C13-C25 compounds.

[0132] A kerosene cut typically has boiling points ranging from 130 °C to 300 °C. According to ASTM D86-12, it typically has an initial boiling point of 130 to 160 °C and a final boiling point of 220 °C to 300 °C. Such a kerosene cut generally originates from the direct distillation of crude oil or from fractionation after hydrotreating and / or hydroisomerization and / or hydrocracking, and typically comprises C9-C15 compounds.

[0133] Preferably, according to this embodiment, the mixture to be treated consists of the mixture of phenolic compounds (preferably lignin oil) and the effluent intended to be hydrotreated.

[0134] According to a second embodiment, the effluent intended to be hydrotreated comprises one or more fatty acid esters in C12-C24, preferably in C14-C20, preferably in C16-C18 and / or one or more fatty acids in C12-C24, preferably in C14-C20, preferably in C16-C18.

[0135] Preferably, in this embodiment, the hydrotreatment step is a hydrodeoxygenation step. In this case, the effluent intended for hydrotreatment can be called effluent intended for hydrodeoxygenation.

[0136] The fatty acid can be saturated or unsaturated. It is preferably chosen from linoleic acid, oleic acid, palmitic acid and stearic acid.

[0137] The fatty acid ester can be a saturated or unsaturated fatty acid ester. In particular, these are C12-24 fatty acid triesters, especially glycerol triesters and C12-24 fatty acid triesters.

[0138] The effluent intended for hydrotreatment preferably comprises at least one C12-C24 fatty acid ester, preferably a C14-C20 ester, or preferably a C16-C18 ester, as defined above. More preferably, it is an ester, preferably a triester, of linoleic acid, oleic acid, palmitic acid, and stearic acid, advantageously a triester of glycerol and linoleic acid, oleic acid, palmitic acid, or stearic acid.

[0139] The effluent intended for hydrotreatment preferably comprises at least two, preferably at least three, preferably at least four different esters as defined above.

[0140] Preferably, the effluent intended for hydrotreatment comprises a naturally sourced oil, the naturally sourced oil comprising the C12-C24 fatty acid ester(s) and / or the C12-C24 fatty acid(s). Preferably, the effluent intended for hydrotreatment is (or consists of) a naturally sourced oil.

[0141] Preferably, according to this embodiment, the mixture to be treated can consist of a mixture of phenolic compounds (preferably lignin oil) and an oil of natural origin.

[0142] A naturally sourced oil is defined as an oil derived from biomass and containing no fossil-based mineral oil. In the description "naturally sourced oil(s)" refers indiscriminately to oils, for example vegetable or used oils, fats, and mixtures thereof.

[0143] These oils can be used as is or after pre-treatment.

[0144] Pre-treatments of naturally derived oils include well-known chemical and physical processes such as degumming, neutralization with an alkaline (usually NaOH) or acidic (e.g., citric acid) solution, bleaching, polishing, steam treatment, etc. (e.g., described in US2019338219A1).

[0145] The vegetable oil can be chosen from pine oil, rapeseed oil, sunflower oil, castor oil, peanut oil, linseed oil, babassu oil, hemp oil, linola oil, jatropha oil, peanut oil, rice bran oil, mustard oil, carinata oil, coconut oil, copra oil, olive oil, palm oil, cottonseed oil, corn oil, palm kernel oil, soybean oil, pumpkin seed oil, grapeseed oil, argan oil, jojoba oil, sesame oil, walnut oil, hazelnut oil, tung oil, rice oil, safflower oil, seaweed oil, used oils, nut shell oil (especially cashew nut shell oil), and any combination thereof.

[0146] Used oil includes used cooking oils (used food oils) and oils recovered from wastewater, such as trap and drain grease / oil, gutter oil, sewage oil, e.g. from wastewater treatment plants, and used grease from the food industry.

[0147] Animal fat can be chosen from tallow, lard, fat (yellow and brown fat), fish oil / fat, milk fat.

[0148] In particular, animal fats and used cooking oils can be used, which are animal by-products and whose status as animal by-products within the meaning of Regulation (EC) No 1069 / 2009 of the European Parliament and of the Council of 21 October 2009 and of Commission Regulation (EU) No 142 / 2011 (implementing Regulation of EC No 1069 / 2009).

[0149] Animal fats having the status of animal by-products are fatty residues of animal origin, other than used cooking oils, coming for example from food industries or rendering plants.

[0150] Used cooking oils having the status of animal by-products are used cooking food oils (used cooking oils or UCO), namely residues of fats of vegetable or animal origin used for human consumption, in the agri-food industry, in collective or commercial catering.

[0151] Naturally sourced oil can also be oil produced by microorganisms, whether natural or genetically modified, such as bacteria, yeasts (including oleaginous yeasts), algae, prokaryotes, or eukaryotes. These oils can be recovered using well-established mechanical or chemical extraction methods.

[0152] In a preferred embodiment, the oil of natural origin may be chosen from an animal fat and / or a used oil and / or a vegetable oil, and in particular from an animal fat and / or a used oil having the status of waste.

[0153] In another embodiment, the oil of natural origin is preferably chosen from vegetable oils.

[0154] A naturally sourced oil may contain 50% or more by mass of fatty acid esters (mono-, di-, and triglycerides of fatty acids) and / or free fatty acids, preferably 60% or more by mass, with 70% or more by mass being the most preferable. Typically, a naturally sourced oil, or a blend of naturally sourced oils, may contain fatty acid esters and free fatty acids, containing one to three C12-C24 fatty acid ester groups and / or a C12-C24 C8-C24 acyl fatty acid group, saturated or unsaturated. When multiple acyl groups are present, they may be identical or different.

[0155] Preferably, if the effluent intended for hydrotreatment includes at least one C12-C24 fatty acid ester and / or at least one C12-C24 fatty acid, the mass content of the C12-C24 fatty acid ester and / or of the C12-C2 fatty acid(s) in the mixture to be treated shall be from 2% to 60% by mass, preferably from 5% to 50% by mass, preferably from 8% to 40% by mass, preferably from 10% to 25% by mass, preferably from 15% to 20% by mass relative to the total mass of the mixture to be treated.

[0156] Preferably, if the effluent intended to be hydrotreated includes a C12-C24 fatty acid ester and / or a C12-C24 fatty acid, the mass content of the mixture of phenolic compounds in the mixture to be treated shall be from 1% to 30% by mass, preferably from 2% to 25% by mass, preferably from 3% to 20% by mass, preferably from 4% to 15% by mass, preferably from 5% to 10% by mass relative to the total mass of the mixture to be treated.

[0157] Preferably, the mass ratio between the mass content of the phenolic compound mixture and the total mass content of C12-C24 fatty acid ester and C12-C24 fatty acid (preferably in vegetable oil(s)) ranges from 0.2 to 5, preferably from 0.3 to 3, preferably from 0.5 to 2, preferably from 0.7 to 1.5, preferably from 0.8 to 1, and preferably from 0.85 to 0.95, the mass contents being defined relative to the total mass of the mixture to be treated. c) Diluent

[0158] In some embodiments, the mixture to be treated may also include a diluent, preferably hydrocarbon.

[0159] The diluent is preferably an organic solvent, preferably having a boiling point greater than or equal to 15 °C and preferably less than or equal to 400 °C, preferably comprising one or more linear or branched alkanes and / or one or more naphthenic compounds and / or one or more aromatic compounds, preferably one or more linear alkanes, preferably of the C8-C16 range, advantageously dodecane. It may also comprise a mixture of alkanes, such as, for example, a naphtha cut, kerosene, diesel, or distillate from a refinery, or have a composition such as that of the hydrocarbon mixture obtained by the process according to the invention, or a composition of the fraction of the hydrocarbon mixture consisting of the hydrotreated mixture of phenolic compounds and the effluent (b), or the composition of a mixture obtained after treatment and / or distillation or otherwise of the hydrocarbon mixture obtained by the process according to the invention.

[0160] The presence of a diluent helps to limit exothermicity, which is all the more important when the hydrotreating reaction is carried out in a single step. In one embodiment, the diluent comprises, relative to the total mass of the diluent, at least 30% by mass, preferably at least 40% by mass, preferably at least 50% by mass, preferably at least 60% by mass, preferably from 40% to 100% by mass, preferably from 50% to 80% by mass, of C8-C24 compounds, preferably of C9-C16 compounds. Optionally, the diluent consists of C8-C24 compounds, preferably of C9-C16 compounds. This is advantageous because the diluent can then potentially be used in the jet fuel (C8-C24 cut, preferably C9-C16).Furthermore, if the diluent contains functional groups that can react during the hydrodeoxygenation step (such as unsaturated bonds), it will necessarily react. The fact that the diluent contains a number of carbon atoms compatible with jet fuel production ensures that this byproduct is not lost but can be utilized in the jet fuel fraction. Conversely, a diluent containing fewer than 8 carbon atoms will consume dihydrogen but will not be utilized in the jet fuel fraction that we are trying to optimize.

[0161] In one embodiment, the diluent may consist of hydrocarbons of fossil origin. In this case, it does not include components of renewable origin.

[0162] Fossil hydrocarbons usable in the process can advantageously be chosen from naphtha cuts, diesel cuts, kerosene cuts and distillate cuts, notably from the distillation of crude oil.

[0163] The naphtha, diesel and kerosene cuts are defined above.

[0164] Fossil-derived distillate fractions typically have boiling points ranging from 375 to 600 °C. According to ASTM D86-12, they typically have an initial boiling point of 375 to 450 °C and a final boiling point of 500 to 600 °C. Such distillate fractions are generally obtained from the vacuum distillation of an atmospheric residue of crude oil, also known as vacuum distillates, and typically contain C20-C55 compounds.

[0165] Preferably, the diluent is the hydrocarbon mixture obtained by the process according to the invention, or is the fraction of the hydrocarbon mixture consisting of the hydrotreated phenolic compound mixture and the hydrotreated effluent b).

[0166] Preferably, the diluent has an oxygen atom content of 5% or less by mass, relative to the total mass of the diluent, preferably 3% or less by mass, preferably 1% or less by mass, preferably 0.5% or less by mass, preferably between 0.01% and 5% by mass, and preferably is completely free of oxygen atoms. The mass content of oxygen atoms is defined by ASTM 5622, May 2017. The presence of a diluent advantageously reduces the overall oxygen atom content of the mixture to be treated, which significantly improves the efficiency of the hydrotreating step.

[0167] The presence of a diluent is particularly preferable when the effluent intended for hydrotreatment includes a C12-C24 fatty acid ester and / or a C12-C24 fatty acid.

[0168] Mixture to be treated

[0169] Preferably, the mixture to be treated has, in relation to the total mass of the mixture to be treated, a mass content of oxygen atoms less than or equal to 20% by mass, preferably less than or equal to 15% by mass, preferably less than or equal to 12% by mass, preferably less than or equal to 10% by mass, preferably less than or equal to 8% by mass, preferably less than or equal to 7% by mass, preferably less than or equal to 6% by mass, preferably less than or equal to 5% by mass, preferably between 0.01% and 20% by mass.

[0170] The mass content of oxygen atoms is understood to be the ratio between the mass of all the oxygen atoms present in the mixture to be treated and the total mass of the mixture to be treated.

[0171] The mass content of oxygen atoms is defined by elemental analysis of the mixture to be treated, according to the protocol defined by the ASTM 5622 standard of May 2017.

[0172] The mixture to be treated comprises, or even consists of, a) the mixture of phenolic compounds, b) the mixture intended to be hydrotreated and c) the possible diluent).

[0173] mixture of hydrocarbons

[0174] The process according to the invention produces a mixture of hydrocarbons.

[0175] The present invention therefore also relates to a mixture of hydrocarbons obtained by the process according to the invention.

[0176] By hydrocarbon mixture is meant a mixture consisting essentially of hydrocarbon compounds comprising at least three carbon atoms, preferably at least six carbon atoms.

[0177] Preferably, the hydrocarbon mixture is bio-based, that is, derived from renewable organic matter.

[0178] The bio-based nature of the hydrocarbon mixture can be characterized by its carbon-14 content. In one embodiment in which the mixture to be treated comprises the mixture of phenolic compounds, effluent (b), and a diluent, the hydrocarbon mixture obtained by the process according to the invention comprises a fraction of the hydrocarbon mixture consisting of the hydrotreated mixture of phenolic compounds and the hydrotreated effluent (b), and a fraction corresponding to the diluent. In another embodiment in which the mixture to be treated comprises at least the mixture of phenolic compounds and effluent (b), the hydrocarbon mixture obtained by the process according to the invention comprises at least a fraction of the hydrocarbon mixture consisting of the hydrotreated mixture of phenolic compounds and the hydrotreated effluent (b).In both embodiments, the composition of the product obtained from the process of the invention is preferably expressed with respect to the fraction of the hydrocarbon mixture consisting of the hydrotreated mixture of phenolic compounds and the hydrotreated effluent. This allows the composition of the fraction resulting from the hydrotreatment of the mixture of phenolic compounds (preferably lignin oil) to be highlighted without taking into account the diluent or any other components of the mixture to be treated.

[0179] In an embodiment where the mixture to be treated consists of the mixture of phenolic compounds and the effluent (b), the hydrocarbon mixture obtained by the process according to the invention corresponds to the fraction of the hydrocarbon mixture consisting of the hydrotreated mixture of phenolic compounds and the hydrotreated effluent (b). In this embodiment, the composition of the hydrocarbon mixture is preferably expressed as a percentage of the total mass of the hydrocarbon mixture.

[0180] Preferably, the hydrocarbon mixture (or the fraction of the hydrocarbon mixture consisting of the hydrotreated phenolic compound mixture and the hydrotreated effluent b) comprises from 50% to 99% by mass, preferably from 60% to 98% by mass, preferably from 70% to 95% by mass, preferably from 80% to 90% by mass, preferably from 85% to 90% by mass of C9-C18 compounds relative to the total mass of the hydrocarbon mixture (or the fraction of the hydrocarbon mixture consisting of the hydrotreated phenolic compound mixture and the hydrotreated effluent b). By C9-C18 compounds is meant all the compounds in the hydrocarbon mixture comprising from 9 to 18 carbon atoms.

[0181] According to a first embodiment, the aromatic rings of the compounds in the phenolic compound mixture are not hydrogenated during the hydrotreating step (the aromatic compound content then depends on the amount of phenolic compound mixture in the initial mixture to be treated). Preferably according to this embodiment, the hydrocarbon mixture (or the fraction of the hydrocarbon mixture consisting of the hydrotreated phenolic compound mixture and the hydrotreated effluent b) comprises from 8% to 60%, preferably from 10% to 50%, preferably from 15% to 40%, preferably from 20% to 35%, preferably from 25% to 30% by mass of aromatic compounds relative to the total mass of the hydrocarbon mixture (or the fraction of the hydrocarbon mixture consisting of the hydrotreated phenolic compound mixture and the hydrotreated effluent b)).

[0182] Preferably, the hydrocarbon mixture (or the fraction of the hydrocarbon mixture consisting of the hydrotreated phenolic compound mixture and the hydrotreated effluent b) is substantially free of naphthenic compounds (contains less than 0.1% by mass of naphthenic compounds), preferably is totally free of naphthenic compounds.

[0183] According to a second embodiment, the aromatic rings of the compounds in the phenolic compound mixture are, for the most part, or even all, hydrogenated during the hydrotreating step. Preferably according to this embodiment, the hydrocarbon mixture (or the fraction of the hydrocarbon mixture consisting of the hydrotreated phenolic compound mixture and the hydrotreated effluent b) comprises from 8% to 60%, preferably from 10% to 50%, preferably from 15% to 40%, preferably from 20% to 35%, preferably from 25% to 30% by mass of naphthenic compounds relative to the total mass of the hydrocarbon mixture (or the fraction of the hydrocarbon mixture consisting of the hydrotreated phenolic compound mixture and the hydrotreated effluent b)).

[0184] Preferably according to this embodiment, the hydrocarbon mixture (or the fraction of the hydrocarbon mixture consisting of the hydrotreated phenolic compound mixture and the hydrotreated effluent b)) is substantially free of aromatic compounds (contains less than 0.1% by mass of aromatic compounds), preferably is totally free of aromatic compounds.

[0185] According to a third embodiment, the aromatic rings of the compounds in the phenolic compound mixture are partially hydrogenated during the hydrotreating step, i.e., some are completely hydrogenated and others not at all. Preferably, the hydrocarbon mixture (or the fraction of the hydrocarbon mixture consisting of the hydrotreated phenolic compound mixture and the hydrotreated effluent b)) comprises from 1% to 60%, preferably from 2% to 40%, preferably from 3% to 20%, preferably from 4% to 15%, by mass of aromatic compounds relative to the total mass of the hydrocarbon mixture.

[0186] Preferably according to this embodiment, the hydrocarbon mixture (or the fraction of the hydrocarbon mixture consisting of the hydrotreated phenolic compound mixture and the hydrotreated effluent b)) comprises from 1% to 60%, preferably from 10% to 50%, preferably from 15% to 40%, preferably from 20% to 35%, preferably from 25% to 30% by mass of naphthenic compounds relative to the total mass of the hydrocarbon mixture (or the fraction of the hydrocarbon mixture consisting of the hydrotreated phenolic compound mixture and the hydrotreated effluent b).

[0187] In these three embodiments above, the hydrocarbon mixture (or the fraction of the hydrocarbon mixture consisting of the hydrotreated phenolic compound mixture and the hydrotreated effluent b)) preferably comprises 30% to 95% by mass, preferably 40% to 90% by mass, preferably 50% to 80% by mass, preferably 55% to 70% by mass of aliphatic compounds relative to the total mass of the hydrocarbon mixture (or the fraction of the hydrocarbon mixture consisting of the hydrotreated phenolic compound mixture and the hydrotreated effluent b).

[0188] Preferably, the hydrocarbon mixture (or the fraction of the hydrocarbon mixture consisting of the hydrotreated phenolic compound mixture and the hydrotreated effluent b)) consists of a mixture of naphthenic, aromatic, and aliphatic compounds. The content of two of the selected naphthenic, aromatic, and aliphatic compound types determines the content of the third compound type. For example, for a given percentage content or range of percentages of aromatic and naphthenic compounds, the difference from 100% represents the percentage content of aliphatic compounds.

[0189] Preferably, the hydrocarbon mixture (or the fraction of the hydrocarbon mixture consisting of the hydrotreated phenolic compound mixture and the hydrotreated effluent b) comprises, relative to the total mass of the hydrocarbon mixture (or the fraction of the hydrocarbon mixture consisting of the hydrotreated phenolic compound mixture and the hydrotreated effluent b), less than 10% by mass, preferably less than 8% by mass, preferably less than 5% by mass, preferably less than 3% by mass, preferably less than 2% by mass, preferably less than 1% by mass, preferably less than 0.5% by mass, preferably less than 0.4% by mass, preferably less than 0.2% by mass, preferably from 0.001% to 10% by mass of oxygen atoms.Oxygen atom mass content means the ratio between the mass of all oxygen atoms present in the hydrocarbon mixture (or in the fraction of the hydrocarbon mixture consisting of the hydrotreated phenolic compound mixture and the hydrotreated effluent b) to the total mass of the hydrocarbon mixture (or the fraction of the hydrocarbon mixture consisting of the hydrotreated phenolic compound mixture and the hydrotreated effluent b).

[0190] The mass content of oxygen atoms is defined according to ASTM 5622 of May 2017.

[0191] Jet fuel

[0192] When the process according to the invention further includes a step of fractionating the hydrocarbon mixture, it produces in particular a jet fuel.

[0193] The present invention therefore also relates to a jet fuel obtained by the process according to the invention.

[0194] Jet fuel includes in particular the C9-C18 compounds of the hydrocarbon mixture.

[0195] Preferably, the jet fuel comprises, relative to the total mass of the jet fuel, less than 10% by mass, preferably less than 8% by mass, preferably less than 5% by mass, preferably less than 3% by mass, preferably less than 2% by mass, preferably less than 1% by mass, preferably less than 0.5% by mass, preferably less than 0.4% by mass, preferably less than 0.2% by mass, preferably less than 0.05% by mass, preferably from 0.001% to 10% by mass of oxygen atoms.

[0196] Preferably, the contents of aromatic, naphthenic and aliphatic compounds are as defined above for the hydrocarbon mixture (but expressed on the basis of the total mass of jet fuel).

[0197] The present invention further relates to the use of jet fuel as defined above,

[0198] (i) in a mixture with jet fuel resulting from the distillation of petroleum, or

[0199] (ii) in a mixture with a synthetic jet fuel, preferably produced from the hydrotreated esters and fatty acids (HEFA) conversion process, the alcohols to jet conversion process, or the Fischer-Tropsch process, to power at least one aircraft engine.

[0200] The expressions "between ... and ..." and "ranging from ... to ..." should be understood inclusive of limits, unless otherwise specified.

[0201] The following examples will help to better understand the invention, but are not intended to be exhaustive.

[0202] EXAMPLES

[0203] Example 1: Solubility of lignin oils

[0204] The solubility of a lignin oil as used in the process of the invention was determined according to the following protocol.

[0205] To determine the solubility of lignin oil, 1 g of lignin oil was placed in a 100 mL round-bottom flask, to which 20 mL of vegetable oil was added and heated to 220 °C (heating time ~30 min) with stirring at 700 rpm. After 1 h, when the temperature inside the flask was 220 °C, stirring was stopped and the liquid fraction was collected using a glass pipette and stored in a separate container. The insoluble solid inside the flask was then rinsed with n-hexane to remove residual vegetable oil and placed in an oven at 80 °C overnight. The mass of the solid residue was recorded to calculate the amount of insoluble and soluble fractions of the lignin oil.

[0206] [Math 1]

[0207] Dried solid residues g)

[0208] Insoluble fraction (wt.%) = Initial lignin oil wx 100

[0209] [Math 2]

[0210] > . . . . z

[0211] Soluble fraction (

[0212] The viscosity of the lignin oil was also determined according to the following protocol:

[0213] Viscosity measurements were performed on a controlled-strain rheometer (Anton Paar MCR501). The sample temperature was controlled using a Peltier system (P-PTD200) with a solvent plate base and an evaporation blocker with an accuracy of approximately 0.1 °C.

[0214] For viscosities above 0.1 Pa·s, a PP25 geometry was used, while for viscosities below 0.1 Pa·s, a PP50 geometry was used. Viscosity was determined based on the shear rate at 5 measurement points per decade. The shear rate range was adjusted according to temperature and sample so that measurements were performed in the Newtonian regime and above the instrument's minimum torque level. In the Newtonian regime, the average was calculated over 5 measurement points (1 decade). RheoPlus software (Anton Paar GmbH, Austria) was used for data acquisition and analysis.

[0215] The viscosities of vegetable oils are taken from the following reference: Thermophysical Properties of Cotton, Canola, Sunflower and Soybean Oils as a Function of Temperature Edwin E. Garcia Rojas, Jane SR International Journal of Food Properties.

[0216] The results are summarized in the following table:

[0217] [Table 1]

[0218] RCF lignin oil has a low viscosity compared to other lignin oils, such as those produced using the organosolv process. Its viscosity is closer to that of crude oil. This makes RCF lignin oil unique because it is more easily processed.

[0219] Furthermore, the solubility of RCF lignin oil in dodecane was compared with that of other lignin oils obtained by other biorefinery processes. Conditions: Dodecane (22 ml); temperature (220°C); lignin oil (0.150 g); time (1 h); rpm (700).

[0220] The results are presented in the following table:

[0221] [Table 2]

[0222] M. Dierks, MT Clough, IB Daltro de Castro and R. Rinaldi, Joule, 2018, 2, 1118-1133.

[0223] RCF lignin oil is more soluble than other lignin oils such as kraft lignin or Organosolv lignin oil in different vegetable oils, which makes it possible to consider a co-hydrodeoxygenation process of lignin oil with a vegetable oil.

[0224] Example 2: Hydrodeoxygenation of a mixture of lignin oil and vegetable oil by a process according to the invention

[0225] The lignin oil used in this example was obtained by a process as described in WO 2022 / 090364 (example 1). It has the following characteristics:

[0226] [Table 3]

[0227] Lignin oil contains on average 39 carbon atoms per molecule before H₂DO: Calculation:

[0228] Average molar mass of lignin oil: 712 g / mol Elemental analysis of lignin oil: (%C= 64.5%; %H=7.4%; %O=25.6%)

[0229] Each molecule contains an average mass of 459 g / mol of carbon = Average molar mass x percentage of mass corresponding to carbon. This corresponds to an average of 38 carbon atoms: average mass of carbon atoms per molecule / per atomic mass of carbon. Lignin oil was mixed with rapeseed oil in various formulations, with or without a diluent. The resulting mixture is the mixture to be treated. These different mixtures were then hydrodeoxygenated according to the following protocol:

[0230] Before the hydrodeoxygenation step, the catalysts are synthesized: A Ni-P / SiO2 catalyst containing 65% by weight of Nickel and 5% by weight of Phosphorus on a SiO2 support (designated as Ni-P) was prepared according to the following procedure: A commercial 65%Ni / SiO2 catalyst precursor was purchased from Strem Chemicals Inc. The catalyst precursor, as received, was impregnated with phosphorus using a phosphoric acid solution (H3PO4, aqueous solution at 83% by weight).

[0231] The phosphoric acid solution (0.98 g) is dissolved in deionized water (1 mL) to which the catalyst precursor 65% Ni / SiO2 (2 g) has been added, and the mixture is mechanically stirred for 1 hour to obtain a uniformly mixed solution. The resulting uniformly mixed solution has a phosphorus / nickel (P / Ni) molar ratio of 0.1.

[0232] The mixture is then aged at room temperature for 12 hours, then heated in an oven at 80°C under an air atmosphere for 12 hours, thus preparing the dried Ni-P precursor.

[0233] A U-tube reactor was then filled with 1 gram of dried Ni-P precursor. The reactor temperature was increased to 550 °C at 1 °C / min with a H2 flow rate of 30 mL / min (standard milliliters). Once the temperature reached 550 °C, activation was carried out for 4 h. After activation, the U-tube was cooled to room temperature, and a gas mixture containing approximately 1% oxygen mixed with nitrogen was introduced for 1 h to obtain passivated Ni-P.

[0234] To maintain the activity and stability of the Ni-P catalyst, it is not necessary to introduce sulfide reagents into the mixture to be treated for the hydrodeoxygenation step.

[0235] Regenerated NiMo / Al₂O₃ or CoMo / Al₂O₃ catalysts were activated by a sulfidation process. The regenerated NiMo / Al₂O₃ or CoMo / Al₂O₃ catalysts were ground and sieved into a fine powder. Two g of powdered NiMo / Al₂O₃ or CoMo / Al₂O₃ catalyst were then loaded into the 50 mL reactor (Parr Instruments). The reactor was pre-purged with nitrogen. Optionally, when the reaction is performed in batch mode, 5 mL of dimethyl disulfide (DMDS, grade >99%, Sigma-Aldrich) in 25 mL of dodecane solvent can be added to the reactor. The H₂ pressure in the reactor is 35 bar. The reactor temperature is first increased (25°C / hour) to 230°C and maintained at this temperature for 4 hours (continuous stirring at 700 rpm). The temperature is then increased to 340°C (25°C / hour) and maintained at this temperature for 6 hours (continuous stirring at 700 rpm). The DMDS decomposes and reacts with hydrogen to generate H2S, which acts as a sulfurizing agent.The amount of DMDS used was greater than what was needed for the complete sulfidation of the nickel and molybdenum phases.

[0236] To maintain the activity and stability of the CoMoS and NiMoS catalysts, sulfur-containing reagents can optionally be introduced into the mixture to be treated for the hydrodeoxygenation step. The hydrodeoxygenation step is carried out in a 50 ml Parr reactor supplied by Parr Instrument Company, model 4590. The reactor vessel was loaded with 1 g of activated catalyst (i.e., 16.7% by mass of the lignin oil + rapeseed oil mixture), 6 g of the lignin oil + rapeseed oil mixture (e.g., 2.7 g of lignin oil and 3.3 g of rapeseed oil) (30% by mass of the total feed), and 14 g of dodecane as a diluent (also called carrier fluid, 70% by mass of the total feed). Poplar wood lignin was prepared according to the methods described in 2019 / 0233743 A1. The main characteristics of the poplar wood lignin oil used in the invention are shown in Table 2.

[0237] The hydrodeoxygenation stage includes the following steps:

[0238] (i) Addition of the lignin oil + rapeseed oil mixture into the reactor tank.

[0239] (ii) Addition of the diluent (dodecane) into the reactor vessel.

[0240] (iii) Addition of an activated catalyst to the mixture and hermetically sealing of the reactor vessel to the reactor head assembly.

[0241] (iv) Maintaining reactor pressure and temperature, including

[0242] (a) Purge the nitrogen gas in the mixture obtained in step (iii) at 0.5-0.7 bar three times and add hydrogen gas to achieve the desired pressure of between 0.5-100 bar in the reactor vessel.

[0243] (b) Heat the reactor vessel to the desired temperature of 250 to 340 °C and stir the reaction mixture at 600-700 rpm for 3 to 22 hours.

[0244] (v) Cool the reactor vessel to a temperature between 25 and 30 °C, release the unreacted hydrogen gas, remove the reactor vessel from the head assembly and separate the catalyst to obtain the liquid hydrocarbon product.

[0245] The following table lists the compositions of the different mixtures tested, the conditions under which they were hydrodeoxygenated, the reaction yield, and some details of the composition of the final product.

[0246] [Table 4]

[0247] * : The yield corresponds to the mass of the products obtained divided by the maximum theoretical mass that can be obtained. The diluent is not taken into account since it does not react. The maximum theoretical mass is the mass of the mixture to be treated minus the mass of the oxygens and O-methyl groups in the lignin oil.

[0248] These results show that it is possible to significantly reduce the oxygen content by co-hydrodeoxygenating a lignin oil and a vegetable oil. These results also show that the mass concentration of oxygen in the starting material to be treated influences the hydrotreatment, preferably hydrodeoxygenation, of a mixture of lignin oil and vegetable oil with good yield and low residual oxygen content.

[0249] Example 3: Hydrodeoxygenation of a mixture of lignin oil and vegetable oil by a process according to the invention – effect of the catalyst

[0250] The lignin oil used in this example is identical to that used in Example 2, and the hydrodeoxygenation protocol is also identical, except for the type of catalyst. Three catalysts were tested: Ni-P, CoMoS, and NiMoS.

[0251] The following table summarizes the results obtained:

[0252] [Table 5]

[0253] * : The yield corresponds to the mass of the products obtained divided by the maximum theoretical mass of compound that can be obtained. The diluent is not taken into account because it does not react. The maximum theoretical mass is the mass of the mixture of lignin oil and rapeseed oil minus the mass of the oxygens and O-methyl groups in the lignin oil and minus the mass of the oxygens and glyceryl fraction of the triglycerides in the vegetable oil. ** : The yield of lignin oil corresponds to the mass of the products obtained from the lignin oil divided by the maximum theoretical mass of compounds that can be obtained from the lignin oil. The maximum theoretical mass is the mass of the lignin oil minus the mass of the oxygens and O-methyl groups in the lignin oil.

[0254] ***: The carbon yield of vegetable oil corresponds to the mass of the products obtained from the vegetable oil divided by the maximum theoretical mass of compounds that can be obtained from the vegetable oil. The maximum theoretical mass is the mass of the vegetable oil minus the mass of the oxygens and the glyceryl fraction of the triglycerides in the vegetable oil.

[0255] Example 4: Comparison with the hydrotreatment of a mixture devoid of effluent intended for hydrotreatment

[0256] The results of Ni-P hydrodeoxygenation, as presented in Example 3 above, are compared with the results of hydrodeoxygenation under the same conditions of a treatment mixture consisting solely of lignin oil (13% by mass) and dodecane. This mixture therefore contains no vegetable oil.

[0257] The results are presented in Table 6 below.

[0258] [Table 6]

[0259] ** and ***: see above. These results demonstrate that, for a comparable lignin oil content in the mixture to be treated, the lignin oil is converted with a much higher yield when co-hydrodeoxygenated with vegetable oil. Furthermore, the C9-C18 compound content is greater.

Claims

DEMANDS 1. Process for preparing a mixture of hydrocarbons, comprising a step of hydrotreating a mixture to be treated, the mixture to be treated comprising a) a mixture of phenolic compounds, and b) an effluent intended to be hydrotreated and optionally c) a diluent.

2. A process according to claim 1, wherein the mixture to be treated has, in relation to the total mass of the mixture to be treated, a mass content of oxygen atoms less than or equal to 20% by mass, preferably less than or equal to 15% by mass, preferably less than or equal to 12% by mass, preferably less than or equal to 10% by mass, preferably less than or equal to 8% by mass, preferably less than or equal to 7% by mass, preferably less than or equal to 6% by mass, preferably less than or equal to 5% by mass.

3. A process according to claim 1 or 2, wherein the hydrotreating step is carried out in the presence of a catalyst comprising nickel, cobalt, molybdenum, tungsten or mixtures thereof, preferably comprising oxides, sulfides or phosphides of nickel, cobalt, molybdenum, tungsten or mixtures thereof, preferably supported on a support having at least a specific surface area of ​​75 m² 2 / g and preferably being selected from silica, alumina, titanium oxide, zirconium oxide, carbon, cerium oxide, silicon carbide, silica-alumina, silica-alumina-titanium, phosphated alumina or silica-alumina-phosphate, sulfated zirconia, tungsten zirconia, a zeolite or mixtures thereof.

4. A process according to any one of the preceding claims, wherein the mass of oxygen atoms in carboxylic and carbonyl form of the mixture of phenolic compounds is less than or equal to 20% of the total mass of oxygen atoms present in the mixture of phenolic compounds, preferably less than or equal to 10%, preferably less than or equal to 5% and even more preferably less than or equal to 2%.

5. A process according to any one of the preceding claims, wherein the mixture of phenolic compounds a) comprises at least one mixture of compounds of the following formula (I): in which each and R2 is independently chosen from -O-CH3 and H, and each R3 is independently chosen from H, a methyl, an ethyl, a propyl, a propenyl, a 1-alkoxypropyl and a 3-hydroxypropyl.

6. A process according to any one of the preceding claims, wherein the mixture of phenolic compounds (a) is a lignin oil, preferably having a viscosity at 25 °C less than or equal to 25 Pa.s, preferably obtained from a catalytic reduction fractionation process of lignocellulosic biomass, and preferably exhibiting: - an average molecular mass between 200 and 950 g / mol, preferably between 350 and 830 g / mol, and / or - an average number of carbon atoms between 20 and 60, preferably between 25 and 50, preferably between 30 and 45, preferably between 35 and 40.

7. A process according to any one of the preceding claims, wherein the mass content of the mixture of phenolic compounds in the mixture to be treated ranges from 1% to 30%, preferably from 2% to 25%, preferably from 3% to 20%, preferably from 4% to 15%, preferably from 5% to 10% by mass relative to the total mass of the mixture to be treated.

8. A process according to any one of the preceding claims, wherein the mixture to be treated further comprises a hydrocarbon diluent having an oxygen atom content of less than or equal to 5% by mass relative to the total mass of the diluent, preferably less than or equal to 1% by mass, preferably less than or equal to 0.5% by mass, preferably the hydrocarbon diluent is totally free of oxygen atoms.

9. A process according to any one of the preceding claims, wherein the effluent to be hydrotreated b) is a petroleum cut from a step of a petroleum refining process.

10. A process according to any one of claims 1 to 8, wherein the effluent to be hydrotreated (b) comprises one or more C12-C24 fatty acid esters and / or one or more C12-C24 fatty acids, and the hydrotreatment step is a hydrodeoxygenation step, and preferably the mass ratio between the mass content of the mixture of phenolic compounds and the total mass content of C12-C24 fatty acid ester and C12-C24 fatty acid, ranges from 0.2 to 5, preferably from 0.3 to 3, preferably from 0.5 to 2, preferably from 0.7 to 1.5, preferably from 0.8 to 1, preferably from 0.85 to 0.95, the mass contents being defined in relation to the total mass of the mixture to be treated.

11. A process according to any one of the preceding claims, wherein the hydrotreating step is carried out at a temperature less than or equal to 380°C and / or under a partial pressure of dihydrogen greater than or equal to 1.10 5 Pa.

12. A process according to any one of the preceding claims, further comprising a step of fractionating the hydrocarbon mixture, to produce in particular a jet fuel.

13. Hydrocarbon mixture obtained by the process according to any one of claims 1 to 11, comprising from 50% to 99% by mass of C9-C18 compounds relative to the total mass of the hydrocarbon mixture, preferably comprising less than 10% by mass, preferably less than 8% by mass, preferably less than 5% by mass, preferably less than 1% by mass, preferably less than 0.5% by mass of oxygen atoms relative to the total mass of the hydrocarbon mixture.

14. Jet fuel obtained by the process according to claim 12, preferably comprising less than 1% by mass, preferably less than 0.5% by mass of oxygen atoms relative to the total mass of the jet fuel.

15. Use of jet fuel according to claim 14, (i) in a mixture with jet fuel resulting from the distillation of petroleum, or (ii) in a mixture with a synthetic jet fuel, to power at least one aircraft engine.

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