PROCESS FOR PRODUCING JET FUEL FROM FEEDSTOCKS OF RENEWABLE ORIGIN

Abstract

PROCESS FOR PRODUCING A JET FUEL FROM FEEDSTOCKS OF RENEWABLE ORIGIN The invention relates to a process for producing a jet fuel comprising at least the steps of: a) providing fatty acid ethyl esters from the reaction of animal fats and / or waste oils with methanol in a transesterification reactor, b) providing hydrocarbons of fossil origin, c) preparing a hydrocarbon feedstock containing the hydrocarbons of fossil origin provided by step b) and the fatty acid ethyl esters provided by step a) in a content of at most 5% by volume relative to the hydrocarbon feedstock, d) subjecting the hydrocarbon feedstock prepared in step c) to hydrotreatment and obtaining a treated hydrocarbon feedstock, e) fractionating the treated hydrocarbon feedstock obtained in step d) and recovering a kerosene fraction as jet fuel. Figure 1

Description

Title of the invention: METHOD FOR MANUFACTURING A JET FUEL FROM RE ORIGINAL FEEDSTOCKS NEW Technical field

[0001] The present invention relates to the technical field of refining petroleum feedstocks of fossil origin and feedstocks of biological origin, in particular for the manufacture of jet fuel. More particularly, the invention relates to a method for obtaining a jet fuel having a component of biological (or renewable) origin. Background to the invention

[0002] Conventional jet fuels, also known as "jet fuel", "jet fuel" or "kerosene", are produced from crude oil and contain a complex mixture of hydrocarbons that typically have 6 to 18 carbon atoms. These hydrocarbons include linear and branched alkanes, cycloalkanes and aromatic hydrocarbons. The cut points of the jet fuel fraction typically vary between 140°C and 240°C.

[0003] A commercial jet fuel is typically obtained by blending different fuel bases. These fuel bases may be crude oil distillation cuts, possibly hydrotreated or sometimes subjected to a sweetening treatment (MEROX process for example). These bases may also be cuts from a hydrocracker effluent or an effluent from a catalytic cracker (often after hydrotreatment). Other fuel bases may be prepared by other routes such as Fischer Tropsch synthesis followed by a cracking step. The choice of fuel bases and their relative proportions are made so that the final properties of the blend meet the desired specifications.

[0004] Due to the scarcity of fossil resources and increasing environmental concerns, the use of molecules derived from biomass is increasingly sought to replace molecules of fossil origin. However, the preparation of jet fuel from molecules derived from biomass that can be directly used in the formulation of jet fuel constitutes a real economic and environmental challenge. In particular, certain countries such as France are implementing incentive taxes relating to the incorporation of renewable energy in transport and in particular for the aviation sector. Prior art

[0005] A solution for obtaining jet fuel with an original component Biological jet fuel production consists of mixing a conventional jet with a paraffinic base from renewable feedstocks as provided for by the D7566-21 standard, thus enabling the production of alternative aviation fuels. The bases for aviation fuel from renewable feedstocks that can be incorporated into fossil jet fuels are: • Synthetic paraffinic kerosenes [SPK], produced by processes such as the Fischer-Tropsch process, the hydrotreatment of esters and fatty acids [HEFA-SPK] or produced by the Alcohol-to-jet route (transformation of alcohol into kerosene) [ATJ-SPK], • Synthetic isoparaffins produced by hydrotreatment from fermented sugars [SIP-HFS], • Synthetic aromatic kerosenes obtained by alkylation of light aromatics from non-petroleum sources [SPK / A], • Synthetic kerosenes obtained from the hydrothermal conversion of fatty acid esters and fatty acids, • Synthetic paraffinic kerosenes [SPK] obtained from hydrocarbons, esters and hydrotreated fatty acids.

[0006] This solution, however, requires specific processing installations to produce the paraffinic bases which will be mixed with the conventional jet.

[0007] Another solution consists of co-processing a hydrocarbon of fossil origin with a feedstock of renewable origin, as provided in particular in the ASTM D1655-21C standard.

[0008] Thus, document EP2346962 describes a process for obtaining a kerosene cut, a portion of which is of biological origin. For this purpose, a feedstock of petroleum origin mixed with a feedstock of biological origin is subjected to a hydrotreatment step, then fractionated in order to recover a kerosene cut. The feedstock of biological origin used is an animal oil and / or fat, or a mixture of these oils / fats. The oils and / or fats used are not transesterified.

[0009] Document EP2533895 describes a specific catalyst for producing biodiesel. It describes in particular the use of this catalyst for treating a feedstock which is a mixture of a hydrocarbon of fossil origin (kerosene, diesel, etc.) and a biomass chosen from vegetable or animal oils and fats. The oils and / or fats used are not transesterified. The production of jet is not mentioned.

[0010] Furthermore, document EP3813539 describes a process for producing a purified biodiesel from renewable raw materials (such as fats and oils) containing unsaponifiable matter. The process comprises esterifying vegetable oils or fats to obtain a crude biodiesel which is then subjected to distillation to produce a purified biodiesel and a distillation bottoms. This The latter contains more than 2% by mass of unsaponifiables as well as soaps, phospholipids, proteins, colored compounds, sulfur compounds, high-boiling compounds containing acidic or basic groups, and mono-, di- and triglycerides. This distillation bottoms is then diluted with a fossil-based feedstock of the middle distillate type, before being subjected to a hydrodeoxygenation step in order to produce diesel-type hydrocarbons. Jet production is not mentioned.

[0011] Among the feedstocks of renewable origin available today, feedstocks having the status of animal by-products within the meaning of European Regulation 1069 / 2009 and its implementing acts (EU) 142 / 2011, such as animal fats or used cooking oils (also designated by the acronym UCO for "Used Cooking Oil" in English), are interesting in order to limit the environmental impact of the fuel produced. These feedstocks are however subject to restrictive health regulations. The use of these feedstocks entails traceability constraints and health controls associated in particular with the management of aqueous effluents. Furthermore, the use of these feedstocks having the status of animal by-products requires compliance with the time / temperature and pressure conditions as recommended in European Regulation 1069 / 2009, these conditions not being met by a hydrotreatment step alone.There is therefore a need for a process for manufacturing jet fuel by co-treatment in a hydrotreatment unit, in particular from feedstocks of renewable origin having the status of animal by-products, which makes it possible to overcome the aforementioned problems. Description of the invention

[0012] The invention provides a method for manufacturing a jet fuel comprising at least the steps of:

[0013] a) providing ethyl esters of fatty acids from the reaction of animal fats and / or used oils with ethanol in a transesterification reactor,

[0014] b) supply hydrocarbons of fossil origin,

[0015] c) preparing a hydrocarbon feedstock containing the hydrocarbons of fossil origin provided by step b) and the fatty acid ethyl esters provided by step a) in a content of at most 5% vol relative to the hydrocarbon feedstock,

[0016] d) subjecting the hydrocarbon feedstock prepared during step c) to hydrotreatment and obtaining a treated hydrocarbon feedstock,

[0017] e) fractionating the treated hydrocarbon feedstock obtained in step d) and recovering a kerosene fraction as jet fuel, said kerosene fraction preferably having a final boiling point of less than 300°C, measured in particular according to standard ASTM D86-12.

[0018] The process according to the invention thus makes it possible to obtain an aviation fuel, part of which is of renewable origin, this type of fuel also being called S AF for “Sustainable Aviation Fuel” in English.

[0019] In particular, the method according to the invention can be implemented in existing hydrotreatment units. Detailed description of the invention

[0020] The terms "comprising" and "comprises" as used herein are synonymous with "including," "includes," or "contains," "containing," and are inclusive or unbounded and do not exclude additional features, elements, or method steps not specified.

[0021] The expressions % by weight and % by mass have an equivalent meaning and refer to the proportion of the mass of a product relative to 100g of a composition comprising it.

[0022] Boiling points as mentioned herein are measured at atmospheric pressure, unless otherwise stated. An initial boiling point is defined as the temperature value from which a first vapor bubble is formed. A final boiling point is the highest temperature achievable during a distillation. At this temperature, no more vapor can be transported to a condenser. The determination of the initial and final points uses techniques known in the art and several methods adapted according to the distillation temperature range are applicable, for example NF EN 15199-1 (2020 version) or ASTM D2887-19 for the measurement of boiling points of petroleum fractions by gas chromatography, ASTM D7169-05 for heavy hydrocarbons, ASTM D7500-15(2019), D86-12 or DI 160-18 for distillates. Animal fats and used oils

[0023] The animal fats and used cooking oils from which the ethyl esters used in the present invention are derived are advantageously animal fats and used cooking oils having the status of animal by-products, in particular within the meaning of Regulation (EC) No. 1069 / 2009 of the European Parliament and of the Council of 21 October 2009 and Regulation (EU) No. 142 / 2011 of the Commission (implementing regulation of Regulation EC No. 1069 / 2009).

[0024] Animal fats having the status of animal by-product are fatty residues of animal origin, other than used cooking oils, originating for example from food industries or rendering plants.

[0025] Used cooking oils with the status of animal by-products are used cooking oils (used cooking oils or UCO), namely residues of fatty substances of vegetable or animal origin used for human consumption, in the food industry, in collective or commercial catering. Step a)

[0026] The fatty acid ethyl esters provided in step a) are derived from the reaction of animal fats and / or used oils with ethanol in a transesterification reactor.

[0027] In particular, this step a) may thus comprise, or consist of, a step of transesterification of animal fats and / or used oils with ethanol to obtain ethyl esters of the fatty acids initially contained in the animal fats and / or used oils, and glycerin, followed by a step of separation by distillation, decantation or centrifugation of the ethyl esters produced.

[0028] During the transesterification step, the triglycerides contained in animal fats and / or used cooking oils react with ethanol to obtain ethyl esters of fatty acids in a transesterification reactor. This reaction, well known to those skilled in the art, is usually carried out in the presence of a catalyst, by an acid or basic, homogeneous or heterogeneous catalysis process, typically at a temperature of 25°C to 110°C or 35°C to 90°C and a reaction time of 30 minutes to 50 hours. For example, a catalyst / oil mass ratio of 0.25 to 8% and an ethanol / oil molar ratio of 3:1 to 15:1 may be used.

[0029] This reaction is for example carried out in the presence of acid catalysts (hydrochloric acid, sulfuric acid, sulfonic acid, boron trifloride, zinc chloride, acid ion exchangers, aluminum trioxide, iron trioxide, etc.) or in the presence of basic catalysts such as alkali metal alcoholates and hydroxides as well as sodium or potassium carbonates (sodium hydroxide, potassium hydroxide, sodium ethanolate, potassium ethanolate, etc.).

[0030] The fatty acid ethyl esters used in the present invention are therefore free from impurities such as unsaponifiable compounds, soaps, or other compounds originating from animal fats or used oils used as raw material. In particular, their unsaponifiable content is less than or equal to 1% m / m (measured according to ISO 3596:2001 standard).

[0031] Advantageously, in particular when they are produced from animal fats and / or used cooking oils which are animal by-products, the fatty acid ethyl esters provided in step a) may comprise at least one of the following characteristics: - at least 9%m, typically from 9%m to 64%m, of ethyl esters of fatty acids whose carbon chain contains from 12 to 16 carbon atoms, - at least 25%m, typically from 30%m to 98%m, of ethyl esters of fatty acids whose carbon chain contains 18 carbon atoms, - at most 4%m, typically from 0%m to 2%m, of fatty acid ethyl esters

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[0041] whose carbon chain contains 20 to 22 carbon atoms. Where such esters are produced from animal by-products which are animal fats, the fatty acid ethyl esters provided in step a) may comprise at least one of the following characteristics: - at least 20%m, typically from 20%m to 64%m, - ethyl esters of fatty acids whose carbon chain contains 12 to 16 carbon atoms, - at least 25%m, typically from 25%m to 65%m, of ethyl esters of fatty acids whose carbon chain contains 18 carbon atoms, - at most 4%m, typically from 0%m to 2%m, of ethyl esters of fatty acids whose carbon chain contains 20 carbon atoms, - at most 1%m, typically from 0%m to 1%m, of ethyl esters of fatty acids whose carbon chain contains 22 carbon atoms. Preferably, the content of ethyl esters of fatty acids whose carbon chain contains 20 to 22 carbon atoms will be as low as possible, preferably zero, in order to improve the cold properties and in particular the freezing point. Step a) of supplying fatty acid ethyl esters may in particular comprise (i) obtaining ethanol of renewable origin, (ii) followed by the reaction of animal fats and / or used oils with the ethanol obtained in step (i) in a transesterification reactor. Renewable ethanol means ethanol obtained from biomass and / or by fermentation. A. Obtaining ethanol from renewable sources by fermentation In one embodiment, ethanol may be obtained by ethanolic fermentation in a bioreactor containing a culture of one or more microorganisms. Ethanol of renewable origin can then advantageously be obtained by: - ​​aerobic fermentation of a substrate rich in sugars and / or starch from biomass, or - anaerobic fermentation of a gas containing CO, which may or may not come from biomass. Aerobic fermentation Ethanol can thus be produced by aerobic fermentation of a substrate rich in sugars and / or starch from biomass. This substrate may, for example, comprise, or originate from, sugar cane, sugar beet, sugar sorghum, corn, wheat, barley, rye, sorghum, triticale, potato, sweet potato, cassava, and / or lignocellulosic biomass. The sugar-rich substrate can also be derived from lignocellullosic biomass by a treatment comprising (i) a step of separating the lignin, cellulose and hemicellulose contained in the lignocellullosic biomass, followed by (ii) a step of converting the cellulose and / or hemicellulose into sugars.

[0042] Obtaining this type of substrate from lignocellulosic biomass is well known to those skilled in the art. Lignocellulosic biomass consists essentially of cellulose, hemicellulose and lignin. This biomass comes from agricultural and forestry residues or by-products of wood or crop processing, whether woody plants or herbaceous plants. This lignocellulosic biomass can also include distiller's grains and allow the production of ethanol as described in document EP2675778.

[0043] The first step (i) is a pretreatment step which allows the lignocellulosic matrix to be detached and the cellulose and hemicellulose to be released from the complex formed with the lignin by means of one or more pretreatments. Pretreatments known are steam pretreatment (or steam explosion), hot water pretreatment (hydrothermal), ammonia explosion (AFEX), acid pretreatment or alkaline pretreatment. The steam explosion treatment consists of treating the biomass, preferably previously shredded or ground, with high-pressure saturated steam at temperatures of about 160 to 240°C and pressures of 0.7 to 4.8 MPa. The efficiency of the steam treatment can be improved by adding H2SO4, CO2 or SO2 as a catalyst.In AFEX pretreatment, the biomass is contacted with anhydrous liquid ammonia feed in a ratio of 1 / 1 to 2 / 1 (1 to 2 kg of ammonia / kg of dry biomass) for 10 to 60 min at 60-90°C and pressures above 3 MPa. Hydrothermal pretreatment is similar to steam explosion, but uses liquid water at elevated temperatures instead of steam. In acid pretreatment, typically in the presence of dilute acid, an aqueous suspension of the cellulosic substrate is heated to the desired temperature and pretreated with preheated sulfuric acid (concentrations <4% by mass) in a stainless steel reactor, the treatment is carried out at a temperature of 140 to 215°C. Residence time varies from a few seconds to a few minutes depending on the treatment temperature.Lime pretreatment is an inexpensive physicochemical alkaline treatment that improves the digestibility of cellulosic biomass. Using 0.1g of Ca(OH)2 / g of biomass, the treatment can be carried out over a wide temperature range from 25 to 130°C. The Organosolv process which is a process for the delignification and / or saccharification of cellulosic materials and plant crops can also be used. In general, the Organosolv process involves the use of a mixture of water and a solvent such as alcohols or ketones and sometimes other solvents of a non-polar nature, along with an acidic compound to facilitate hydrolysis. A . A method of this type is described for example in document US4470851A.

[0044] Step (ii) is a step of converting cellulose and / or hemicellulose into sugars. It is also well known to those skilled in the art. It is typically a hydrolysis which can be catalyzed by acid or by enzymes such as cellulases, for example the strain Trichoderma reesei, xylanases, xylosidases and arabinofuranosidases.

[0045] The substrate rich in sugars and / or starch is then subjected to fermentation.

[0046] By way of example, this fermentation can be carried out using specialized microorganisms, and in particular yeasts, which make it possible to optimize the profitability of the production process, in particular the following yeasts: Ethanol Red® (Fermentie), Thermosacc® (Lallemand)), Angel Super Alcohol® (Angel®) and Fali® (AB Mauric)), the Saccharomyces cerevisiae yeast strains described in document FR3015985, the Candida Shehatae or Pichia stipitis yeast strains, or any other suitable microorganism. Anaerobic fermentation

[0047] Ethanol may also be produced by anaerobic fermentation of a gas comprising CO. The substrate is then a gaseous substrate (a gas) containing CO. This gaseous substrate may be a by-product of an industrial process or automobile exhaust gases. In some embodiments, the industrial process is selected from the group consisting of the manufacture of ferrous metal products, including steel mills, the manufacture of non-ferrous products, petroleum refining processes, coal gasification, electric power production, carbon black production, ammonia production, methanol production, coke production and methane reforming. In these embodiments, the gaseous substrate may be captured from the industrial process before it is emitted into the atmosphere, using any suitable method.Depending on the composition of the gas thus captured, it may also be desirable to treat it to remove any unwanted impurities, such as dust particles, before introducing it into the fermentation. For example, the gas may be filtered or purified by known methods.

[0048] In other embodiments of the invention, the gaseous substrate may be derived from the gasification of biomass. The gasification process involves partial combustion of the biomass in a restricted supply of air or oxygen. The resulting gas generally comprises primarily CO and H2, with minimal volumes of CO2, methane, ethylene, and ethane. For example, biomass byproducts obtained during the extraction and processing of food products, such as sugar from sugarcane or starch from corn or grains, or non-food biomass waste generated by the forestry industry, may be gasified to produce a CO-containing gas that may be used in the present invention.

[0049] The gaseous substrate used typically has a significant proportion of CO. The CO content of the gaseous substrate is typically 15% to 100% by volume, 15% to 95% by volume, 40% to 95% by volume, 40% to 60% by volume, and 45% to 55% by volume or is in any range defined by two of these limits. Advantageously, the CO-containing gas may comprise 25%, 30%, 35%, 40%, 45%, 50%, 55% or 60% CO by volume. Gases having lower CO contents, such as 6% by volume, may also be suitable, particularly when H2 and CO2 are also present.

[0050] The gaseous substrate need not contain hydrogen, but this is not considered detrimental to ethanol production. The gaseous substrate may also contain CO2, for example, in a proportion of 1% to 80% by volume, or 1% to 30% by volume, or 5% to 10% by volume, or in any range defined by two of these limits.

[0051] Typically, carbon monoxide will be added to the fermentation reaction in a gaseous state, or alternatively in a liquid state. For example, carbon monoxide may be provided in a liquid. For example, a liquid may be saturated with a gas containing carbon monoxide, and then this liquid may be added to a bioreactor. This may be accomplished using standard methodology. For example, a microbubble dispersion generator (Hensirisak et. al. Scale-up of microbubble dispersion generator for aerobic fermentation; Applied Biochemistry and Biotechnolo RV Volume 101, Number 3 / October, 2002) could be used.

[0052] Furthermore, it is often desirable to increase the CO concentration of the gas (or the partial pressure of CO in the gas) and thereby increase the efficiency of fermentation reactions using CO as a substrate. Increasing the partial pressure of CO in the gas increases the mass transfer of CO into a fermentation medium. The composition of the gas streams used to feed a fermentation reaction can have a significant impact on the efficiency and / or costs of that reaction. For example, O2 can reduce the efficiency of an anaerobic fermentation process. Processing unwanted or unnecessary gases in the steps of a fermentation process before or after fermentation can increase the load on those steps (e.g., when the gas stream is compressed before entering a bioreactor, unnecessary energy may be used to compress gases that are not needed for fermentation).Therefore, it may be desirable to treat substrate streams, particularly substrate streams derived from industrial sources, to remove undesirable components and increase the concentration of desirable components.

[0053] Any microorganism capable of fermenting a gaseous substrate comprising CO to produce ethanol may be used in the present invention. For example, microorganisms of the genus Moorella, Clostridia, Ruminococcus, Aceto- bacterium, Eubacterium, Butyribacterium, Oxobacter, Methanosarcina, Metha-nosarcina, and Desulfotomaculum can be used.

[0054] By way of example, use may be made of the microorganism(s) of the genus Clostridium, including strains of Clostridium ljungdahlii, Clostridium carboxydivorans, Clostridium ragsdalei and Clostridium autoethanogenum, of the genus Moorella, including Moorella sp HUC22-1, of the genus Carboxydothermus, Moorella thermoacetica, Moorella thermoautotrophica, Ruminococcus productus, Acetobacterium woodii, Eubacterium limosum, Butyribacterium methylotrophicum, Oxobacter pfennigii, Methanosarcina barkeri, Methanosarcina acetivorans, or Desulfotomaculum kuznetsovii. Other specific examples of microorganisms are anaerobic carboxydotrophic bacteria. Examples of usable strains are described in document WO201226833.

[0055] It should be noted that the invention can be applied to a mixed culture of two or more microorganisms. Fermentation medium and conditions

[0056] Regardless of the nature of the substrate (gaseous or not) used, for ethanol fermentation to occur by growth of one or more microorganisms, a suitable nutrient medium will need to be introduced into the bioreactor in addition to a substrate, under appropriate conditions. A nutrient medium will contain components, such as vitamins and minerals, sufficient to allow the growth of the microorganism used. Reaction conditions to be considered are temperature, flow rate of the medium, pH, redox potential of the medium, stirring rate (if using a continuously stirred reactor), inoculum level, maximum substrate concentrations and rates of introduction of the substrate into the bioreactor to ensure that the substrate level does not become limiting, and maximum product concentrations to avoid product inhibition.The optimal reaction conditions will depend in part on the particular microorganism used. Methods for culturing microorganisms are known in the art and those skilled in the art know how to optimize the culture conditions for each microorganism, depending on its nature. Examples of fermentation conditions suitable for the anaerobic fermentation of a substrate comprising CO are detailed in WO2007 / 117157, WO2008 / 115080, WO2009 / 022925 and WO02 / 08438. Bioreactor

[0057] The fermentation reactions may be carried out in any suitable bioreactor. In some embodiments of the invention, the bioreactor may comprise a first growth reactor in which the microorganisms are cultured, and a second fermentation reactor, in which the broth from the growth reactor is introduced and in which most of the fermentation product (ethanol, for example) is produced. Recovery of the fermentation product

[0058] The fermentation will result in a fermentation broth comprising a desirable product (ethanol) and / or one or more by-products (such as acetate and butyrate when the substrate is a CO containing gas) as well as microorganism cells, in a nutrient medium.

[0059] The recovery of ethanol may include continuously removing a portion of the broth and recovering ethanol from the removed portion of the broth.

[0060] For example, the removed portion of the ethanol-containing broth may be passed through a separation unit to separate, for example by filtration, the bacterial cells from the broth and produce a cell-free ethanol-containing permeate, and the microorganism cells may be returned to the bioreactor. The cell-free ethanol-containing permeate may then be used for the subsequent transesterification reaction.

[0061] In some embodiments, recovering ethanol and / or one or more other products or by-products produced in the fermentation reaction comprises continuously removing a portion of the broth and separately recovering the ethanol and one or more other products from the removed portion of the broth.

[0062] For example, ethanol may be recovered from the fermentation broth using methods such as filtration, distillation or fractional evaporation, pervaporation, and extractive fermentation. Distillation of ethanol from a fermentation broth yields an azeotropic mixture of ethanol and water (i.e., 95% ethanol and 5% water). Anhydrous ethanol may then be obtained by the use of molecular sieve ethanol dehydration technology, which is also well known in the art.

[0063] Extractive fermentation procedures involve the use of a water-miscible solvent that poses a low risk of toxicity to the fermentation organism, in order to recover ethanol from the diluted fermentation broth. For example, oleyl alcohol is a solvent that can be used in this type of extraction process. The oleyl alcohol is continuously introduced into a fermenter, whereupon this solvent rises to form a layer at the top of the fermenter which is continuously extracted and passed through a centrifuge. The water and cells are then easily separated from the oleyl alcohol and returned to the bioreactor, while the ethanol-laden solvent is introduced into a rapid vaporization unit. Most of the ethanol is vaporized and condensed, while the oleyl alcohol is non-volatile and is recovered for reuse in the fermentation.

[0064] B. Obtaining ethanol of renewable origin from biomass

[0065] Ethanol of renewable origin can also be obtained from biomass by converting a synthesis gas rich in CO / H2, this synthetic gas being derived from biomass.

[0066] The biomass can for example be gasified to produce a synthesis gas (or "syngas" in English) rich in CO / H2, this synthetic gas then being converted into methanol in the presence of a catalyst. A process of this type is for example described in document WO2012003901.

[0067] Synthesis gas suitable for subsequent conversion to ethanol can also be obtained by pyrolysis of biomass.

[0068] Biomass used to produce syngas may include, but is not limited to, wood fuels from natural forests and woodlands (e.g., sawdust), agricultural residues (e.g., rice hulls, straw manure), energy crops that are grown exclusively for energy production (e.g., corn and oil palm), municipal waste (e.g., wood waste, rice, straw manure), energy crops that are grown exclusively for energy production (e.g., corn and oil palm), municipal waste (e.g., municipal solid waste and wastewater), and waste-derived biomass fuel (e.g., wood pellets). Step b)

[0069] The fossil hydrocarbons usable in the present invention can be chosen from kerosene cuts.

[0070] A kerosene cut of fossil origin has boiling points ranging from 130°C to 300°C. It typically has an initial boiling point according to ASTM D86-12 of 130 to 160°C and a final boiling point according to ASTM D86-12 of 220°C to 300°C. These kerosene cuts can be:

[0071] - a kerosene cut from the direct distillation of crude oil,

[0072] - a kerosene cut from different conversion processes such as cracking catalytic, hydrocracking and / or visbreaking.

[0073] In the context of hydrotreatment, the hydrocarbons of fossil origin are advantageously a kerosene cut or a mixture of kerosene cuts, preferably originating from the direct distillation of crude oil or from hydrocracking. Step c)

[0074] The hydrocarbon feedstock prepared in step c) contains the hydrocarbons of fossil origin provided by step b) and the ethyl esters of fatty acids provided by step a) in a content of at most 5% vol relative to the hydrocarbon feedstock.

[0075] Advantageously, the content of fatty acid ethyl esters in the hydrocharge carbonaceous may be from 0.1% by volume to 1% by volume, preferably from 0.1% by volume to 0.9% by volume, or from 0.1% to 0.6% by volume, more preferably from 0.1% to 0.5% by volume, or in any included range defined by two of these limits.

[0076] This preparation step can be carried out by simple mixing of the constituents of the hydrocarbon feedstock supplied in steps a) and b), in particular upstream of the hydrotreatment step of step d), or during step d).

[0077] It will thus be possible to provide for mixing the constituents of the hydrocarbon feedstock supplied in steps a) and b) upstream of a hydrotreatment reactor in which step d) is carried out, or inside this reactor. Step d)

[0078] Step d) of hydrotreatment of the hydrocarbon feedstock can be carried out in one or more reactors. Any type of reactor normally used for this type of reaction can be used, for example a fixed bed reactor, an ebullated bed reactor, a slurry reactor, etc., preferably a fixed bed reactor.

[0079] In particular, it will be possible to use a reactor of the type usually used for the hydrotreatment of hydrocarbons of fossil origin.

[0080] Advantageously, step d) is carried out under a pressure of 15 to 130 bars and at a temperature of 250 to 380°C, preferably 280 to 340°C, in the presence of a hydrotreatment catalyst and dihydrogen.

[0081] Typically, a liquid hourly space velocity (WH in French, LHSV in English - Liquid Hourly Space Velocity) may be provided: from 0.2 to 9 hr1, preferably 0.5 to 7, and more preferably 0.8 to 1.8, and a dihydrogen ratio: 50 to 1500 Nm3 / m3 of charge, preferably 120 to 250 Nm3 / m3 and more preferably 120 to 200 Nm3 / m3.

[0082] Step d) is typically carried out in a fixed bed reactor, comprising one or more catalyst beds.

[0083] More specifically, step d) can be carried out under a pressure of 15 to 50 bars and at a temperature of 280°C to 340°C, in the presence of a hydrotreatment catalyst and dihydrogen, typically with a dihydrogen content of 120 to 180 Nm3 / m3 of charge. Typically, a liquid hourly space velocity of 1 to 1.6 h1 can be expected.

[0084] The hydrotreatment catalyst is a conventional hydrotreatment catalyst. Conventional hydrotreatment catalysts include in particular an active metal compound such as nickel, platinum, palladium, rhenium, rhodium, nickel tungstate, nickel molybdenate, molybdenum, cobalt molybdenate, nickel molybdenate, this metal compound being able to be deposited or not on a support. This support can generally include oxides such as silicas, aluminas, alumino-silicates (in particular zeolites), titanium oxides, or still carbon, molecular sieves, salts or alkaline earth metals. When a support is present, it advantageously has a specific surface area varying from 100 to 250 m2 / g, preferably from 150 to 200 m2 / g.

[0085] Advantageously, the catalyst comprises at least two metals from groups 6, 9, 10, 11 of the periodic table of elements, preferably at least two metals such as NiMo, CoMo, or CoNiMo, preferably on an alumina support.

[0086] When supported, conventional hydrotreating catalysts typically comprise a metal content of 0.01 to 25% by weight relative to the total mass of the catalyst, preferably 15 to 20% by weight, for example 20% by weight relative to the total mass of the catalyst.

[0087] In a preferred embodiment, the catalyst used does not have an isomerizing function or has negligible isomerizing activity under the reaction conditions. In other words, the catalyst does not promote the isomerization of the hydrocarbon compounds present in the feedstock. When a support is present, it is preferably slightly acidic or not at all acidic.

[0088] Thus, a catalyst not having an isomerizing function may comprise at least one metal from groups 6, 9, 10, 11 of the periodic table of elements, optionally on a support chosen from alumina, silica alumina, phosphated alumina, borated alumina, phosphated silica alumina, alone or as a mixture.

[0089] The hydrotreatment step d) produces an effluent containing a liquid fraction containing the kerosene fraction, and a gaseous fraction. Step e)

[0090] The hydrotreated feed obtained at the outlet of step d) undergoes fractionation. This fractionation can be carried out by distillation or stripping, in particular by adding a separation column, for example a distillation column, or even a stripping column.

[0091] After the hydrotreatment step, the effluent leaving the reactor is fractionated, typically by stripping, in order to recover a kerosene cut. This fractionation can be carried out so that the kerosene cut forms a jet fuel, in particular meeting the desired specifications.

[0092] The recovered kerosene fraction has a final boiling point less than or equal to 300°C, notably measured according to the ASTM D86-12 standard.

[0093] The initial boiling point according to ASTM D86-12 may be 120 to 185°C. The final boiling point according to ASTM D86-12 may be 220 to 300°C.

[0094] The recovered kerosene fraction advantageously has one or more of the following properties: - a kinematic viscosity at -20°C of 1.2 to 8.0 mm2 / s (NF EN ISO 3104-August 1996), - a density at 15°C of 775 to 840 kg / m3 (ASTM D4052-18 or IP 365), - a freezing point of at most -47°C (ASTM D5972-16 or IP435), - a flash point of at least 38°C (IP170-21 or ASTM D56-21A).

[0095] In particular, the cutting points of the recovered kerosene fraction may be adapted in order to obtain a kerosene fraction meeting the desired specifications, for example those of an Al jet according to standard ASTM D1655-21, in particular at least with regard to the final distillation point and / or the freezing point and / or the flash point.

[0096] The fractionation step also makes it possible to recover the gas produced, in particular methane, during the hydrotreatment step. Description of figures

[0097] [Fig. 1]: simplified diagram of a hydrotreatment unit allowing the implementation of the process according to one embodiment of the invention.

[0098] [Fig.l] represents a simplified diagram of a hydrotreatment unit 1 making it possible to implement the process according to the invention.

[0099] This unit 1 comprises a reactor 2 into which the feedstock to be treated is introduced by means of a line 3. This reactor contains one or more beds of hydrotreatment catalysts.

[0100] The feedstock (C), in the present invention, is a mixture of a kerosene feedstock of fossil origin and ethyl esters of fatty acids of renewable origin.

[0101] A line 4 recovers the effluent at the outlet of reactor 2 and leads it to a separation section 5.

[0102] A heat exchanger 6 is placed downstream of the reactor on line 4 in order to heat the load circulating in line 3, upstream of the reactor.

[0103] Upstream of this heat exchanger 6, a line 7, connected to line 3, provides to the charge to treat a gas rich in H2.

[0104] Downstream of the heat exchanger 6, and upstream of the reactor 2, the charge mixed with the H2-rich gas circulating in the line 3 is heated by a furnace 8.

[0105] Thus, the feedstock is mixed with the hydrogen-rich gas, then brought to the reaction temperature by the heat exchanger 6 and the furnace 8 before entering the reactor 2. It then passes into the reactor 2.

[0106] At the outlet of the reactor, the mixture obtained is cooled, then separated in the separation section 5, for example by stripping, which makes it possible to obtain:

[0107] - a gaseous fraction (G), containing in particular water from stripping, gaseous hydrocarbons, an acid gas rich in H2S, part of which is reinjected into the H2-rich gas mixed with the feed, by means of a line 9,

[0108] - a kerosene cut (K). 16

Claims

Claims

1. A method for manufacturing a jet fuel comprising at least the steps of: a) providing fatty acid ethyl esters from the reaction of animal fats which are animal by-products with ethanol in a transesterification reactor, step a) comprising: (i) obtaining ethanol of renewable origin, (ii) followed by the reaction of the animal fats with the ethanol obtained in step (i) in a transesterification reactor, and the provided fatty acid ethyl esters comprising: - from 20%m to 64%m of fatty acid ethyl esters whose carbon chain contains from 12 to 16 carbon atoms, - from 25%m to 65%m of fatty acid ethyl esters whose carbon chain contains 18 carbon atoms, b) providing hydrocarbons of fossil origin,c) preparing a hydrocarbon feedstock containing the hydrocarbons of fossil origin provided by step b) and the fatty acid ethyl esters provided by step a) in a content of at most 5% by volume relative to the hydrocarbon feedstock, d) subjecting the hydrocarbon feedstock prepared during step c) to hydrotreatment and obtaining a treated hydrocarbon feedstock, e) fractionating the treated hydrocarbon feedstock obtained in step d) and recovering a kerosene fraction as jet fuel, said kerosene fraction preferably having a final boiling point below 300°C.,

2. Manufacturing process according to claim 1, wherein the fatty acid ethyl esters provided in step a) comprise at least one of the following characteristics: - at most 4% m of fatty acid ethyl esters whose carbon chain contains 20 carbon atoms, - at most 1% m of fatty acid ethyl esters whose carbon chain contains 22 carbon atoms.

3. Manufacturing process according to any one of claims 1 or 2, in which the hydrocarbons of fossil origin provided in step b) are chosen from kerosene cuts.

4. A manufacturing process according to any one of claims 1 to 3, wherein, during step (i), the ethanol of renewable origin is obtained by ethanolic fermentation in a bioreactor containing a culture of one or more microorganisms.

5. Manufacturing process according to 4, in which, during step (i), the ethanol is obtained by: - ​​aerobic fermentation of a substrate rich in sugars and / or starch from biomass, or - anaerobic fermentation of a gaseous substrate comprising CO.

6. Manufacturing process according to any one of claims 1 to 3, in which, during step (i), the ethanol of renewable origin is obtained by conversion of a synthesis gas rich in CO / H2, this synthesis gas being derived from biomass.

7. Manufacturing process according to any one of claims 1 to 6, in which step d) is carried out under a pressure of 15 to 130 bars and at a temperature of 250 and 380°C, in the presence of a hydrotreatment catalyst and dihydrogen.

8. Manufacturing method according to any one of claims 1 to 7, in which the hydrotreatment catalyst comprises at least one metal from groups 6, 9, 10, 11 of the periodic table of elements, optionally on a support chosen from alumina, silica alumina, phosphated alumina, borated alumina, phosphated silica alumina, alone or as a mixture.

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