PROCESS FOR PRETREATMENT BY HYDROLYSIS OF A HYDROCARBON FEED OF NATURAL ORIGIN MIXED WITH A FEED OF FOSSIL ORIGIN

Abstract

METHOD FOR PRETREATING BY HYDROLYSIS A HYDROCARBON FEED OF NATURAL ORIGIN MIXED WITH A FEED OF FOSSIL ORIGIN The invention relates to a method for pretreating by hydrolysis a hydrocarbon feed of natural origin containing fatty acid esters, in which said hydrocarbon feed of natural origin is brought into contact with water in a hydrolysis zone (10) to produce a first effluent enriched in free fatty acids and a second effluent rich in alcohol and water. According to the invention, a diluent consisting of a hydrocarbon feed of fossil origin is introduced into the hydrolysis zone upstream of the hydrocarbon feed of natural origin relative to the direction of circulation thereof. The invention also relates to a method and a unit for manufacturing hydrocarbon fluids integrating the pretreatment according to the invention upstream of a hydroconversion. Abstract figure: figure 1

Description

Title of the invention: PROCESS FOR PRETREATMENT BY HYDROLYSIS OF A HYDROCARBON FEED OF NATURAL ORIGIN MIXED WITH A FEED OF FOSSIL ORIGIN Technical field

[0001] The present invention relates to the pretreatment by hydrolysis of hydrocarbon feedstocks of natural origin in admixture with a feedstock resulting from the refining of hydrocarbon feedstocks of fossil origin and a method for manufacturing hydrocarbon fluids from complex mixtures of hydrocarbons of renewable and fossil origin comprising this pretreatment. In particular, the present invention relates to a method for the coprocessing conversion of a biological raw material comprising fatty acid esters (FAE) into free fatty acids (FFA) and then into oxygen-free paraffinic compounds, which can be used as fuels. Background to the invention

[0002] Due to the scarcity of fossil resources and growing environmental concerns, the use of molecules derived from biomass is increasingly sought to replace molecules of fossil origin. In particular, some countries such as France are implementing taxes on aviation fuels. In particular, the regulation on establishing a level playing field for a sustainable aviation sector within the European Union (also known as the "ReFuelEU Aviation initiative") aims to increase the use of sustainable fuels by aircraft and ships in order to reduce their environmental footprint. Thus, by 2025, 2% of the jet used in the European Union must be of renewable origin.Thus, the preparation of jet fuel, or other hydrocarbon fuels or fluids, from molecules derived from biomass constitutes a real economic, environmental and strategic challenge. Prior art.

[0003] Today there are many processes for manufacturing a fuel comprising a component of biological origin.

[0004] A well-known process for manufacturing a renewable fuel and other hydrocarbon fluids consists of subjecting a vegetable or animal fat or oil and a feedstock of fossil origin to hydrotreatment in the presence of dihydrogen and a catalyst. Such coprocessing makes it possible to limit the high exothermicity of the hydrotreatment of triglycerides. Corrosion phenomena are, however, observed due to the acidity of the processed vegetable and / or animal oils.

[0005] Typically, in this type of process, unreacted hydrogen from the hydrotreatment step is separated from the hydrotreatment effluent and reused. However, when a vegetable or animal fat or oil is co-treated with a fossil feedstock, dilution of the hydrogen with propane (from glycerol) produced during hydrotreatment occurs, increasing propane ballast in the unconverted hydrogen stream to be recycled or the need to separate the hydrogen-propane gas mixture before recycling the unconverted hydrogen or purging this stream to maintain propane ballast below a certain concentration (and thus overall hydrogen consumption).

[0006] This increase in the overall consumption of dihydrogen is also observed in the hydrotreatment processes of feedstocks of biological origin alone. One way of reducing the formation of propane is then to pretreat the feedstock of biological origin by hydrolysis. Hydrolysis also makes it possible to reduce the consumption of dihydrogen to the extent that the triglycerides present are partly "cut" during this pretreatment and consequently the glycerol is no longer converted during the hydrotreatment.

[0007] Document WO2021 / 028833 describes a hydrolysis pretreatment in which a crude used oil (which may be cooking oil, category 1 animal fats or residual oils) is hydrolyzed in the presence of an effluent containing mono-, di- and triglycerides of fatty acids free of impurities leaving an esterification unit. The addition of this effluent makes it possible to dilute the contaminants present in the used oil, to improve the homogenization of the feedstock and the removal of impurities. The free fatty acids produced during the hydrolysis are then sent to a hydrotreatment unit and then to an isomerization and cracking unit. The glycerol produced during the hydrolysis is sent with a portion of the fatty acids produced by the hydrolysis to an esterification unit producing the effluent which is hydrolyzed with the crude oil.This process, however, requires the integration of an esterification unit in addition to the hydrotreatment and isomerization units.

[0008] Documents US 10,071,322 and US 8,686,198 also describe a pretreatment by hydrolysis of a renewable feedstock mixed or not with a feedstock of fossil origin making it possible to reduce the contaminant content of the treated feedstocks. The feedstocks of fossil origin used are crude oil and bottoms from atmospheric or vacuum distillation columns, or used lubricants or used paraffin waxes.

[0009] However, there is still a need to improve existing processes.

[0010] The invention aims in particular to propose a method of pretreatment by hydrolysis of a hydrocarbon charge of natural origin, intended in particular to be integrated into an existing hydrocarbon fluid manufacturing process without major modification thereof. Description of the invention

[0011] The invention provides a process for pretreatment by hydrolysis of a hydrocarbon feedstock of natural origin containing fatty acid esters, in which: - said hydrocarbon feedstock of natural origin is brought into contact with water in a hydrolysis zone to produce a first effluent enriched in free fatty acids, optionally containing fatty acid esters, and a second effluent rich in alcohol and water.

[0012] According to the invention, a diluent consisting of a hydrocarbon feedstock of fossil origin is introduced into the hydrolysis zone, this diluent being introduced upstream of the hydrocarbon feedstock of natural origin relative to the direction of circulation thereof.

[0013] The dilution with a mixture of hydrocarbons thus carried out can make it possible to better dephase the polar / apolar phases present in the hydrolysis zone, and thus to improve the hydrolysis reaction (for example to promote the completion of the hydrolysis reaction). This dilution also makes it possible to reduce corrosion phenomena and to improve the elimination of impurities. In particular, the inorganic species of said charge will be detached from the fatty acid esters and, preferably, dissolve in the aqueous phase.

[0014] Furthermore, the introduction of the diluent upstream of the naturally occurring feedstock makes it possible to achieve better hydrolysis rates and better temperature control.

[0015] The diluent can advantageously be chosen from a naphtha cut, a kerosene cut, a diesel cut, a distillate cut.

[0016] The quantity of diluent introduced into the hydrolysis zone can advantageously represent 0.5 to 150% by mass of the total charge introduced into said zone.

[0017] Advantageously, the diluent may be introduced into the hydrolysis zone at a temperature of 200°C to 350°C, for example following preheating. In this case, the naturally occurring hydrocarbon feedstock may be introduced into the hydrolysis zone at a temperature of 50 to 250°C.

[0018] Advantageously, the hydrocarbon feedstock of natural origin containing fatty acid esters used in the pretreatment process may comprise, or consist of, an oil of natural origin, an esterified oil of natural origin or mixtures thereof. This oil of natural origin may in particular be chosen from a vegetable oil, an animal oil or fat, a used oil, an oil produced by microorganisms, as well as mixtures thereof. A used oil will preferably be used.

[0019] In one embodiment, it is possible to further introduce into said hydrolysis zone at least one liquefaction oil of a hydrocarbon feedstock chosen from a biomass oil and a plastics oil, the at least one liquefaction oil of a hydrocarbon feedstock representing at most 10% by mass of the hydrocarbon feedstock of natural origin, and being introduced into said hydrolysis zone upstream of the injection of the hydrocarbon feedstock of natural origin relative to the direction of circulation of the hydrocarbon feedstocks in the hydrolysis zone.

[0020] Whatever the embodiment, the hydrolysis can be carried out under one or more of the following conditions: - a temperature of 130 to 350°C, - a pressure of 7 to 100 barg, - a water / natural hydrocarbon feedstock mass ratio of 0.1 to 2, preferably 0.25 to 1.5.

[0021] Another subject of the invention relates to a process for manufacturing hydrocarbon fluids from a hydrocarbon feedstock of natural origin containing fatty acid esters, and from a hydrocarbon feedstock of fossil origin, in particular chosen from a naphtha cut, a kerosene cut, a diesel cut and a distillate cut, the process comprising at least: a. a pretreatment step by hydrolysis implemented according to the invention in which said hydrocarbon feedstock of natural origin is brought into contact with water in the presence of at least a portion of said hydrocarbon feedstock of fossil origin in a hydrolysis zone to produce a first effluent enriched in free fatty acids, optionally containing fatty acid esters, and a second effluent rich in alcohol and water, b. an optional step of separation and / or purification of the first effluent enriched in free fatty acids from step a) during which residual alcohols, inorganic impurities and / or water are removed from the first effluent to obtain a first purified effluent, c. a hydroconversion step, in which the first effluent from step a), optionally purified in step b), is brought into contact alone or in a mixture with another part of said hydrocarbon feedstock of fossil origin, in particular with the remaining part of hydrocarbon feedstock of fossil origin, with dihydrogen in a hydroconversion zone in the presence of at least one catalyst under conditions suitable for carrying out a hydroconversion and forming a hydroconverted effluent comprising a hydroconverted liquid fraction and a fraction of incondensable components, d. a step of separating the hydroconverted effluent from step c) during which the fraction of incondensable components is separated from the hydroconverted liquid fraction.

[0022] The pretreatment process according to the invention can thus be easily integrated into a conventional hydrocarbon fluid manufacturing process in that it is sufficient to add a pipe for introducing the feedstock of fossil origin into the hydrolysis zone, without having to add additional treatment units such as in particular an esterification unit.

[0023] The process according to the invention may further comprise a step e) of fractionation of the hydroconverted liquid fraction from step d), in which said hydroconverted liquid fraction is separated into at least one liquid fraction chosen from a naphtha fraction, a diesel fraction and a kerosene fraction.

[0024] The quantity of first effluent introduced into the hydroconversion zone may advantageously represent 0.5 to 100% by mass, preferably 0.5 to 90% by mass, more preferably 0.5 to 50% by mass, more preferably 5 to 25% by mass of the total feedstock introduced into the hydroconversion zone of step c).

[0025] In the manufacturing process according to the invention, at least a portion of the incondensable components separated in step d) can be sent to the hydrolysis zone, optionally after removal of the components other than dihydrogen.

[0026] The invention also relates to a unit for manufacturing hydrocarbon fluids suitable for implementing the manufacturing method according to the invention.

[0027] Thus, another object of the invention relates to a unit for manufacturing hydrocarbon fluids from a hydrocarbon feedstock of natural origin containing fatty acid esters and a hydrocarbon feedstock of fossil origin, comprising: - a hydrolysis zone comprising at least a first inlet pipe for the hydrocarbon feedstock of natural origin containing fatty acid esters, a second inlet pipe for water, a third inlet pipe for the hydrocarbon feedstock of fossil origin, a first outlet pipe for a first effluent and a second outlet pipe for a second effluent, and optionally an additional inlet pipe, - an optional separation and / or purification treatment zone connected to the first outlet pipe of the hydrolysis zone, - a hydroconversion zone comprising at least one inlet connected to the first outlet pipe of the hydrolysis zone or to an outlet of the optional treatment zone, an inlet pipe for a gas containing dihydrogen, optionally an inlet pipe for a feedstock of fossil origin, and an outlet pipe for a hydroconverted effluent, - a separation zone connected to the outlet pipe of the hydroconversion zone, characterized in that the third inlet pipe opens into the hydrolysis zone in a position located upstream of the first inlet pipe by relative to a direction of circulation of the hydrocarbon feedstocks in the hydrolysis zone.

[0028] In one embodiment, the unit may further comprise a fractionation zone having an inlet connected to an outlet pipe of the first separation zone, and at least one outlet pipe. Detailed description of the invention

[0029] 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.

[0030] 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.

[0031] 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 for the measurement of boiling points of petroleum fractions by gas chromatography, ASTM D7169 for heavy hydrocarbons, ASTM D7500, D86 or DI 160 for distillates.

[0032] Naturally occurring hydrocarbon feedstock containing fatty acid esters

[0033] By “hydrocarbon feedstock of natural origin” is meant a hydrocarbon feedstock not containing components of fossil origin.

[0034] The naturally occurring hydrocarbon feedstock containing fatty acid esters used in the present invention may comprise, or consist of, a naturally occurring oil, an esterified naturally occurring oil, or mixtures thereof.

[0035] The hydrocarbon feedstock of natural origin used in the present invention may thus comprise, or consist of, an oil of natural origin or a mixture of oils of natural origin, esters resulting from the transesterification of fatty acid esters and / or from the esterification of fatty acids contained in one or more oils of natural origin, as well as their mixtures.

[0036] The oil of natural origin can be chosen from a vegetable oil, an animal oil or fat, a used oil, an oil produced by microorganisms, as well as their mixtures.

[0037] A naturally occurring oil is defined as an oil that does not contain mineral oil of fossil origin.

[0038] Typically, an oil of natural origin may contain 50%m or more, preferably 60%m or more, preferentially 70%m or more, of fatty acids and / or fatty acid esters (mono-, di-, triglycerides).

[0039] In one embodiment, a naturally occurring oil may contain fatty acid esters (mono-, di- or triglycerides) and / or free fatty acids, containing one to three C8-C24 acyl groups, saturated or unsaturated. When multiple acyl groups are present, they may be the same or different.

[0040] The vegetable oil may be chosen from pine oil, rapeseed oil, sunflower oil, castor oil, peanut oil, linseed oil, babasu 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 oil, grapeseed oil, argan oil, jojoba oil, sesame oil, walnut oil, hazelnut oil, tungsten carbide oil, rice oil, safflower oil, algae oil, waste oils, nut shell oil (including cashew nut shell oil), and any combination thereof.

[0041] Used oil includes used cooking oils or used edible oils and oils recovered from waste water, such as trap and drain greases / oils, gutter oils, sewer oils, e.g. from water treatment plants, used greases from the food industry, and used cooking oils that are animal by-products.

[0042] The animal fat may be chosen from tallow, lard, fat (yellow and brown fat), fish oil / fat, milk fat, animal fats which are animal by-products.

[0043] In particular, animal fats and used cooking oils which are animal by-products have the status of 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 Commission Regulation (EU) No 142 / 2011 (implementing regulation of Regulation EC No 1069 / 2009).

[0044] 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.

[0045] Used cooking oils with the status of animal by-products are used cooking oils (used cooking oils or UCO), namely the residues of fatty substances of vegetable or animal origin used for human food, in the food industry, in collective or commercial catering.

[0046] Oil of natural origin may also be an oil produced by microorganisms, natural or genetically modified, such as bacteria, yeasts, in particular oleaginous yeasts, algae, prokaryotes or eukaryotes. In particular, these oils may be recovered by well-known mechanical or chemical extraction methods.

[0047] The above-mentioned oils, most of which are rich in triglycerides, further contain varying amounts of non-triglyceride components such as free fatty acids, mono- and diglycerides, and many other organic and inorganic components, including phosphatides, sterols, tocopherols, tocotrienols, hydrocarbons, pigments (gossypol, chlorophyll), vitamins (carotenoids), sterol glucosides, glycolipids, protein fragments, traces of pesticides and traces of metals, as well as resinous and mucilaginous materials.

[0048] Preferably, the oils of natural origin used in the present invention have not undergone any pretreatment, such as the chemical and physical pretreatments usually carried out by those skilled in the art, similar to those carried out for the treatment of edible oils, such as degumming, neutralization with an alkaline solution (generally NaOH), bleaching, finishing or polishing, steam treatment, cavitation, etc.

[0049] Compositions resulting from the transesterification of fatty acid esters and / or from the esterification of fatty acids contained in the aforementioned oils of natural origin, such as compositions comprising alkyl esters of fatty acids, and in particular methyl esters of fatty acids or ethyl esters of fatty acids, and comprising impurities originating from the oils, may also form part of the hydrocarbon feedstocks of natural origin considered in the present invention.

[0050] The hydrocarbon feedstock of natural origin used in the present invention may thus contain 50% by weight or more, preferably 60% by weight or more, preferentially 70% by weight or more, of fatty acids and / or fatty acid esters (mono-, di-, triglycerides, alkyl esters of fatty acids, and in particular ethyl esters of fatty acids, methyl esters of fatty acids). In general, the hydrocarbon feedstock of natural origin comprises at most 99% by weight of fatty acids and / or fatty acid esters.

[0051] The phosphorus content of the naturally occurring hydrocarbon feedstock may be 20 ppm or more or 50 ppm or more, for example 50 ppm to 1500 ppm, or 200 ppm to 1200 ppm, measured for example by X-ray fluorescence or ICP by the UOP 389 method, or by ICP AES Dilution or ICP microwave digestion in medium farm.

[0052] The nitrogen content of the naturally occurring hydrocarbon feedstock may be 20 ppm or more, for example 50 ppm to 1200 ppm or 200 ppm to 2000 ppm, measured for example by X-ray fluorescence or chemiluminescence.

[0053] The naturally occurring hydrocarbon feedstock may further comprise one or more other heteroatoms such as alkali metals, in particular potassium, alkaline earth metals, and / or chlorine. The content of these heteroatoms may vary depending on the constituents of the composition. It may be determined by elemental analysis of the X-ray fluorescence type or by ICP.

[0054] Liquefaction oil for a hydrocarbon feedstock

[0055] By "liquefaction oil" is meant an oil resulting from a pyrolysis process and / or a hydrothermal liquefaction process of a hydrocarbon feedstock. This hydrocarbon feedstock may comprise plastics and / or biomass, alone or in a mixture, in particular in the form of waste. A liquefaction oil may be formed from a mixture of two or more liquefaction oils resulting from the liquefaction of different hydrocarbon feedstocks, each obtained by pyrolysis or hydrothermal liquefaction.

[0056] The pyrolysis process must be understood as a thermal cracking process in the absence of air, typically carried out at a temperature of 300 to 1000°C or 400 to 700°C, carried out in the presence or absence of a catalyst and / or a gas (fast pyrolysis, flash pyrolysis, catalytic pyrolysis, hydropyrolysis, steam pyrolysis, etc.).

[0057] The hydrothermal liquefaction process (or HTL for "Hydrothermal Liquefaction" in English) is a thermochemical conversion process using water as a solvent, reactant and catalyst for the degradation reactions of a hydrocarbon feedstock, the water typically being in a subcritical or supercritical state. The hydrothermal liquefaction process is typically carried out at a temperature of 250 to 500 °C and at pressures of 10 to 25-40 Mpa in the presence of water.

[0058] The liquefaction oil optionally used in the present invention may comprise, or consist of, a plastics oil, a biomass oil, and mixtures thereof. In one embodiment, the liquefaction oil optionally used in the present invention may comprise, or consist of, a biomass oil.

[0059] The expression “plastic oil” designates the liquid hydrocarbon products obtained at the end of pyrolysis or hydrothermal liquefaction of thermoplastic and / or thermosetting and / or elastomeric polymers, alone or in a mixture, and generally in the form of waste, optionally in a mixture with at least one other filler, in particular in the form of waste, such as biomass, for example chosen from lignocellulosic biomass, herbaceous biomass, biomass aquifer, paper and cardboard, organic waste (forestry, agricultural, industrial and / or household waste), food waste, alone or in a mixture.

[0060] The plastic can be of any type, including any type of new or used plastic, included in household (post-consumer) or industrial waste. By plastics is meant materials consisting of polymers and optionally auxiliary components such as plasticizers, fillers, colorants, catalysts, flame retardants, stabilizers, etc.For example, these polymers can be polyethylene, halogenated polyethylene (Cl, F), polypropylene, polystyrene, polybutadiene, polyisoprene, poly(ethylene terephthalate) (PET), acrylonitrile-butadiene-styrene (ABS), polybutylene, poly(butylene terephthalate) (PBT), polyvinyl chloride (PVC), polyvinylidene chloride, polyester, polyamide, polycarbonate, polyether, epoxy polymer, polyacetal, polyimide, polyesteramide, biopolymers such as polylactic acid, polyhydroxy acid(s), polyethylene furanate (PEF), polybutyl succinate (PBS) etc. Elastomers are linear or branched polymers transformed by vulcanization into a weakly crosslinked three-dimensional network that is infusible and insoluble. They include natural or synthetic rubbers.They may be part of tire-type waste or any other household or industrial waste containing elastomers, natural and / or synthetic rubber, mixed or not with other components, such as plastics, plasticizers, fillers, vulcanizing agents, vulcanization accelerators, additives, etc. Examples of elastomeric polymers include ethylene-propylene copolymers, ethylene-propylene-diene terpolymer (EPDM), polyisoprene (natural or synthetic), polybutadiene, styrene-butadiene copolymers, isobutene-based polymers, isobutylene isoprene copolymers, chlorinated or brominated, butadiene acrylonitrile copolymers (NBR), and polychloroprenes (CR), polyurethanes, silicone elastomers, etc.

[0061] Generally, any polymer or mixture of polymers capable of producing hydrocarbons by liquefaction may be used.

[0062] In one embodiment, the plastic oil may be derived from the liquefaction of plastic waste that does not include tires and / or latex (vulcanized or not).

[0063] Plastic oils contain, in particular, paraffins, i-paraffins (iso-paraffins), dienes, alkynes, olefins, naphthenes and aromatics. Plastic liquefaction oils also contain impurities containing heteroatoms, such as chlorinated, oxygenated, sulfurous, nitrogenous and / or silylated organic compounds, metals, salts, phosphorus compounds.

[0064] The composition of a plastic oil depends on the nature of the liquefied plastic, and optionally on any other waste liquefied with the plastic, and is essentially (in particular at more than 80% m, most often at more than 90% m) consisting of hydrocarbons having 1 to 150 carbon atoms and impurities.

[0065] A plastic oil typically comprises from 5 to 80%m of paraffins (including cycloparaffins), from 10 to 95%m of unsaturated compounds (including olefins, dienes and acetylenes), from 5 to 70%m of aromatics. These contents can be determined by gas chromatography. In particular, a plastic oil can comprise a Bromine number of 10 to 130 g Br2 / 100g, as measured according to ASTM DI 159, and / or a maleic anhydride number (UOP326-82) of 1 to 55 mg maleic anhydride / 1g.

[0066] A plastic oil may have an initial boiling point of at least 15°C, and a final boiling point of at most 800°C, preferably at most 600°C, even more preferably at most 560°C, more preferably at most 450°C, even more preferably at most 350°C, preferably 250°C (measured according to standard NF EN 15199-1 / 2).

[0067] A plastic oil typically comprises at least 20 ppm of heteroatoms, or even at least 30 ppm of heteroatoms.

[0068] A plastic oil may in particular comprise one or more of the following heteroatom contents: from 0 to 8%m of oxygen (measured according to the ASTM D5622 standard), from 1 to 13000 ppm of nitrogen (measured according to the ASTM D4629 standard), from 2 to 1000 ppm of sulfur (measured according to the ISO 20846 standard), from 1 to 1000 ppm of metals (measured by ICP), from 50 to 6000 ppm of chlorine (measured according to the ASTM D7359-18 standard), from 0 to 200 ppm of bromine (measured according to the ASTM D7359-18 standard), from 1 to 40 ppm of fluorine (measured according to the ASTM D7359-18 standard), 1 to 2000 ppm of silicon (measured by XRF).

[0069] The expression “biomass oil” designates the liquid hydrocarbon products obtained following pyrolysis or hydrothermal liquefaction of one or more biomasses.

[0070] Biomass can be defined as an organic plant or animal product.

[0071] In one embodiment, the biomass oil may advantageously be derived from a biomass chosen from lignocellulosic biomass, herbaceous biomass, aquifer biomass, paper and cardboard, organic waste (forestry, agricultural, industrial and / or household waste), alone or as a mixture.

[0072] Biomass can thus include (i) biomass produced by surplus agricultural land, preferably not used for human or animal food: dedicated crops, called energy crops (short rotation coppice (SRC), very short rotation coppice (VRC); (ii) biomass produced by deforestation (forest maintenance) or clearing of agricultural land, etc.; (iii) agricultural residues from crops, in particular cereal crops, vines, orchards, olive trees, fruits and vegetables including nuts, food industry residues, etc.; (iv) forest residues from forestry and wood processing; (v) agricultural residues from livestock farming (manure, slurry, bedding, droppings, etc.); (vi) household organic waste (paper, cardboard, green waste, etc.); (vii) industrial organic waste (paper, cardboard, wood, putrescible waste, etc.); (viii) algal biomass, namely biomass formed from algae, for example micro-algae (algal biomass can be an algae suspension obtained by harvesting algae from, for example, a bioreactor, or an algae residue obtained by dehydrating an algae suspension) or macro-algae; (ix) herbaceous biomass; (x) vegetable oils contained in certain waste (cashew nut shells or other), (xi) industrial waste (wood type B), (xii) sludge from sewage treatment plants, (xiii) digestates from methanizers.

[0073] Biomass oil may contain from 8 to 55% by mass of oxygen. This oxygen is present in oxygenated compounds containing at least one hydroxyl group (-OH) and / or at least one carbonyl group (>C=O). A biomass oil may in particular contain carboxylic acids, ketones, aldehydes, phenols.

[0074] Hydrocarbon charge of fossil origin

[0075] The fossil-based hydrocarbon feedstock used in the present invention comprises fossil-based hydrocarbons.

[0076] In one embodiment, the hydrocarbon feedstock of fossil origin may consist of hydrocarbons of fossil origin. In this case, it does not comprise components of renewable origin.

[0077] Hydrocarbons of fossil origin which can be used in the process can advantageously be chosen from naphtha cuts, diesel cuts, kerosene cuts and distillate cuts, originating in particular from the distillation of crude oil.

[0078] A naphtha cut of fossil origin typically has boiling points ranging from 15°C to 220°C. It typically has, according to ASTM D86-12, an initial boiling point of 15°C to 42°C and a final boiling point less than or equal to 220°C. Such a naphtha cut generally comes from the direct distillation of crude oil or from fractionation after the hydrotreatment and / or hydroisomerization and / or hydrocracking step and typically comprises C5-C12 compounds.

[0079] A diesel cut of fossil origin typically has boiling points ranging from 180°C to 360°C. It typically has, according to the ASTM D86-12 standard, an initial boiling point of 180 to 240°C and a final boiling point less than or equal to 360°C. Such a diesel cut generally comes from the direct distillation of crude oil or from fractionation after the hydrotreatment and / or hydroisomerization and / or hydrocracking step and typically comprises C13-C25 compounds.

[0080] A kerosene cut of fossil origin typically has boiling points ranging from 130 °C to 300 °C. It typically has, according to ASTM D86-12, 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 comes from the direct distillation of crude oil or from fractionation after the hydrotreatment and / or hydroisomerization and / or hydrocracking step and typically comprises C9-C15 compounds.

[0081] Distillate cuts of fossil origin typically have boiling points ranging from 375 to 600 °C. They typically have, according to ASTM D86-12, an initial boiling point of 375 to 450 °C and a final boiling point of 500 °C to 600 °C. Such distillate cuts generally come from the vacuum distillation of an atmospheric residue of crude oil, also called vacuum distillates, and typically comprise C20-C55 compounds. A. Hydrolysis pretreatment process

[0082] The pretreatment process according to the invention makes it possible to hydrolyze at least part of the esters present in a hydrocarbon feedstock of natural origin in order to obtain free fatty acids and alcohols. It is therefore the reverse reaction of an esterification reaction.

[0083] During this step, the naturally occurring hydrocarbon feedstock reacts with water under appropriate conditions to form the free fatty acids and alcohols resulting from the dissociation of the esters.

[0084] The hydrocarbon feedstock may contain mono-, di- or tri-glycerides of fatty acids, and / or alkyl esters of fatty acids, and in particular ethyl esters of fatty acids and methyl esters of fatty acids. The alcohols thus include glycerol, alkyl alcohols, and in particular ethanol and methanol, and other alcohols resulting from the partial or total hydrolysis of the fatty acid esters present. The fatty acids released depend on the nature of the oil of natural origin used.

[0085] Typically, the hydrolysis may be carried out at a temperature of 130 to 350°C, preferably 140 to 300°C, more preferably 140 to 250°C, and at a pressure of 7 to 100 barg (bar gauge), preferably 7 to 50 barg.

[0086] The hydrolysis is typically carried out in the presence of an excess of water. The water / hydrocarbon feedstock mass ratio may be from 0.1 to 2, preferably from 0.25 to 1.5, more preferably from 0.35 to 1 and even more preferably from 0.4 to 0.75 (this corresponds to weight percents of approximately from 9%m to 66%m, preferably from 20%m to 60%m of water in the combined feedstock, preferably from 25%m to 50%m and even more preferably from 28%m to 42%m).

[0087] The water may be introduced in liquid form, for example using a pump or a regulating valve, then heated to produce a mixture of liquid water and water vapor at a high temperature, for example at least 250°C, this introduction being able to be carried out at one or more points in the hydrolysis zone. may optionally also introduce superheated steam in order to also bring heat to further heat the load, for example water vapor of 300 to 500 °C at the hydrolysis pressure (typically 50 barg). This introduction can be carried out at one or more points in the hydrolysis zone. Also, a combination of preheated water and water vapor can be used and introduced at one or more points in the hydrolysis zone.

[0088] Hydrolysis is typically carried out without a catalyst.

[0089] The hydrolysis products form a mixture of fatty acids and alcohols. This mixture is biphasic and composed of a denser aqueous phase containing a portion of the alcohols and a less dense phase containing the fatty acids and a portion of the alcohols. The aqueous phase also includes most of the impurities initially present in the hydrocarbon feedstock, such as, for example, metals, chlorine, sulfur (essentially in the form of sulfate ions) and phosphorus (essentially in the form of phosphate ions).

[0090] The hydrolysis zone may comprise one or more reactors operating in batch or continuous mode. For example, a countercurrent reactor or a cocurrent reactor equipped with a static mixer may be used. The hydrolysis zone may contain a packing to improve contact between the different phases of the reactor.

[0091] Preferably, the hydrocarbon feedstocks and the water circulate counter-currently in the hydrolysis zone, the latter being then “counter-current”.

[0092] When the hydrolysis zone is counter-current, the hydrocarbon feeds circulate in the same direction, generally from bottom to top, and the water circulates counter-current, namely from top to bottom.

[0093] When the hydrolysis zone is co-current, the hydrocarbon feeds and the water circulate in the same direction, generally from bottom to top. The water is then generally introduced at the same height in the hydrolysis zone as the hydrocarbon feeds.

[0094] Typically, in countercurrent mode, the two phases of the two-phase mixture are extracted separately from the hydrolysis zone, the phase containing the fatty acids being extracted from an upper part of the first zone and forming a first effluent enriched in free fatty acids, and optionally containing fatty acid esters, and the denser aqueous phase typically being withdrawn from a lower part of the first zone and forming a second effluent rich in alcohol and water, typically downstream of the point of injection of the hydrocarbon feedstocks into the hydrolysis zone.

[0095] Typically, in co-current mode, the two phases of the two-phase mixture are extracted together from the hydrolysis zone and are separated after the hydrolysis zone. in a settling zone (optionally the settling zone is integrated into an outlet part of the hydrolysis zone), where the phase forming a first effluent enriched in free fatty acids, and optionally containing fatty acid esters, is extracted from an upper part of the settling zone, and the denser aqueous phase typically being drawn off from a lower part of the settling zone and forming a second effluent rich in alcohol and water.

[0096] According to the invention, a diluent is also introduced into the hydrolysis zone, which is a charge of fossil origin, this charge of fossil origin being introduced upstream of the charge of natural origin relative to the direction of circulation thereof.

[0097] Adding a diluent can allow:

[0098] - better phase shifting of polar products, such as glycerol and impurities in organic non-polar products such as free fatty acids,

[0099] - a limitation of corrosion in the hydrolysis zone due to free fatty acids present in the naturally occurring hydrocarbon feedstock,

[0100] - better thermal integration when the diluent is introduced into the zone hydrolysis directly at the outlet of a hydroconversion or separation zone, without intermediate cooling.

[0101] Furthermore, hydrolysis itself allows: - elimination of metals and heteroatoms present (notably P) in the hydrocarbon feedstock of natural origin, these contaminants being found in the aqueous phase which is separated from the hydrocarbon feedstock of natural origin, - a limitation of propane production during subsequent hydroconversion, - a reduction in the consumption of dihydrogen during subsequent hydroconversion.

[0102] In one embodiment, the diluent may be introduced into the hydrolysis zone at a temperature of 200 to 350°C, typically 230 to 280°C.

[0103] The introduction of the diluent at a temperature of 200°C or more into the hydrolysis zone makes it possible to limit the preheating of the naturally occurring hydrocarbon feedstock before it enters the hydrolysis zone and thus to avoid its degradation. The naturally occurring hydrocarbon feedstock can then be introduced into the hydrolysis reaction zone at a temperature sufficient to ensure its fluidity, for example from 50°C to 250°C.

[0104] Advantageously, the amount of diluent introduced into the hydrolysis zone may represent 0.5 to 150% by mass, preferably 5 to 100% by mass, more preferably 5 to 40% by mass, even more preferably 10 to 20% by mass, of the total feedstock introduced into the hydrolysis zone, or in any range defined by two of these limits.

[0105] In one embodiment of the invention, it is also possible to introduce into said hydrolysis zone, upstream of the hydrocarbon feedstock of natural origin relative to the circulation thereof, at least one liquefaction oil of a hydrocarbon feedstock chosen from a biomass oil and a plastics oil, the at least one liquefaction oil of an introduced hydrocarbon feedstock representing at most 10% by mass of the hydrocarbon feedstock of natural origin introduced into said hydrolysis zone, for example from 0.5 to 10% by mass, more preferably from 0.5 to 5% by mass. This can make it possible to incorporate more components of renewable and / or natural origin, and possibly to add aromatic compounds.

[0106] The first effluent produced by the hydrolysis pretreatment process thus comprises a component of natural origin enriched in free fatty acids, typically containing at least 10% by mass of free fatty acids. It generally also contains fatty acid esters, typically in a content of at most 90% by mass.

[0107] The hydrolysis may be partial. In this case, the content of free fatty acids formed and present in the naturally occurring component may then be limited, for example to at most 20% by mass, the content of fatty acid esters in the naturally occurring component being, for example, at most 80% by mass. Partial hydrolysis may be achieved at moderate temperatures (temperatures close to the lower limit of the aforementioned ranges, and generally at low pressure) and / or by reducing the reaction time.

[0108] The hydrolysis may be total. In this case, the content of free fatty acids formed and present in the naturally occurring component may then be high, for example of the order of 60% by mass. Total hydrolysis may be obtained at high temperatures (temperatures close to the upper limit of the aforementioned ranges, generally at high pressure) and / or by increasing the reaction time. In this case, the naturally occurring component of the effluent no longer contains fatty acid esters.

[0109] The hydrolysis can also be carried out in the presence of a catalyst.

[0110] The catalysts which accelerate the hydrolysis reaction are acids, such as sulfuric acid, acids with an organic chain containing a sulfonic group, choric acid. Other heterogeneous catalysts which accelerate the hydrolysis reaction are zinc-based catalysts. Non-exclusively, the catalyst used in the process according to the invention is a solid containing zinc oxide, at least one solid solution of general formula ZnxAl2O(3+X), and in the presence of at least one heterogeneous catalyst based on a silicic, aluminum or titanium solid containing zinc. [YES] B. Process for manufacturing hydrocarbon fluids

[0112] The hydrolysis pretreatment process according to the invention is particularly advantageous when integrated into a process for manufacturing hydrocarbon fluids from a hydrocarbon feedstock of natural origin containing fatty acid esters and a hydrocarbon feedstock of fossil origin.

[0113] Thus, the invention also relates to a process for manufacturing hydrocarbon fluids from a hydrocarbon feedstock of natural origin containing fatty acid esters as previously defined, and from a hydrocarbon feedstock of fossil origin. This process is thus a coprocessing process.

[0114] The fossil fuel load is as defined above.

[0115] The fossil fuel load to be treated can be entirely introduced at the level of step a) of hydrolysis of the process according to the invention, or its introduction can be divided between steps a) of hydrolysis and c) of hydroconversion.

[0116] Step a) of hydrolysis

[0117] According to the invention, step a) of pretreatment by hydrolysis is carried out according to the method of pretreatment by hydrolysis of the present invention, the diluent introduced into the hydrolysis zone consisting of all or part of the feedstock of fossil origin to be treated.

[0118] Optional step b) of separation and / or purification

[0119] The first effluent from the hydrolysis step may still contain alcohol residues, inorganic impurities and / or water.

[0120] The manufacturing process according to the invention may then comprise an optional step b) of treatment, in particular separation and / or purification, of the first effluent enriched in free fatty acids, and optionally containing fatty acid esters, produced during step a) during which the free fatty acids are separated from the alcohols, inorganic impurities and / or residual water present in this first effluent. This treatment step b) may be carried out in a treatment zone comprising one or more separation and / or purification zones.

[0121] This treatment zone may comprise, for example, a separation tank making it possible to separate at least a portion of an aqueous phase containing the residual alcohols as well as the contaminants dissolved in the water initially contained in the first effluent, and the first purified effluent containing the free fatty acids.

[0122] The treatment zone may comprise a water washing zone, preferably implemented in a contactor, typically upstream of the separation tank when present.

[0123] Preferably, the treatment zone may comprise, for example, a contactor for washing the first effluent with water followed by a separation tank for separating at least a portion of an aqueous phase containing the residual alcohols as well as the contaminants dissolved in the water initially contained in the first effluent, and the first purified effluent containing the free fatty acids.

[0124] The treatment zone may comprise a guard bed purification zone, typically downstream of the separation tank when it is present, making it possible to retain inorganic impurities present in the effluent.

[0125] This optional purification step may also include a demetallation step (HDM) implemented upstream of the hydroconversion or at the top of the latter, typically downstream of the separation tank. This demetallation may be carried out in one or more guard reactors containing a suitable catalyst located upstream of the hydroconversion or by means of one or more guard beds positioned at the entrance to the hydroconversion zone.

[0126] Cl step of hydroconversion

[0127] During this step, the first effluent leaving step a), or the first purified effluent leaving step b), alone or in a mixture with another part of said hydrocarbon feedstock of fossil origin, are brought into contact with dihydrogen in a hydroconversion zone in the presence of at least one catalyst under conditions suitable for transforming the free fatty acids of the first effluent into paraffins and for carrying out a hydroconversion of the feedstock of fossil origin. This hydroconversion step produces a hydroconverted effluent which thus comprises components of fossil origin and components of natural origin. During this step, the free fatty acids, and optionally the fatty acid esters, present in the first effluent are converted into paraffins.

[0128] When the entire hydrocarbon feedstock of fossil origin to be treated has not been introduced into the hydrolysis zone during step a), the remainder of the feedstock to be treated is thus introduced into the hydroconversion zone of step c).

[0129] In this case, the hydrocarbon feedstock of fossil origin and the first effluent, optionally purified, can be introduced into the hydroconversion zone separately or as a mixture.

[0130] The hydroconversion step is typically carried out in a hydroconversion zone comprising one or more reactors. Any type of reactor usually used for this type of reaction may be used, for example a fixed bed reactor, an ebullated bed reactor, a slurry reactor, etc. The hydroconversion zone may in particular comprise one or more catalysts promoting the hydroconversion step.

[0131] The quantity of first effluent, purified or not, introduced into the hydroconversion zone can advantageously represent 0.5 to 100% by mass, preferably 0.5 to 90% by mass, more preferably 0.5 to 50% by mass, more preferably 0.5 to 25% by mass of the total feedstock introduced into the hydroconversion zone.

[0132] This hydroconversion step may comprise, or consist of, a step hydrodesulfurization, a hydroisomerization step, a hydrocracking step, a hydrotreatment step, or two or more of these steps.

[0133] The hydroconversion treatment may comprise hydrodesulfurization, hydrocracking, hydroisomerization or hydrotreatment of a hydrocarbon feedstock of fossil origin chosen from a naphtha cut, a diesel cut, a kerosene cut and a distillate cut.

[0134] The hydroconversion treatment may for example be chosen from (i) hydrodesulfurization of a diesel cut of fossil origin, (ii) hydrodesulfurization of a kerosene cut of fossil origin, (iii) hydrocracking of distillates of fossil origin, (iv) hydrotreatment of a kerosene cut of fossil origin, (v) hydroisomerization of a kerosene or diesel cut of fossil origin.

[0135] 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.

[0136] In the context of hydrocracking, the hydrocarbons of fossil origin are advantageously one or more distillate cuts, preferably originating from the direct distillation of crude oil.

[0137] In the context of hydrodesulfurization, the hydrocarbons of fossil origin are advantageously one or more kerosene cuts or one or more diesel cuts, preferably originating from the direct distillation of crude oil.

[0138] In the context of hydroisomerization, the hydrocarbons of fossil origin are advantageously one or more kerosene or diesel cuts.

[0139] The catalyst may be chosen from (i) oxides, phosphides or sulfides of Ni, Mo, W, Co or mixtures of NiW, NiMo, CoMo, NiCoW, NiCoMo, NiMoW and CoMoW, (ii) metals or mixtures of metal alloys from group 10 and group 11 of the periodic table, (iii) basic oxides such as alkali metal oxides, alkaline earth oxides, lanthanide oxides, zinc oxide, spinels, perovskites, calcium silicates.

[0140] The catalyst may have a supported or unsupported catalytic active phase.

[0141] When the catalyst comprises a support for the catalytic active phase, it is preferable that the support has a high specific surface area. In one embodiment, the specific surface area must be at least 5 m2 / g, preferably at least 50 m2 / g and more preferably at least 75 m2 / g, this specific surface area can be measured by methods known in the art such as the BET method where nitrogen adsorption makes it possible to estimate the specific surface area of ​​the solid material.

[0142] It is also preferable that the support of the catalytic active phase has a low acidity, preferably neutral or basic, in order to avoid hydroisomerization reactions which would give rise to branched paraffins and to cracking at high temperature and pressure in the presence of dihydrogen.

[0143] The hydroconverted effluent leaving the hydroconversion zone typically comprises a liquid part and a gaseous part. The liquid part essentially comprises a mixture of n-paraffins, typically comprising from 5 to 60 carbon atoms. The gaseous part comprises H2, H2S, CO2, and optionally CO, NH3. The hydrotreated effluent further contains water.

[0144] During this hydroconversion step, the fatty acid esters and the free fatty acids contained in the first effluent (purified or not) are transformed into paraffins, in particular into linear or substantially linear paraffins, via hydrodeoxygenation and / or decarboxylation and / or decarbonylation reactions:

[0145] hydrodeoxygenation (HDO), removes oxygen from the treated oils and leads to the formation of linear paraffins while preserving the number of carbons of the initial fatty chains and is accompanied by the formation of water and propane, this reaction can be carried out on fatty acid esters, free fatty acids or their mixtures;

[0146] a decarboxylation and / or a decarbonylation (DCOX), leads to the formation of paraffins comprising one carbon atom less than the initial fatty chain and is accompanied by the formation of carbon oxides (CO and CO2) and propane, this reaction can be carried out on glycerides, any esters or with free fatty acids.

[0147] The hydroconverted effluent thus comprises a hydroconverted liquid fraction enriched in paraffins of natural origin and a fraction of non-condensable components. Paraffins of natural origin typically comprise from 9 to 24 carbon atoms, depending on the biological origin feedstock used.

[0148] The hydroconversion step may be carried out at a temperature of 100 to 550°C in the presence of dihydrogen at pressures ranging from 0.01 to 25 MPa. The ratio of dihydrogen to feedstock may be from 50 to 3000 Nl / l.

[0149] The hydroconversion step can be implemented under hydrocracking conditions, in particular to treat a hydrocarbon feedstock of heavy fossil origin, such as a distillate cut.

[0150] The reactions carried out under hydrocracking conditions are typically hydrotreatment reactions (hydrodesulfurization, denitrogenation, catalytic hydrogenation) and the hydrocracking reactions themselves (cleavage of CC bonds) or CC rearrangement (hydroisomerization).

[0151] Typical hydrocracking conditions include a temperature of 250 to 480°C, a hydrogen partial pressure of 1.5 to 25 MPa abs. and an hourly volumetric flow rate of 0.1 to 10 h *.

[0152] Typical hydrocracking conditions generally include a dihydrogen level of 100 to 3000 Nm3 / m3 of feed.

[0153] The catalyst used is a typical hydrocracking catalyst. It is generally a bifunctional catalyst comprising a hydro-dehydrogenating function and an acid function.

[0154] A usable hydrocracking catalyst comprises, for example, a support chosen from halogenated aluminas, combinations of boron and aluminum oxides, amorphous silica-aluminas and zeolites and a hydro-dehydrogenating function comprising at least one metal from group 6 chosen from chromium, molybdenum and tungsten, alone or as a mixture, and / or at least one metal from groups 8, 9, 10 chosen from iron, cobalt, nickel, ruthenium, rhodium, palladium and platinum.

[0155] The hydroconversion step can be implemented under hydrodesulfurization conditions, in particular to treat a hydrocarbon feedstock of fossil origin such as a diesel cut or kerosene cut.

[0156] The reactions carried out under hydrodesulfurization conditions are typically hydrotreatment reactions (hydrodesulfurization, denitrogenation, catalytic hydrogenation). Hydrodesulfurization reactions are characterized by the breaking of the CS bonds of the sulfur derivatives contained in petroleum, namely mercaptans, sulfides and thiophene compounds.

[0157] Typical hydrodesulfurization conditions include a temperature of 320 to 420°C, preferably 320°C to 400°C, a hydrogen partial pressure of 1 to 15 MPa abs. and an hourly volumetric flow rate of 0.3 to 5h*.

[0158] Typical hydrodesulfurization conditions generally include a dihydrogen level of 100 to 2000 Nm3 / m3 of feed.

[0159] A conventional catalyst promoting hydrodesulfurization reactions may be used. An example of a usable catalyst comprises a catalyst based on metal oxides chosen from oxides of metals from group 6 (Mo, W, etc.) and 8-10 (Co, Ni, Pt, Pd, Ru, Rh, etc.) supported on a support chosen from alumina, silica-alumina, zeolite, ferrierite, phosphated alumina, phosphated silica-alumina, etc., preferably oxides, phosphides or sulfides of Ni, Mo, W, Co, NiW, CoMo, NiMo, NiCoMo, NiWMo, NiCoW, or CoWMo, or PtPd, or a mixture of two or more of these. The most widespread industrial catalysts are of the Co-Mo (cobalt-molybdenum) and Ni-Mo (nickel-molybdenum) type on alumina support.

[0160] The hydroconversion step can be implemented under hydrotreatment conditions, in particular to treat a hydrocarbon feedstock of fossil origin such as a kerosene cut.

[0161] Typical hydrotreatment conditions include a temperature of 250 to 380°C, preferably 280 to 340°C, a hydrogen partial pressure of 1 to 15 MPa.

[0162] Typically, it will be possible to provide an hourly volumetric velocity of the liquid of 0.2 to 9 hr-1, preferably 0.5 to 7 hr-1, and more preferably 0.8 to 1.8 hr-1, and a di-hydrogen ratio: 50 to 1500 Nm3 / m3 of charge, preferably 120 to 250 Nm3 / m3 and more preferably 120 to 200 Nm3 / m3.

[0163] Typical hydrotreating conditions generally include a dihydrogen level of 120 to 1800 Nm3 / m3 of feed.

[0164] 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 carbon oxides, molecular sieves, salts or alkaline earth metals. When a support is present, it advantageously has a specific surface area varying from 100 to 550 m2 / g, preferably from 150 to 300 m2 / g.

[0165] Advantageously, the catalyst may comprise at least two or three oxides, phosphides or sulfides of metals from groups 6, 9, 10, 11 of the periodic table of elements, preferably at least two or three oxides, phosphides or sulfides of metals such as Ni, Mo, W, Co, NiW, CoMo, NiMo, NiCoMo, NiWMo, NiCoW or CoWMo, preferably on an alumina support.

[0166] The hydroconversion zone may advantageously comprise at least one catalytic bed containing at least in part a catalyst with an isomerizing and / or hydrocracking function, based on oxides, phosphides or sulfides of Ni, Mo, W, Co, NiW, CoMo, NiMo, NiCoMo, NiWMo, NiCoW or CoWMo or precious metals such as Pt, Pd or mixtures, and preferably oxides, phosphides or sulfides of Ni, Mo, W, Co, NiW, CoMo, NiMo, NiCoMo, NiWMo NiCoW or CoWMo on an acid support. Catalytic beds containing oxides, phosphides or sulfides of Ni, Mo, W, Co, NiW, CoMo, NiMo, NiCoMo, NiWMo NiCoW or CoWMo or precious metals such as Pt, Pd or mixtures on acidic support have the advantage of promoting isomerization reactions, which can improve, i.e. reduce, the cloud point of the finished product.This type of catalyst with an isomerizing function is advantageously placed just before the exit from the hydroconversion zone. The presence of a catalyst with an isomerizing function is particularly advantageous when the hydroconversion step is a hydrodesulfurization step.

[0167] The hydroconversion step can be carried out under hydroisomerization and / or hydrocracking conditions.

[0168] Suitable hydroisomerization and / or hydrocracking catalysts used in hydroisomerization and / or hydrocracking processes are typically all of the bifunctional type combining an acid function with a (de)hydrogenating function.

[0169] The acid function is typically provided by a support (amorphous or crystalline) whose specific surfaces are generally between 100 and 700 m2 / g and which has a surface acidity, such as halogenated aluminas (in particular sulfated, phosphated, chlorinated or fluorinated), aluminas (possibly containing boron), amorphous silica-aluminas, amorphous silica-aluminas-titaniums, phosphated alumina or phosphated silica-alumina, sulfated zirconas, tungsten zirconas and zeolites or mixtures thereof. The acidity can be measured by methods well known to those skilled in the art. It can, for example, be measured by temperature-programmed desorption (TPD) with ammonia, by infrared measurement of the absorbed molecules (pyridine, CO . . .), by a catalytic cracking test or by hydroconversion using a model molecule.

[0170] Hydroisomerization catalysts have a weak acid function, preferably halogenated aluminas (in particular sulfated, phosphated, chlorinated or fluorinated), aluminas (possibly containing boron), amorphous silica-aluminas, phosphated alumina or phosphated silica-alumina and amorphous silica-aluminas-titaniums.

[0171] Hydrocracking catalysts have a strong acid function, preferably sulfated zirconias, tungsten zirconias and zeolites or their mixtures.

[0172] The (de)hydrogenation function is typically provided either by one or more metals from group 6 of the periodic table of elements, or by a combination of at least one metal from group 6 of the periodic table and at least one metal from groups 8, 9, 10. The distance between the two functions, acid and (de)hydrogenating, is one of the key parameters governing the activity and selectivity of the catalyst.

[0173] A weak acid function and a strong (de)hydrogenating function give low activity catalysts, generally requiring a high temperature (greater than or equal to 390-400°C), and long residence times or low hourly space velocity (the VSLH expressed as liquid volume of feedstock to be treated per unit volume of catalyst and per hour is generally less than or equal to 2), but have very good selectivity for middle distillates (jet fuels and diesels). Generally, the term "middle distillates" as used in the present invention applies to one or more fractions whose initial boiling point is at least 150°C and whose end point is generally less than about 350°C, preferably less than 370°C.

[0174] Conversely, a strong acid function and a weak (de)hydrogenating function give catalysts which are active, but which have a lower selectivity for the middle distillates and the result is more cracked hydrocarbons in the naphtha and jet fuel range.

[0175] One type of conventional hydroisomerization catalyst is based on amorphous supports that are moderately acidic, such as silica-aluminas for example. These systems are used to maximize middle distillates with good cold flow properties.

[0176] One type of conventional hydrocracking catalyst is based on crystalline supports such as zeolites and sulfated zirconias which are strongly acidic, such as zeolites for example. These systems are used to reduce the number of carbons in the chain having good cold flow properties. Hydrocracking produces non-condensable gases, naphtha, kerosene and diesel.

[0177] The catalysts and conditions for hydroisomerization and / or hydrocracking are well known in the art.

[0178] The hydrocarbons are contacted with a hydroisomerization and / or hydrocracking catalyst in the presence of dihydrogen under hydroisomerization and / or hydrocracking conditions to isomerize and / or hydrocrack the normal paraffins into branched and / or shorter paraffins. The hydroisomerization and / or hydrocracking of the paraffinic product may be accomplished in any manner known in the art or by using any suitable catalyst known in the art.

[0179] The acidic support material may be amorphous or crystalline. Suitable support materials include amorphous alumina, amorphous silica-alumina, amorphous silica borate, amorphous silica-alumina-titanium, zeolites or modified zeolites having the following structures: ferrierite, zeolite beta, zeolite Y, zeolite mordenite and molecular sieves of the type SAPO-11, SAPO-31, SAPO-37, SAPO-41, SM-3, MgAPSO-31, FU-9, NU-10, NU-23, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48, ZSM-50, ZSM-57, theta-1, EU-1, EU-13, ISL1, KZ-2, ISL4 and KZ-1, MeAPO-11, MeAPO-31, MeAPO-41, MeAPSO-11, MeAPSO-31, MeAPSO-41, MeAPSO-46, ELAPO-11, ELAPO-31, ELAPO-41, ELAPSO-11, ELAPSO-31, ELAPSO-41, each of which may be used alone or in combination.

[0180] The production of the bifunctional hydroisomerization and / or hydrocracking catalyst can be carried out by any method known in the art. The (de)hydrogenation function can be added to the acid support by impregnation of metal-containing solutions, by ion exchange and by mixing.

[0181] During a hydroisomerization reaction, hydrocracking side reactions may occur. Similarly, during a hydrocracking reaction, hydroisomerization may occur. Those skilled in the art will know how to choose appropriate conditions for treating the effluent under hydroisomerization conditions, respec tively under hydrocracking conditions, namely conditions in which predominantly hydroisomerization reactions, respectively hydrocracking reactions, occur.

[0182] Separation step d)

[0183] The hydroconverted effluent from step c) is subjected, in part or in whole, before being optionally sent to step e), to a separation step d) in which the non-condensable components such as propane, CO2, CO, methane, dihydrogen and vaporized water are separated from the liquid fraction.

[0184] In one embodiment, the dihydrogen may be separated from the other non-condensable components and returned in part or in whole to the hydrolysis step a) to be dissolved in the reaction mixture. This may make it possible to promote the hydroconversion reaction of step c). Alternatively or in combination, the dihydrogen may be separated and returned, in part or in whole, to the inlet of step c).

[0185] In one embodiment, the effluent from step c) can thus be separated into:

[0186] - a gaseous flow containing H2, H2S, CO2, and possibly small quantities of CO and NH3,

[0187] - water,

[0188] - a hydroconverted liquid fraction.

[0189] This separation can be implemented in a high pressure separator.

[0190] The gas stream may undergo further treatment to separate the dihydrogen from the other gases for reuse in the process.

[0191] The liquid fraction can be sent to a steam stripping column to separate the gases still present in the liquid fraction.

[0192] The liquid fraction may then be fractionated into at least one fraction chosen from a naphtha fraction, a diesel fraction and a kerosene fraction, for example during a subsequent fractionation step e).

[0193] This separation step d), implemented in a separation zone, may be a high-pressure separation, a flash separation and / or be carried out in a stripping section. Depending on the operating conditions, part of the remaining water may be condensed and removed in this step by decantation or drainage, for example in a high-pressure separator. The flash separation and the removal of the liquid water may be carried out simultaneously or not.

[0194] In particular, a separator tank may be provided for separating the water, the gases and a liquid organic phase, the latter then being sent to a stripping section to remove the light hydrocarbons. The gases may be sent to a treatment section, for example to amines, to separate the dihydrogen from the other gaseous components.

[0195] The water produced in the hydroconversion may be used in step a) of hydrolysis or in purification step b) and thus reduce the net need for water to carry out this step a) and / or b).

[0196] Step e) of fractionation

[0197] In one embodiment of the invention, the process for manufacturing hydrocarbon fluids may further comprise a fractionation step e) in which the effluent from step d) is separated into at least one fraction chosen from a naphtha fraction, a diesel fraction and a kerosene fraction.

[0198] The effluent leaving step d) may undergo fractionation, for example carried out by adding a separation column, for example a distillation column, or by lateral withdrawal.

[0199] This fractionation makes it possible to recover at least one fraction chosen from a naphtha fraction, a diesel fraction and a kerosene fraction. This fractionation step can also make it possible to separate non-condensable fractions and / or unreacted dihydrogen, which can optionally be sent to the inlet of step c).

[0200] The recovered naphtha fraction preferably has an initial boiling point of 30°C and a final boiling point of 80°C to 220°C. This fraction can be used as fuel for combustion engines, in particular without the addition of other components such as esters. This fraction can be used as a feedstock for a steam cracker, in particular to produce olefins such as ethylene and propylene.

[0201] The recovered diesel fraction preferably has an initial boiling point of 180 to 240°C and a final boiling point of less than or equal to 360°C. This fraction can be used as fuel for diesel engines, in particular without the addition of other components such as esters.

[0202] The recovered kerosene fraction preferably has a final boiling point of less than 300°C. The initial boiling point may be 120 to 185°C. The kerosene fraction may be used as jet fuel, in particular without the addition of other components such as esters.

[0203] In particular, the cutting points of the recovered fractions can be adapted in order to obtain products meeting particular specifications, in particular without having to add other components such as esters. Detailed description of the figures

[0204] Other features and advantages of the invention will emerge from reading the description given below of a particular embodiment of the invention, given for informational purposes but not as a limitation, with reference to the appended drawings in which:

[0205] [Fig.l] schematically represents a unit for manufacturing hydrocarbon fluids according to one embodiment of the invention.

[0206] [Fig.l] represents a hydrocarbon fluid manufacturing unit 100 comprising a hydrolysis zone 10, a hydroconversion zone 20, a separation zone 30 and a fractionation zone 40. Depending on the objective sought, the fractionation zone 40 can be omitted.

[0207] The hydrolysis zone 10 may be a co-current mixer reactor or a counter-current reactor, preferably a counter-current reactor. The feedstock of natural origin to be treated enters the hydrolysis zone 10 via a first pipe 1. This feedstock is a hydrocarbon feedstock of natural origin containing fatty acid esters as previously defined, and typically containing fatty acid triglycerides and / or fatty acid alkyl esters. This feedstock may be introduced at a temperature above 150°C but preferably below 250°C.

[0208] Via the same pipe 1 or another pipe 2, another feedstock can optionally be co-processed. This other feedstock is for example a liquefaction oil of a hydrocarbon feedstock, namely a biomass oil and / or a plastic oil, introduced upstream of the feedstock of natural origin relative to the direction of circulation thereof.

[0209] According to the invention, a feedstock of fossil origin is introduced via a pipe 3, upstream of the feedstock of natural origin relative to the direction of circulation thereof. In the example shown, the hydrolysis zone is counter-current, the water circulating from top to bottom and the hydrocarbon feedstocks from bottom to top. Thus, in the example, the feedstock of natural origin and the feedstock of fossil origin, as well as the liquefaction oil when present, circulate from bottom to top in the hydrolysis zone 10.

[0210] Water, typically at a temperature of at least 250°C, is introduced into the hydrolysis zone 10 via a line 4. In the example, an optional line 5 allows steam to be introduced.

[0211] At the outlet of the hydrolysis zone 10, a first effluent enriched in free fatty acids formed during the hydrolysis is recovered via a pipe 6 and a second effluent which is an aqueous phase containing the majority of the alcohols produced during the hydrolysis via a pipe 7. This aqueous phase also contains a majority of the pollutants initially contained in the hydrocarbon feedstock of natural origin.

[0212] The organic phase is then sent to a hydroconversion zone 20 of a hydrocarbon feedstock of fossil origin to be hydrotreated there in coprocessing with the latter and to produce a hydroconverted effluent discharged via line 8.

[0213] The hydroconversion zone 20 thus comprises a pipe 9 for supplying di-hydrogen, a pipe 23 for possibly introducing the remainder of the fossil-origin feedstock to be treated, and one or more catalytic beds. The hydroconversion zone 20 may comprise one or more reactors operated in series, or in parallel or both.

[0214] In the example shown, the pipe 23 is connected to the pipe 6 before it enters the hydroconversion zone 20, so that the two feeds enter the latter as a mixture. However, it could be provided that these pipes 6 and 23 are each connected directly to the hydroconversion zone.

[0215] The hydroconverted effluent comprises a liquid fraction enriched in paraffins of natural origin, and a fraction of non-condensable components.

[0216] In the example shown, the unit 100 also comprises an optional separator tank 11 located on the pipe 6 for discharging the first effluent enriched in free fatty acids. This separator tank makes it possible to condense a portion of the water contained in the first effluent, as well as the alcohols and pollutants present in this water, discharged via a pipe 12. It is then a first effluent enriched in free fatty acids and having a reduced content of water, alcohols and pollutants which enters the hydroconversion zone 20.

[0217] In the embodiment shown, the hydroconversion zone 20 further has at least one catalytic bed 21 dedicated to demetallation (guard bed) and making it possible to eliminate chlorine, metals and silicon. Isolated, lead-lag, series and / or parallel guard reactors may be envisaged depending on the nature and quantity of contaminants in the flow to be treated. Depending on the pollutant content of the first effluent, one or more guard beds may be provided. It is also possible not to provide a guard bed.

[0218] In the embodiment shown, the hydroconversion zone 20 also has a catalytic isomerization zone 22 comprising at least one isomerizing catalytic bed in order to carry out an isomerization of at least a portion of the n-paraffins. This catalytic zone is preferably located in the immediate vicinity of the outlet of the hydroconversion zone so that it is the last catalytic zone crossed by the effluent.

[0219] Note that depending on the fossil feedstock treated, the composition of the first effluent and the desired objective, the guard bed and / or the catalytic isomerization zone may or may not be present.

[0220] The separator tank 11 and / or the guard bed(s) 21 are part of an optional purification zone 15 implementing the optional purification treatment step b),

[0221] At the outlet of the hydroconversion zone 20, the hydroconverted effluent discharged via the pipe 8 comprises a hydroconverted liquid fraction enriched with paraffins of natural origin and a fraction of incondensable components. In this embodiment, the hydroconverted effluent is sent to a separation zone 30 comprising a separator drum 31 and a stripping column 32. The separator drum separator 31 makes it possible to separate the water present in the effluent via a pipe 33 and non-condensable gases (G) via a pipe 34. Note that the water recovered via the pipe 33 could be returned to the hydrolysis zone 10, optionally after having undergone treatment in order to reduce its acidity.

[0222] The liquid organic phase leaves the flask 31 via a pipe 35 to enter the stripping column 32 into which steam is introduced via a pipe 36. The gases are evacuated from the stripping column 32 via a pipe 37 and the liquid fraction is recovered at the bottom of the column 32 via the pipe 38.

[0223] This liquid fraction is brought to a fractionation zone 40 via the pipe 38.

[0224] The fractionation zone 40, for example a distillation column, makes it possible to separating the effluent entering via line 38 into several streams discharged via lines 41, 42, 43, typically a naphtha fraction, a kerosene fraction and a diesel fraction.

[0225] Examples of temperatures and pressures of circulating effluents are given in [Fig.l].

Claims

Claims

1. A method of pretreatment by hydrolysis of a hydrocarbon feedstock of natural origin containing fatty acid esters, in which: - said hydrocarbon feedstock of natural origin is brought into contact with water in a hydrolysis zone (10) to produce a first effluent enriched in free fatty acids, optionally containing fatty acid esters, and a second effluent rich in alcohol and water, said method being characterized in that a diluent consisting of a hydrocarbon feedstock of fossil origin is introduced into the hydrolysis zone, introduced upstream of the hydrocarbon feedstock of natural origin relative to the direction of circulation thereof.

2. Pretreatment process according to claim 1, characterized in that the hydrocarbon feedstock of fossil origin is chosen from a naphtha cut, a kerosene cut, a diesel cut, a distillate cut.

3. Pretreatment process according to claim 1 or 2, characterized in that the quantity of diluent introduced into the hydrolysis zone represents 0.5 to 150% by mass of the total charge introduced into said zone.

4. Pretreatment process according to any one of claims 1 to 3, characterized in that the diluent is introduced into the hydrolysis zone at a temperature of 200°C to 350°C.

5. A method of pretreating any one of claims 1 to 4, characterized in that the hydrocarbon feedstock of natural origin containing fatty acid esters comprises an oil of natural origin, an esterified oil of natural origin or mixtures thereof.

6. Pretreatment method according to any one of claims 1 to 5, characterized in that at least one liquefaction oil of a hydrocarbon feedstock chosen from a biomass oil and a plastics oil is also introduced into said hydrolysis zone, the at least one liquefaction oil of a hydrocarbon feedstock representing at most 10% by mass of the hydrocarbon feedstock of natural origin, and being introduced into said hydrolysis zone upstream of the injection of the hydrocarbon feedstock of natural origin relative to the direction of circulation of the hydrocarbon feedstocks in the hydrolysis zone.

7. Pretreatment process according to any one of claims 1 to 6, characterized in that the hydrolysis is carried out under one or more of the following conditions: - a temperature of 130 to 350 °C, - a pressure of 7 to 100 barg, - a water / natural hydrocarbon feedstock mass ratio of 0.1 to 2.

0.

8. A method for manufacturing hydrocarbon fluids from a hydrocarbon feedstock of natural origin containing fatty acid esters and a hydrocarbon feedstock of fossil origin, said method comprising at least: a) a pretreatment step by hydrolysis carried out according to the pretreatment method of any one of claims 1 to 7, in which said hydrocarbon feedstock of natural origin is brought into contact with water in the presence of at least a portion of said hydrocarbon feedstock of fossil origin in a hydrolysis zone (10) to produce a first effluent enriched in free fatty acids, optionally containing fatty acid esters, and a second effluent rich in alcohol and water, b) an optional step of separation and / or purification of the first effluent enriched in free fatty acids from step a) during which the alcohols are removed from the first effluent,residual inorganic impurities and / or water to obtain a first purified effluent, c) a hydroconversion step, in which the first effluent from step a), optionally purified in step b), is brought into contact alone or in a mixture with another part of said hydrocarbon feedstock of fossil origin, with dihydrogen in a hydroconversion zone (20) in the presence of at least one catalyst under conditions suitable for carrying out a hydroconversion and forming a hydroconverted effluent comprising a hydroconverted liquid fraction and a fraction of incondensable components, d) a step of separating the hydroconverted effluent from step c) during which the fraction of incondensable components is separated from the hydroconverted liquid fraction.,

9. Process for manufacturing hydrocarbon fluids according to claim 8 further comprising: e) a step e) of fractionating the hydroconverted liquid fraction of step d), in which said hydroconverted liquid fraction is separated into at least one liquid fraction chosen from a naphtha fraction, a diesel fraction and a kerosene fraction.

10. Manufacturing method according to any one of claims 8 to 9, characterized in that the quantity of first effluent introduced into the hydroconversion zone (20) represents 0.5 to 100% by mass, preferably 0.5 to 90% by mass, more preferably 0.5 to 50% by mass, more preferably 5 to 25% by mass of the total feedstock introduced into the hydroconversion zone.

11. Manufacturing process according to any one of claims 8 to 10, characterized in that at least a part of the incondensable components separated in step d) are sent to the hydrolysis zone, optionally after removal of the components other than dihydrogen.

12. Manufacturing unit (100) for hydrocarbon fluids from a hydrocarbon feedstock of natural origin containing fatty acid esters and a hydrocarbon feedstock of fossil origin, comprising: - a hydrolysis zone (10) comprising at least a first inlet pipe (1) for the hydrocarbon feedstock of natural origin containing fatty acid esters, a second inlet pipe (4, 5) for water, a third inlet pipe (3) for the hydrocarbon feedstock of fossil origin, a first outlet pipe (6) for a first effluent and a second outlet pipe (7) for a second effluent, and optionally an additional inlet pipe (2), - an optional separation and / or purification treatment zone (15) connected to the first outlet pipe (6) of the hydrolysis zone,- a hydroconversion zone (20) comprising at least one inlet connected to the first outlet pipe (6) of the hydrolysis zone or to an outlet of the optional treatment zone (15), an inlet pipe (9) for a gas containing dihydrogen, optionally an inlet pipe (23) for a feedstock of fossil origin, and an outlet pipe (8) for a hydroconverted effluent, - a separation zone (30) connected to the outlet pipe (8) of the hydroconversion zone, characterized in that the third inlet pipe (3) opens into the hydrolysis zone in a position located upstream of the first inlet pipe (1) relative to a direction of circulation of the hydrocarbon feedstocks in the hydrolysis zone.,

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