PROCESS FOR MANUFACTURING HYDROCARBONATE FLUIDS WITH DIHYDROGEN PRODUCTION AT LEAST PART-INTEGRATED

Abstract

METHOD FOR MANUFACTURING HYDROCARBON FLUIDS WITH AT LEAST PART-INTEGRATED DIHYDROGEN PRODUCTION The invention relates to a method for manufacturing hydrocarbon fluids, in particular paraffins, from a hydrocarbon feedstock of natural origin containing at least 50% by mass of glycerides, said method comprising: a) a step of hydrolysis of the hydrocarbon feedstock of natural origin, b) a step of recovery of the products of step a) separating a first effluent containing free fatty acids and a second effluent containing alcohols and water, c) a step of hydrotreating said first effluent to transform the free fatty acids into paraffins, e) a step of reforming in aqueous phase the second effluent recovered in step b) during which at least a part of the alcohols it contains is converted into dihydrogen, carbon dioxide and carbon monoxide, f) a step of separation of the dihydrogen formed during step e),The separated dihydrogen is sent to step c) hydrotreatment, and optionally to a step d) hydroisomerization and / or hydrocracking of the hydrotreated effluent. Abbreviated figure: Figure 1.

Description

Title of the invention: METHOD FOR MANUFACTURING HYDROCARBONATE FLUIDS WITH DIHYDROGEN PRODUCTION AT LEAST PART-INTEGRATED Technical field

[0001] The present invention relates to a process for manufacturing hydrocarbon fluids from complex mixtures of renewable hydrocarbons with at least partially integrated dihydrogen production. In particular, the present invention relates to a process for converting a biological feedstock comprising fatty acid esters (FAEs) into free fatty acids (FFAs) and subsequently into oxygen-free paraffinic compounds, which can be used as fuels. The process according to the invention comprises a series of steps enabling the production of at least a portion of the dihydrogen required for the hydrotreating of renewable hydrocarbons. Background of the invention

[0002] Due to the depletion of fossil resources and growing environmental concerns, the use of molecules derived from biomass is increasingly sought after to replace fossil-based molecules. In particular, the regulation on levelling competition 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 fuel used in the European Union must be of renewable origin. Therefore, the production of jet fuel, or other hydrocarbon fuels or fluids, from molecules derived from biomass represents a significant economic, environmental, and strategic challenge. Prior art

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

[0004] A well-known process for manufacturing renewable fuels and other hydrocarbon fluids involves subjecting vegetable or animal fat or oil to hydrotreatment in the presence of dihydrogen and a catalyst, typically leading to hydrodeoxygenation, generally followed by hydroisomerization to obtain the required cold-weather properties. In this case, the term used is not biodiesel, which is reserved for fuels produced by transesterification, but rather renewable fuel.

[0005] This hydrotreatment step is often preceded by a pretreatment step by hydrolysis.

[0006] For example, documents WO 2015 / 181279 and US 8 686 198 describe processes for producing hydrocarbons from mixtures of biological origin containing glycerides by hydrolysis, hydrodeoxygenation and hydroisomerization.

[0007] In the first hydrolysis step, water is brought into contact with the glycerides to produce free fatty acids and glycerol. The free fatty acids are then subjected to hydrodeoxygenation, followed by hydroisomerization to produce isoparaffins. The hydrodeoxygenation of free fatty acids is less exothermic than the hydrodeoxygenation of glycerides, thus limiting the need for a recycler to control the exothermicity of the reaction. Furthermore, the hydrodeoxygenation of fatty acids limits propane production, unlike the hydrodeoxygenation of glycerides, thereby reducing the dilution of dihydrogen by propane and thus reducing the propane ballast in the unconverted dihydrogen stream to be recycled, or the need to separate the dihydrogen-propane gas mixture before recycling the unconverted dihydrogen.The hydrolysis step also purifies the feedstock by reducing its content of alkali metals, alkaline earth metals, and other heteroatoms such as phosphorus. Finally, the hydrolysis step limits the hydrogen consumption during the hydrotreating step. However, expensive hydrogen must be supplied for both hydrotreating and hydrodeoxygenation.

[0008] Furthermore, when the hydrolysis reaction is complete, a by-product consisting of a glycerol / water / contaminant mixture is formed. This by-product is generally considered waste. It is possible to recover the glycerol it contains, but this recovery, particularly in the food or pharmaceutical sectors, requires costly purification and separation steps.

[0009] Document CN109868151A describes a process for preparing green diesel in one This single-pot process uses used oil. The following reactions then occur in the same reactor: hydrolysis of the glycerides in the used oil, producing fatty acids and glycerol; aqueous reforming of the glycerol to produce hydrogen and carbon dioxide; conversion of unsaturated fatty acids to saturated fatty acids by hydrogenation; and decarboxylation of the saturated fatty acids to produce green diesel. However, this one-pot process raises several issues. In particular, impurities (contaminants and / or gums) present in the used oil remain in the reactor and can foul the catalyst used for hydrotreating and / or clog the installation. Furthermore, this process appears to be better suited to batch operation than continuous operation.

[0010] There is therefore a need to improve existing processes, in particular to valorize by-products by limiting the external supply of dihydrogen required for hydro treatment.

[0011] Description of the invention

[0012] The invention proposes a process for manufacturing hydrocarbon fluids, in particular paraffins, from a hydrocarbon feedstock of natural origin containing at least 50% by mass of glycerides, said process comprising: a. a step of hydrolysis of the naturally occurring hydrocarbon feedstock in which said naturally occurring hydrocarbon feedstock is brought into contact with water in a first reaction zone under conditions of total hydrolysis to produce free fatty acids, alcohols including glycerol, and water, b. a step for recovering the products of step a) in which a first effluent containing free fatty acids and a second effluent containing alcohols and water are extracted separately from the first reaction zone, c. a hydrotreating step, in which the first effluent recovered in step b) is contacted with dihydrogen in at least a second reaction zone in the presence of at least one catalyst under suitable conditions to transform the free fatty acids contained in the first effluent into paraffins and form a hydrotreated effluent containing paraffins, d. an optional hydroisomerization and / or hydrocracking step in which the hydrotreated effluent from step c) is subjected to a hydroisomerization and / or hydrocracking reaction in a hydroisomerization and / or hydrocracking zone in the presence of dihydrogen and at least one catalyst to produce an isomerized and / or hydrocracking effluent rich in isoparaffins, e. an aqueous phase reforming step of the second effluent recovered in step b) in a third reaction zone, during which at least some of the alcohols it contains are converted into dihydrogen, carbon dioxide and carbon monoxide, f. a step of separating the dihydrogen formed during step f), the dihydrogen thus separated being sent to step c) of hydrotreatment, and optionally to step d).

[0013] The process thus makes it possible to recover the alcohols, and in particular glycerol, produced during hydrolysis and to use them to produce at least part of the dihydrogen during the aqueous phase reforming step. Steps a), c), and d) are in particular implemented in separate reaction zones, which helps to preserve the catalyst from steps c) and d) and to avoid premature aging.

[0014] Advantageously, before being sent to the reforming step e), the second effluent recovered in step b) can be subjected to at least one purification treatment selected from (i) a solids removal step, such as gums, and (ii) a contaminant removal step, such as metals and / or salts. This can facilitate the implementation of the dihydrogen separation step.

[0015] Advantageously, step f) of dihydrogen separation may include at least one step selected from a membrane separation step, an adsorption separation step, in particular a pressure-modulated adsorption separation step, and a CO2 liquefaction step, preferably a pressure- or temperature-modulated adsorption separation step.

[0016] Regardless of the embodiment, step a) of 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 mass ratio of water / naturally occurring hydrocarbon load of 0.1 to 2, preferably of 0.25 to 1.5.

[0017] Advantageously, the naturally sourced hydrocarbon feedstock used in the pretreatment process may comprise, or be composed of, a naturally sourced oil. This naturally sourced oil may, in particular, be selected from vegetable oil, animal oil or fat, used oil, oil produced by microorganisms, and mixtures thereof. Used oil is preferred.

[0018] Advantageously, at least one liquefaction oil of a hydrocarbon feedstock selected from a biomass oil and a plastics oil may also be introduced into said first reaction zone, this at least one liquefaction oil of a hydrocarbon feedstock representing at most 10% by mass, preferably at most 5% by mass, and more preferably at most 1% by mass, of the naturally occurring hydrocarbon feedstock introduced into said first reaction zone. This may allow for the removal of some of the contaminants present in the liquefaction oil.

[0019] Advantageously, a diluent may be introduced into said first reaction zone, said diluent being selected from a fossil-based hydrocarbon feedstock, a portion or fraction of the hydrotreated effluent produced in step c), or a portion or fraction of the isomerized and / or hydrocracked effluent produced in step d) of hydroisomerization and / or hydrocracking. Preferably, the diluent is a recycle selected from a portion or fraction of the hydrotreated effluent produced in step c) and / or a portion or fraction of the isomerized and / or hydrocracked effluent. produced during step d) of hydroisomerization and / or hydrocracking when present.

[0020] Dilution with a hydrocarbon mixture thus achieved can better separate the polar / nonpolar phases present in the hydrolysis zone, thereby improving the hydrolysis reaction (for example, promoting the completion of the hydrolysis reaction). This dilution also reduces corrosion and improves the removal of impurities. In particular, the inorganic species of said feedstock will be detached from the fatty acid esters and preferably dissolve in the aqueous phase.

[0021] The amount of diluent introduced into said first reaction zone may advantageously represent 0.5 to 50% by mass of the feed to be treated introduced into said zone, said feed to be treated consisting of the feed of natural origin, and optionally the liquefaction oil. The diluent content may be determined to maintain a glyceride content of at least 50% by mass within the first reaction zone.

[0022] Advantageously, the diluent can be introduced into said first reaction zone at a temperature of 200 °C to 350 °C. This can notably be achieved without preheating the diluent when it is taken directly from the outlet of the second or third reaction zone, without intermediate cooling. In this case, the naturally occurring hydrocarbon feedstock can be introduced into said first reaction zone at a temperature of 50 to 250 °C.

[0023] Advantageously, a fossil-based hydrocarbon feedstock may be introduced in step c) and / or in step d) when this step is present. In a particular embodiment, the quantity of first effluent recovered in step b) and / or of hydrotreated effluent from step c) when step d) is present, may represent from 0.5 to 90% by mass, more preferably from 0.5 to 50% by mass, preferably from 5 to 25% by mass, of the total feedstock introduced in step c) and / or in step d) when this step is present. The process can then be integrated into a process for treating a fossil feedstock.

[0024] Advantageously, the process may further include a step g) for producing syngas containing dihydrogen. The syngas produced in step g) is then sent to the reforming step e) or the dihydrogen separation step f), preferably to step f). The dihydrogen separation step can then be carried out in a single separation unit processing both the gases produced in step f) and syngas produced by another production process. This pooling of equipment reduces manufacturing and operating costs and to increase the overall quantity of dihydrogen produced and usable in the present invention.

[0025] This step g) of syngas production may include a steam methane reforming step.

[0026] In a particularly advantageous embodiment, step g) of syngas production may comprise the following substeps: (i) a biogas production stage by biomass methanation, the biogas containing at least methane and CO2, (ii) an optional step of purifying the methane produced in step (i), (iii) a steam reforming step of the methane produced in step (i) or of the methane purified in step (ii).

[0027] The dihydrogen produced is then entirely produced from renewable resources. Detailed description of the invention

[0028] The terms "including" and "includes" as used herein are synonymous with "including", "includes" or "contains", "containing", and are inclusive or boundless and do not exclude additional features, elements or unspecified method steps.

[0029] The expressions % by weight and % by mass (also noted %m) have an equivalent meaning and refer to the proportion of the mass of a product relative to 100g of a composition comprising it.

[0030] Boiling points as mentioned herein are measured at atmospheric pressure, unless otherwise specified. An initial boiling point is defined as the temperature at which the first vapor bubble forms. A final boiling point is the highest temperature attainable during distillation. At this temperature, no more vapor can be transported to a condenser. The determination of the initial and final boiling points relies on techniques known in the trade, and several methods adapted according to the distillation temperature range are applicable, for example, NF EN 15199-1 (version 2020) or ASTM D2887 for measuring the boiling points of petroleum fractions by gas chromatography, ASTM D7169 for heavy hydrocarbons, and ASTM D7500, D86, or DI 160 for distillates.

[0031] Naturally occurring hydrocarbon filler

[0032] By "hydrocarbon feed of natural origin", we mean a hydrocarbon feed not containing components of fossil origin.

[0033] The naturally occurring hydrocarbon filler contains at least 50% by mass of glycerides, namely mono-, di- and / or triglycerides. The glyceride content of the The charge is typically 50 to 95% by mass, preferably 60 to 95% by mass, the remainder being typically free fatty acids and / or alkyl esters of fatty acids.

[0034] The naturally sourced hydrocarbon filler containing at least 50% by mass of glycerides used in the present invention may comprise, or consist of, a naturally sourced oil, an esterified naturally sourced oil or mixtures thereof, preferably a non-esterified naturally sourced oil.

[0035] The naturally sourced hydrocarbon filler used in the present invention may thus comprise, or consist of, a naturally sourced oil or a mixture of naturally sourced oils, esters resulting from the trans-esterification of fatty acid esters and / or the esterification of fatty acids contained in one or more naturally sourced oils, as well as mixtures thereof.

[0036] In a preferred embodiment, the naturally sourced hydrocarbon filler used in the present invention comprises only one or more non-esterified naturally sourced oils.

[0037] The naturally sourced hydrocarbon oil can be chosen from a vegetable oil, an animal oil or fat, a used oil, an oil produced by microorganisms, as well as mixtures thereof.

[0038] A naturally sourced oil is defined as an oil that does not contain mineral oil of fossil origin.

[0039] Typically, an oil of natural origin may contain more than 50%m, preferably 60%m or more, preferably 70%m or more, of fatty acids and fatty acid esters (mono-, di-, triglycerides).

[0040] In one embodiment, a naturally derived oil may contain fatty acid esters (mono-, di-, or triglycerides) and free fatty acids, containing one to three C8-C24 acyl groups, saturated or unsaturated. When several acyl groups are present, they may be identical or different.

[0041] The vegetable oil may be chosen from pine oil, rapeseed oil, sunflower oil, castor oil, peanut oil, linseed oil, babassu oil, hemp oil, linola oil, jatropha oil, peanut oil, rice bran oil, mustard oil, carinata oil, coconut oil, copra oil, olive oil, palm oil, cottonseed oil, corn oil, palm kernel oil, soybean oil, pumpkin seed oil, grapeseed oil, argan oil, jojoba oil, sesame oil, walnut oil, hazelnut oil, tung oil, rice oil, safflower oil, oil algae, used oils, nut shell oil (especially cashew nut shell oil), and any combination thereof.

[0042] Used oil includes used cooking oils or used food oils and oils recovered from wastewater, such as grease / Trap and drain oils, gutter oils, sewage oils, for example from wastewater treatment plants, used fats from the food industry, and used cooking oils which are animal by-products.

[0043] Animal fat can be chosen from tallow, lard, fat (yellow and brown fat), fish oil / fat, milk fat, animal fats which are animal by-products.

[0044] 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 of Commission Regulation (EU) No 142 / 2011 (implementing Regulation of EC No 1069 / 2009).

[0045] Animal fats having the status of animal by-product are fatty residues of animal origin, other than used cooking oils, coming for example from food industries or rendering plants.

[0046] Used cooking oils having the status of animal by-products are used cooking food oils (used cooking oils or UCO), namely residues of fats of vegetable or animal origin used for human consumption, in the food industry, in collective or commercial catering.

[0047] Naturally derived oil can also be oil produced by microorganisms, whether natural or genetically modified, such as bacteria, yeasts (including oleaginous yeasts), algae, prokaryotes, or eukaryotes. In particular, these oils can be recovered by well-known mechanical or chemical extraction methods.

[0048] The aforementioned oils, most of which are rich in triglycerides, also 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.

[0049] Preferably, the natural oils used in the present invention are so-called "crude" oils that have not undergone pretreatments such as the chemical and physical pretreatments usually carried out by those skilled in the art, similar to those used for the treatment of edible oils, such as degumming, neutralization with an alkaline solution (generally NaOH), bleaching, finishing or polishing (" polishing (in English), steam treatment, cavitation, etc. Preferably, these crude oils are non-esterified.

[0050] Compositions resulting from the trans-esterification of fatty acid esters and / or from the esterification of fatty acids contained in the aforementioned natural oils, such as compositions comprising alkyl esters of fatty acids, and in particular methyl esters of fatty acids and / or ethyl esters of fatty acids, and comprising impurities from the oils, may nevertheless also be part of the naturally sourced hydrocarbon fillers considered in the present invention.

[0051] The naturally derived hydrocarbon filler used in the present invention may thus contain more than 50%, preferably 60% or more, preferably 70% or more, of fatty acids and 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 naturally derived hydrocarbon filler comprises at most 99% of fatty acids and fatty acid esters.

[0052] The phosphorus content of the naturally occurring hydrocarbon load can be 20 ppm or more or 50 ppm or more, for example from 50 ppm to 1500 ppm, or from 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 a closed medium.

[0053] The nitrogen content of the naturally occurring hydrocarbon feed can be 20 ppm or more, for example from 50 ppm to 1200 ppm or from 200 ppm to 2000 ppm, measured for example by X-ray fluorescence or by chemiluminescence.

[0054] The naturally occurring hydrocarbon filler 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 such as X-ray fluorescence or by ICP.

[0055] Liquefaction oil for a hydrocarbon feedstock

[0056] The term "liquefaction oil" means an oil obtained from a pyrolysis process and / or a hydrothermal liquefaction process of a hydrocarbon feedstock. This hydrocarbon feedstock may include plastics and / or biomass, alone or in mixtures, including waste. A liquefaction oil may be formed from a mixture of two or more liquefaction oils obtained from the liquefaction of different hydrocarbon feedstocks, each obtained by pyrolysis or hydrothermal liquefaction.

[0057] The pyrolysis process should 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, implemented in the presence or absence of a catalyst and / or a gas (rapid pyrolysis, flash pyrolysis, catalytic pyrolysis, hydropyrolysis, steam pyrolysis, ...).

[0058] The hydrothermal liquefaction (or HTL) process is a thermochemical conversion process using water as a solvent, reactant, and catalyst for the degradation reactions of a hydrocarbon feedstock, with 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.

[0059] The liquefaction oil used optionally in the present invention may comprise, or be composed of, a plastics oil, a biomass oil, and mixtures thereof. In one embodiment, the liquefaction oil used optionally in the present invention may comprise, or be composed of, a biomass oil.

[0060] The expression "plastic oil" refers to hydrocarbon liquid products obtained from pyrolysis or hydrothermal liquefaction of thermoplastic and / or thermosetting and / or elastomer polymers, alone or in mixture, and generally in the form of waste, optionally in mixture with at least one other feedstock, in particular in the form of waste, such as biomass, for example selected from lignocellulosic biomass, herbaceous biomass, aquifer biomass, paper and cardboard, organic waste (forestry, agricultural, industrial and / or household waste), food waste, alone or in mixture.

[0061] The plastic can be of any type, including any type of new or used plastic, whether found in household (post-consumer) or industrial waste. Plastics are defined as materials composed of polymers and optionally of 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), polybutylene succinate (PBS), etc. Elastomers are linear or branched polymers transformed by vulcanization into a weakly cross-linked, infusible, and insoluble three-dimensional network. 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 materials. other components, such as plastics, plasticizers, fillers, vulcanizing agent, 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, acrylonitrile butadiene copolymers (NBR), and polychloroprenes (CR), polyurethanes, silicone elastomers, etc.

[0062] In general, any polymer or mixture of polymers capable of producing hydrocarbons by liquefaction may be used.

[0063] In one embodiment, the plastic oil can be obtained from the liquefaction of plastic waste that does not include tires and / or latex (vulcanized or not).

[0064] Plastic oils contain, in particular, paraffins, i-paraffins (isoparaffins), 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, and phosphorus compounds.

[0065] 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 (especially at more than 80% w, most often at more than 90% w) made up of hydrocarbons having from 1 to 150 carbon atoms and impurities.

[0066] A plastics oil typically comprises 5 to 80 wt% of paraffins (including cycloparaffins), 10 to 95 wt% of unsaturated compounds (including olefins, dienes, and acetylenes), and 5 to 70 wt% of aromatics. These contents can be determined by gas chromatography. In particular, a plastics oil may comprise a bromine count of 10 to 130 g Br2 / 100 g, as measured according to ASTM DI 159, and / or a maleic anhydride value (UOP326-82) of 1 to 55 mg maleic anhydride / lg.

[0067] A plastics 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).

[0068] A plastics oil typically comprises at least 20 ppm of heteroatoms, or even at least 30 ppm of heteroatoms.

[0069] A plastics oil may, in particular, comprise one or more of the following heteroatom contents: from 0 to 8 wt% oxygen (measured according to ASTM D5622), from 1 to 13,000 ppm nitrogen (measured according to ASTM D4629), from 2 to 1,000 ppm sulfur (measured according to ISO 20846), from 1 to 1,000 ppm of metals (measured by ICP), 50 to 6000 ppm of chlorine (measured according to ASTM D7359-18), 0 to 200 ppm of bromine (measured according to ASTM D7359-18), 1 to 40 ppm of fluorine (measured according to ASTM D7359-18), 1 to 2000 ppm of silicon (measured by XRF).

[0070] The expression "biomass oil" refers to liquid hydrocarbon products obtained from pyrolysis or hydrothermal liquefaction of one or more biomasses.

[0071] Biomass can be defined as an organic product of plant or animal origin.

[0072] In one embodiment, the biomass oil can advantageously be derived from biomass selected from lignocellulosic biomass, herbaceous biomass, aquifer biomass, paper and cardboard, organic waste (forestry, agricultural, industrial and / or household waste), alone or in mixture.

[0073] Biomass can thus include (i) biomass produced from surplus agricultural land, preferably not used for human or animal consumption: dedicated crops, called energy crops (short-rotation coppice (SRC), very short-rotation coppice (VSRC); (ii) biomass produced by deforestation (forest maintenance) or the clearing of agricultural land, ...; (iii) agricultural residues from crops, in particular cereal crops, vines, orchards, olive trees, fruits and vegetables including nuts, agri-food residues, ...; (iv) forestry residues from silviculture and wood processing; (v) agricultural residues from livestock farming (manure, slurry, bedding, droppings, ...); (vi) household organic waste (paper, cardboard, green waste, ...); (vii) industrial organic waste (paper, cardboard, wood, putrescible waste, ...(viii) algal biomass, namely biomass formed from algae, for example microalgae (algal biomass can be an algal suspension obtained by harvesting algae from, for example, a bioreactor, or an algal residue obtained by dehydrating an algal suspension) or macroalgae; (ix) herbaceous biomass; (x) vegetable oils contained in certain waste (cashew nut shells or other), (xi) industrial waste (type B wood), (xii) sewage sludge, (xiii) digestate from methanizers.

[0074] Biomass oil can contain from 8 to 55% oxygen by mass. 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, and phenols.

[0075] Fossil-derived hydrocarbon charge

[0076] The fossil-based hydrocarbon feed used as a diluent in step a) or in coprocessing during the implementation of steps c) and / or d) comprises fossil-based hydrocarbons.

[0077] In one embodiment, the fossil-based hydrocarbon feedstock may consist of fossil-based hydrocarbons. In this case, it does not include components of renewable origin.

[0078] Fossil hydrocarbons usable in the process can advantageously be chosen from naphtha cuts, diesel cuts, kerosene cuts and distillate cuts, in particular from the distillation of crude oil.

[0079] A fossil-derived naphtha cut typically has boiling points ranging from 15°C to 220°C. According to ASTM D86-12, it typically has an initial boiling point of 15°C to 42°C and a final boiling point of 220°C or less. Such a naphtha cut generally originates from the direct distillation of crude oil or from fractionation after hydrotreating and / or hydroisomerizing and / or hydrocracking and typically comprises C5-C12 compounds.

[0080] A fossil-based diesel fraction typically has boiling points ranging from 180 °C to 360 °C. According to ASTM D86-12, it typically has an initial boiling point of 180 to 240 °C and a final boiling point of 360 °C or less. Such a diesel fraction generally originates from the direct distillation of crude oil or from fractionation after hydrotreating and / or hydroisomerization and / or hydrocracking and typically comprises C13-C25 compounds.

[0081] A fossil-based kerosene fraction typically has boiling points ranging from 130 °C to 300 °C. According to ASTM D86-12, it typically has an initial boiling point of 130 to 160 °C and a final boiling point of 220 °C to 300 °C. Such a kerosene fraction generally originates from the direct distillation of crude oil or from fractionation after hydrotreating and / or hydroisomerizing and / or hydrocracking and typically comprises C9-C15 compounds.

[0082] Fossil-derived distillate fractions typically have boiling points ranging from 375 to 600 °C. According to ASTM D86-12, they typically have an initial boiling point of 375 to 450 °C and a final boiling point of 500 to 600 °C. Such distillate fractions are generally obtained from the vacuum distillation of an atmospheric residue of crude oil, also called vacuum distillates, and typically comprise C20-C55 compounds.

[0083] In the context of hydrotreating, the hydrocarbons of fossil origin are advantageously a kerosene cut or a mixture of kerosene cuts, preferably from the direct distillation of crude oil.

[0084] In the context of hydrocracking, the hydrocarbons of fossil origin are advantageously one or more distillate cuts, preferably from the direct distillation of crude oil.

[0085] In the context of hydrodesulfurization, the hydrocarbons of fossil origin are advantageously one or more kerosene cuts or one or more diesel cuts, preferably from the direct distillation of crude oil.

[0086] In the context of a hydroisomerization, the hydrocarbons of fossil origin are advantageously one or more kerosene or diesel cuts.

[0087] Step a) of hydrolysis

[0088] This step is carried out in a first reaction zone (also called the hydrolysis zone hereafter) under conditions of total (i.e., complete) hydrolysis in order to hydrolyze the esters present in the naturally occurring hydrocarbon feedstock into free fatty acids and alcohols, including glycerol. It is therefore the reverse reaction of an esterification reaction.

[0089] During this step, the naturally occurring hydrocarbon charge reacts with water under appropriate conditions to form free fatty acids and alcohols, including glycerol resulting from the dissociation of esters.

[0090] The hydrocarbon filler contains at least 50% by mass of mono-, di-, or triglycerides of fatty acids, and optionally alkyl esters of fatty acids, in particular ethyl esters of fatty acids and methyl esters of fatty acids. The alcohols formed thus include glycerol, alkyl alcohols, in particular ethanol and / or methanol, and other alcohols resulting from the hydrolysis of the fatty acid esters present. The fatty acids released depend on the nature of the natural oil used.

[0091] Typically, hydrolysis can 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.

[0092] Hydrolysis is typically carried out in the presence of excess water. The water / hydrocarbon feed mass ratio can 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 percentages of about 9%m to 66%m, preferably from 20%m to 60%m of water in the combined feed, preferably from 25%m to 50%m and even more preferably from 28%m to 42%m).

[0093] Water may be introduced in liquid form, for example by means of a pump or a regulating valve, and then heated to produce a mixture of liquid water and water vapor at a high temperature, for example at least 250 °C. This introduction may be carried out at one or more points in the hydrolysis zone. Superheated steam may also be introduced optionally to bring Heat can also be added to further heat the charge, for example, steam at 300 to 500 °C at the hydrolysis pressure (typically 50 barg). This can be introduced at one or more points within the hydrolysis zone. Alternatively, a combination of preheated water and steam can be used and introduced at one or more points within the hydrolysis zone.

[0094] Hydrolysis is typically carried out without a catalyst.

[0095] The hydrolysis products form a mixture of fatty acids and alcohols. This mixture is biphasic and consists of a denser aqueous phase containing some of the alcohols and a less dense phase containing the fatty acids and some 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 (mainly in the form of sulfate ions) and phosphorus (mainly in the form of phosphate ions).

[0096] The hydrolysis zone may comprise one or more reactors operating in batch or continuous mode, preferably continuous. For example, a countercurrent reactor or a cocurrent reactor equipped with a static mixer, or a reactor capable of generating turbulent flow (with a Reynolds number greater than 10,000), may be used. The hydrolysis zone may contain packing to improve contact between the different phases of the reactor.

[0097] In one embodiment of the invention, a diluent is also introduced into the hydrolysis zone. This diluent may be a feedstock of fossil origin, a portion or fraction of the hydrotreated effluent produced in step c), or a portion or fraction of the isomerized and / or hydrocracking effluent produced during the hydroisomerization and / or hydrocracking step d). Preferably, the diluent may contain at least branched hydrocarbons. Preferably, the diluent may contain at least hydrocarbons having the same number of carbons in the chain as the feedstock of natural origin.

[0098] This diluent is thus introduced into the hydrolysis zone along with said naturally occurring hydrocarbon feedstock. This introduction of the diluent may be carried out mixed with said naturally occurring hydrocarbon feedstock or not.

[0099] Adding a diluent can allow:

[0100] Improved phase separation of polar products, such as alcohols including glycerol, and inorganic impurities from non-polar products such as free fatty acids,

[0101] a limitation of corrosion in the hydrolysis zone due to free fatty acids present in the naturally occurring hydrocarbon feedstock,

[0102] better thermal integration when the diluent is introduced into the hydrolysis zone directly from the outlet of a hydrotreating, hydrocracking and / or hydroisomerizing zone, without intermediate cooling.

[0103] Furthermore, hydrolysis itself allows:

[0104] an elimination of metals and heteroatoms present (in particular P) in the naturally occurring hydrocarbon feedstock, and possibly in the liquefaction oil present, these contaminants being found in the aqueous phase which is separated from the naturally occurring hydrocarbon feedstock,

[0105] a limitation of propane production during subsequent hydrotreatment of the first fatty acid-rich effluent,

[0106] a reduction in dihydrogen consumption during a subsequent hydrotreatment of the first fatty acid-rich effluent.

[0107] Thus, in one embodiment, the diluent can be introduced into the hydrolysis zone at a temperature of 200 to 350 °C, typically 230 to 280 °C.

[0108] Advantageously, the diluent can come directly from the hydrotreating step and / or the hydrocracking step and / or the hydroisomerization step, without intermediate cooling. It can then be at a temperature of 200 to 350 °C, typically 230 to 300 °C.

[0109] Introducing the diluent at a temperature of 200 °C or higher into the hydrolysis zone limits the preheating of the naturally occurring hydrocarbon feedstock before it enters the hydrolysis zone, thus preventing its degradation. The naturally occurring hydrocarbon feedstock, alone or mixed with the liquefaction oil, can then be introduced into the hydrolysis zone at a temperature sufficient to ensure its fluidity, for example, from 50 °C to 250 °C.

[0110] Advantageously, the quantity of diluent introduced into the hydrolysis zone can represent 0.5 to 50% by mass of the feed to be treated introduced into the hydrolysis zone, this feed to be treated consisting of the feed of natural origin, and optionally of the liquefaction oil.

[0111] Whether or not in combination with the introduction of a diluent, at least one liquefaction oil of a hydrocarbon feedstock selected from a biomass oil and a plastics oil may also be introduced into said hydrolysis zone. This at least one liquefaction oil of a hydrocarbon feedstock introduced may represent at most 10% by mass of the naturally sourced hydrocarbon feedstock introduced into said hydrolysis zone, for example, from 0.5 to 10% by mass, preferably from 0.5 to 5% by mass, and more preferably from 0.5 to 1% by mass. This may allow for the incorporation of more components of renewable and / or natural origin, and possibly the addition of aromatic compounds.

[0112] The proportions of diluent and / or liquefaction oil introduced into the hydrolysis zone can advantageously be chosen so that the quantity of glycerides in the hydrolysis zone represents 50 to 95%, preferably 60 to 95%, of the total mass of hydrocarbon filler present in the hydrolysis zone, namely the sum of the mass of the naturally occurring charge, the mass of the diluent when present, and the mass of the liquefaction oil when present).

[0113] The hydrolysis is complete. The content of free fatty acids formed is then high, for example 60% by mass or more. Complete hydrolysis can be achieved 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 effluent no longer contains fatty acid esters or contains less than 1% by mass.

[0114] Hydrolysis can also be carried out in the presence of a catalyst.

[0115] Catalysts that accelerate the hydrolysis reaction include acids, such as sulfuric acid, and acids with an organic chain containing a sulfonic acid group, such as choric acid. Other heterogeneous catalysts that accelerate the hydrolysis reaction include 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 the general formula ZnxAl2O(3+x), and at least one heterogeneous catalyst based on a silicic, aluminic, or titaniumic solid containing zinc.

[0116] Step b) of recovery of the products of step a) of hydrolysis

[0117] During step b) of recovery of the present invention, the two phases of the biphasic mixture which forms in the hydrolysis zone are extracted separately from the latter.

[0118] Typically, the phase containing the fatty acids is extracted from an upper part of the hydrolysis zone and forms a first effluent rich in free fatty acids, and the denser aqueous phase is drawn from a lower part of the hydrolysis zone and forms a second effluent rich in alcohols and water.

[0119] Alternatively, the two phases can be separated by centrifugation, in particular carried out continuously, of the products of step a). In this case, the entire effluent from step a) is sent to centrifugation.

[0120] In general, step b) of recovery is carried out continuously, as the two-phase mixture is formed.

[0121] Optional step of separation and / or purification of the first effluent

[0122] The first effluent may still contain alcohol residues, inorganic impurities and / or water.

[0123] The manufacturing process according to the invention may then include an optional treatment step, in particular separation and / or purification, of the first effluent rich in free fatty acids produced during step a), in which the free fatty acids are separated from the residual alcohols, inorganic impurities and / or water present in this first effluent. This optional step may be carried out in a treatment area comprising one or more separation and / or purification areas.

[0124] This treatment zone may include, for example, a separation flask allowing at least part of an aqueous phase containing residual alcohols and water-dissolved contaminants initially contained in the first effluent to be separated from the first purified effluent containing free fatty acids.

[0125] The treatment zone may include a water washing zone, preferably implemented in a contactor, typically upstream of the separation tank when present. The water washing may optionally be carried out in the presence of an acid, for example citric acid or any other suitable acid, particularly to remove any metals still present in the feed.

[0126] Preferably, the treatment zone may include, for example, a contactor allowing the first effluent to be washed with water followed by a separation tank allowing at least part of an aqueous phase containing residual alcohols and water-dissolved contaminants initially contained in the first effluent to be separated from the first purified effluent containing free fatty acids.

[0127] The treatment zone may include a purification zone on a guard bed, typically downstream of the separation tank when present, allowing the retention of inorganic impurities present in the effluent.

[0128] This optional purification step may also include a demetallization (HDM) step implemented upstream or at the beginning of the hydrotreating process, typically downstream of the separation vessel. This demetallization can be carried out in one or more guard reactors containing a suitable catalyst located upstream of the hydrotreating process or by means of one or more guard beds positioned at the inlet of the hydrotreating zone.

[0129] Step c) of hydrotreatment

[0130] The first effluent recovered in step b), optionally purified, is then subjected to hydrotreatment in a second reaction zone in the presence of dihydrogen and at least one catalyst under suitable conditions to transform the free fatty acids contained in the first effluent into paraffins, and to form a paraffin-rich effluent.

[0131] This second reaction zone is distinct from the hydrolysis zone.

[0132] This hydrotreating step is typically carried out in the presence of dihydrogen and at least one suitable catalyst to transform fatty acid esters and free fatty acids contained in the effluent into paraffins, in particular into linear or substantially linear paraffins.

[0133] Step c) of hydrotreating the manufacturing processes can be carried out at a temperature of 100 to 550 °C, in the presence of dihydrogen at pressures ranging from 0.01 to 10 MPa.

[0134] The ratio between dihydrogen and feed charge can be from 100 to 2000 Nl / 1.

[0135] The catalyst can be selected 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 of Group 10 and Group 11 of the Periodic Table, (iii) basic oxides such as alkali metal oxides, alkali-earth oxides, lanthanide oxides, zinc oxide, spinels, perovskites, calcium silicates.

[0136] The catalyst may have a supported or unsupported catalytic active phase.

[0137] When the catalyst includes a support for the catalytic active phase, it is preferable that the support have a high specific surface area. In one embodiment, the specific surface area should 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 allows the specific surface area of ​​the solid material to be estimated.

[0138] 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 cracking at high temperature and pressure in the presence of dihydrogen.

[0139] Step c) of hydrotreating can be carried out in one or more reactors. Any type of reactor commonly used for this type of reaction may be used, for example a fixed-bed reactor, a stirred-tank reactor, a bubbling-bed reactor, a slurry-type reactor, etc., preferably a fixed-bed reactor.

[0140] The hydrotreated effluent exiting the hydrotreatment zone typically comprises a liquid portion and a gaseous portion. The liquid portion essentially comprises a mixture of n-paraffins, typically comprising 9 to 24 carbon atoms. The gaseous portion comprises H2, H2S, CO2, and possibly CO, NH3. The hydrotreated effluent also contains water.

[0141] In one embodiment, a portion of the total hydrotreated effluent exiting step c) can be sent, prior to any separation, to the hydrolysis step as a diluent. This can help retain the dihydrogen present in the effluent in solution, and thus limit the amount of dihydrogen that is separated at the outlet of step c). This can promote the hydrotreatment reaction.

[0142] Alternatively or in combination, part of the total hydrotreated effluent exiting step c) can be sent, before any separation, to the hydrolysis step, allowing the exothermicity of this step to be managed and more dihydrogen to be supplied in dissolved form to the hydrotreatment zone.

[0143] This hydrotreating step can be implemented in coprocessing with a fossil-based hydrocarbon feedstock. This fossil-based hydrocarbon feedstock can be as previously described.

[0144] The quantity of first effluent, purified or not, introduced into the second reaction zone can advantageously represent 0.5 to 90% by mass, more preferably 0.5 to 50% by mass, preferably 0.5 to 25% by mass of the total load (first effluent and hydrocarbon load of fossil origin) introduced into the second reaction zone.

[0145] During this step c) of hydrotreatment, different reactions can take place:

[0146] a hydrodeoxygenation (HDO), which removes oxygen from the treated oils and leads to the formation of linear paraffins while preserving the number of carbons of the initial fat chains and is accompanied by the formation of water and possibly propane, this reaction can be carried out on fatty acid esters, free fatty acids or their mixtures;

[0147] a decarboxylation and / or a decarbonylation (DCOX), which leads to the formation of paraffins having one less carbon atom than the initial fatty chain and is accompanied by the formation of carbon oxides (CO and CO2) and possibly propane, this reaction can be carried out on glycerides, any esters or with free fatty acids.

[0148] The implementation of the pretreatment step by hydrolysis of the present invention makes it possible to reduce the formation of propane.

[0149] This hydrotreatment step c) can thus comprise one or more steps selected from hydrodeoxygenation, decarboxylation and decarbonylation, namely, this step c) can be carried out under hydrodeoxygenation and / or decarboxylation and / or decarbonylation conditions.

[0150] Hydrodeoxygenation

[0151] Several reactions occur under hydrodeoxygenation conditions. The easiest is the hydrogenation of the double bonds in the alkyl chain. The most difficult reaction is the removal of oxygen atoms from the CO bonds. The carboxyl group of the fatty acid and the hydroxyl group of the glycerol fraction are hydrodeoxygenated. This results in the production of linear paraffin, from the acyl fraction, and propane, from the glycerol. Depending on the conditions (catalyst, temperature, dihydrogen, etc.), the carboxyl group can also be decomposed into CO / CO2. (decarboxylation or decarbonylation), which can in turn be hydrogenated to methane. These hydrodeoxygenation reactions consume a lot of dihydrogen.

[0152] Hydrodeoxygenation can be carried out at a temperature of 200 to 500°C, preferably 220 to 400°C, under a pressure of 1 MPa to 10 MPa (10 to 100 bar), for example 6 MPa, and with a dihydrogen / hydrocarbon feed ratio of 100 to 2000, but preferably 350 to 1500, for example 800 NiH2 / l of hydrocarbon feed. The catalyst is typically a solid catalyst which can be selected from oxides, phosphides or sulfides of Ni, Mo, W, Co or mixtures such as NiW, NiMo, CoMo, NiCoW, NiCoMo, NiMoW and CoMoW as the catalytic phase, preferably supported on carbon, alumina, silica, titanium oxide or zirconia.

[0153] For optimal performance and stable continuous operation, it is preferable that the active metallic component of the catalyst, in the case of Ni, Mo, W, Co, or mixtures thereof, be in the form of sulfides or phosphides. Therefore, in the case of sulfides, it is preferable that traces of decomposable (thermally or catalytically) sulfide compounds be present or intentionally added to the feedstock to maintain the metallic sulfide in its sulfide state. By way of example, these sulfur compounds may be H₂S, COS, CS₂, mercaptans (e.g., methyl sulfide), thioethers (e.g., dimethyl sulfide), disulfides (e.g., dimethyl disulfide), thiophenic and tetrahydrothiophenic compounds.

[0154] Hydrodeoxygenation is preferably carried out in continuous fixed bed reactors, continuous stirred tank reactors or slurry type reactors, particularly in the presence of a solid catalyst.

[0155] Decarboxylation and / or decarbonylation

[0156] Under decarboxylation and / or decarbonylation conditions, in addition to the decarboxylation and / or decarbonylation reactions with the formation of CO2, CO, H2O, hydrogenation reactions of unsaturated bonds and / or hydrodeoxygenation of fatty acids may occur. Further hydrogenation of the CO / CO2 produced may also occur depending on the amount of dihydrogen available, the catalyst, and the reaction conditions.

[0157] The decarboxylation and / or decarbonylation step can be carried out at a temperature of 100 to 550°C in the presence of dihydrogen at pressures ranging from 0.01 to 10 MPa. The ratio between dihydrogen and feedstock can be from 100 to 2000 Nl / 1.

[0158] Decarboxylation and / or decarbonylation is preferably carried out in the presence of a solid catalyst, generally in batch reactors, continuous fixed bed reactors, continuous stirred tank reactors or slurry type reactors.

[0159] The catalyst can be chosen from: - oxides, phosphides or sulfides of Ni, Mo, W, Co, NiW, NiMo, CoMo, NiCoW, NiCoMo, NiMoW and CoMoW as a catalytic phase, preferably supported on carbon, alumina, silica, titanium oxide or zirconia, or - metals or alloy mixtures of group 10 (Ni, Pt and Pd) and group 11 (Cu and Ag), preferably supported by carbon, magnesia, zinc oxide, spinels (Mg2Al2O4, ZnAl2O4), perovskites (BaTiO3, ZnTiO3), calcium silicates (such as xonotlite), alumina, silica or silica-aluminas or mixtures thereof, or - basic oxides, such as alkali metal oxides (MgO, ZnO), alkali-earth oxides, lanthanide oxides, zinc oxide, spinels (Mg2Al2O4, ZnAl2O4), perovskites (BaTiO3, ZnTiO3), calcium silicates (such as xonotlite), either in bulk or dispersed on neutral or basic supports, on basic zeolites (such as alkali or alkaline-earth zeolites with low silica / alumina content obtained by exchange or impregnation).

[0160] For optimal performance and stable continuous operation, it is preferable that the active metallic component of a catalyst containing Ni, Mo, W, Co, or mixtures thereof, be in the form of sulfides or phosphides. It is therefore preferable that traces of decomposable (thermally or catalytically) sulfide compounds be present or intentionally added to the feedstock to maintain the metallic sulfide in its sulfide state. The same compounds mentioned above may be used.

[0161] Optional separation step

[0162] The hydrotreated effluent from step c) may be subjected, in part or in whole, optionally before being sent to the optional step d), to a separation step in which non-condensable components such as propane, CO2, CO, methane, dihydrogen and vaporized water are separated from the liquid fraction.

[0163] In one embodiment, the dihydrogen can be separated from the other non-condensable components and returned, in part or in whole, to step a) of hydrolysis to be dissolved in the reaction mixture. This can promote the hydrotreating reaction of step c). Alternatively, or in combination, the dihydrogen can be separated and returned, in part or in whole, to the inlet of step c).

[0164] In one embodiment, the effluent from step c) can thus be separated into:

[0165] a gaseous stream containing H2, H2S, CO2, and possibly small amounts of CO and NH3,

[0166] water,

[0167] a liquid fraction containing a mixture of paraffins.

[0168] The gas stream can undergo further treatment in order to separate the dihydrogen from the other gases for reuse in the process.

[0169] Part of this liquid fraction, after separation, can be used as hydrocarbon recycling to the hydrotreating zone in order to absorb the heat of reaction, to dilute the deteriorating effect of the remaining impurities.

[0170] According to one embodiment of the invention, part of this liquid fraction can serve as a diluent during the hydrolysis step.

[0171] This separation, implemented in a separation zone, can be a flash separation or be carried out in a stripping section. Depending on the operating conditions, some of the remaining water can be condensed and removed in this stage by sedimentation or drainage, for example in a high-pressure separator. The flash separation and the removal of the liquid water can be carried out simultaneously or not.

[0172] A separator vessel may also be provided to separate the water, gases, and a liquid organic phase, the latter then being sent to a stripping section to remove light hydrocarbons. The gases can be sent to a treatment section, for example, to an amines section, to separate the dihydrogen from the other gaseous components.

[0173] The water produced in the hydrotreatment can be used in step a) of the hydrolysis or in the optional step of separation and / or purification of the first solvent and thus reduce the net need for water to carry out these steps.

[0174] Optional step d) of hydroisomerization and / or hydrocracking

[0175] All or part of the hydrotreated effluent from step c) may be subjected to a hydroisomerization step and / or a hydrocracking step in a hydroisomerization and / or hydrocracking zone in the presence of dihydrogen and at least one catalyst to produce an isomerized effluent rich in iso-paraffins and / or to produce a hydrocraced effluent rich in hydrocarbons having less carbon in the chain than the feed, forming an isomerized and / or hydrocraced effluent.

[0176] This step can be carried out at a temperature of 150 °C to 500 °C and at a pressure of 1 MPa to 15 MPa.

[0177] Suitable hydroisomerization and / or hydrocracking catalysts used in hydroisomerization and / or hydrocracking processes are all of the bifunctional type combining an acid function with a (de)hydrogenating function.

[0178] The acid function is typically provided by a support (amorphous or crystalline) with specific surface areas generally ranging from 100 to 700 m² / g and exhibiting surface acidity, such as halogenated aluminas (particularly sulfated, phosphated, chlorinated, or fluorinated), aluminas (possibly containing boron), amorphous silica-aluminas, amorphous silica-aluminas-titaniums, sulfated zirconias, tungsten zirconias, and zeolites or mixtures thereof. The acidity can be measured by methods well known to those skilled in the art. For example, it can be measured by temperature-programmed desorption (TPD) with ammonia, by infrared measurement of absorbed molecules (pyridine, CO₂, etc.), by a catalytic cracking test, or by hydroconversion using a model molecule.

[0179] Hydroisomerization catalysts possess a weak acid function, preferably halogenated aluminas (in particular sulfated, phosphated, chlorinated or fluorinated), aluminas (possibly containing boron), amorphous silica-aluminas, amorphous silica-aluminas-titaniums,

[0180] Hydrocracking catalysts possess a strong acid function, preferably sulfated zirconias, tungsten zirconias and zeolites or mixtures thereof.

[0181] The (de)hydrogenation function is typically ensured 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.

[0182] The distance between the two functions, acid and (de)hydrogenating, is one of the key parameters governing the activity and selectivity of the catalyst.

[0183] A weak acid function and a strong (de)hydrogenating function result in catalysts with low activity, generally requiring a high temperature (greater than or equal to 390-400°C), and long residence times or low spatial velocity per hour (the VSLH expressed as the liquid volume of feed per unit volume of catalyst per hour is generally less than or equal to 2), but exhibiting very good selectivity for middle distillates (jet fuel and diesel). 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 final boiling point is generally less than about 350°C, preferably less than 370°C.

[0184] Conversely, a strong acid function and a weak (de)hydrogenating function give catalysts which are active, but which have a lower selectivity for middle distillates and the result is more cracked hydrocarbons in the range of naphthas and jet fuels.

[0185] One type of conventional hydroisomerization catalyst is based on amorphous supports that are moderately acidic, such as silica-alumina for example. These systems are used to maximize middle distillates with good cold flow properties.

[0186] One type of conventional hydrocracking catalyst is based on crystalline supports such as zeolites and sulfated zirconia, which are highly acidic. These systems are used to reduce the number of carbons in the chain and provide good cold-flow properties. Hydrocracking produces non-condensable gases, naphtha, kerosene, and diesel fuel.

[0187] The catalysts and the conditions for hydroisomerization and / or hydrocracking are well known in art.

[0188] Hydrocarbons from hydrotreated natural oil 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 can be accomplished in any manner known in the art or by using any suitable catalyst known in the art.

[0189] The acid support material can 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, beta zeolite, Y zeolite, mordenite zeolite 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 can be used alone or in combination.

[0190] 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 with metal-containing solutions, by ion exchange, and by mixing.

[0191] The hydroisomerization and / or hydrocracking step can be carried out using one or more types of catalysts in a plurality (one or more) of catalytic beds in the same reactor or in a plurality of different reactors. The feed for hydroisomerization and / or hydrocracking can be fed onto the catalyst simultaneously with the hydrogen-containing gases in a downward flow mode, in an upward flow mode, or the liquid feed can flow in a downward flow while the gases containing Dihydrogen flows in an upward flow mode through the catalyst beds.

[0192] Typical hydroisomerization and / or hydrocracking conditions include a temperature of 150°C to 500°C or more, preferably 220°C to 450°C and more preferably 250°C to 420°C, and a pressure of 1 MPa to 15 MPa or more, preferably 1.5 MPa to 9 MPa and more preferably 2 MPa to 6 MPa. The hourly space velocity can be about 0.1 to 20 h1, more preferably 0.2 to 10 h1 and most preferably 0.3 to 4 h1. The supplied hydrogen-containing gases can be introduced simultaneously with the feed charge at a ratio of 75 to 2500 NI (H2) / l of charge, more preferably 150 to 1500 NI or more preferably 250 to 1000 NI.

[0193] During a hydroisomerization reaction, secondary hydrocracking reactions may occur. Similarly, during a hydrocracking reaction, hydroisomerization may occur. A person skilled in the art will be able to select appropriate conditions for treating the effluent under hydroisomerization conditions, or under hydrocracking conditions respectively, that is, conditions under which hydroisomerization reactions, or hydrocracking reactions respectively, predominantly occur.

[0194] This hydroisomerization and / or hydrocracking step can be carried out in coprocessing with a fossil-based hydrocarbon feedstock. This fossil-based hydrocarbon feedstock can be as previously described.

[0195] The quantity of hydrotreated effluent from step c), separated or not, introduced into the hydroisomerization and / or hydrocracking zone may advantageously represent 0.5 to 90% by mass, more preferably 0.5 to 50% by mass, preferably 0.5 to 25% by mass of the total load (hydrotreated effluent and hydrocarbon load of fossil origin) introduced into the hydroisomerization and / or hydrocracking zone.

[0196] Thus, the hydrocarbon feed of fossil origin can be introduced entirely in step c) or entirely in step d) or distributed between steps c) and d).

[0197] Optional separation step

[0198] In one embodiment of the invention, the process for manufacturing hydrocarbon fluids may further include a separation step in which the effluent from step c), preferably after separation of non-condensables, or the effluent from step d), preferably the effluent from step d), is separated into at least one fraction selected from a naphtha fraction, a kerosene fraction and a diesel fraction.

[0199] The effluent from step c), preferably after separation of non-condensables, or the effluent from step d), preferably the effluent from step d), in particular in hydrocracking conditions, can undergo fractionation, for example carried out by adding a separation column, for example a distillation column, or by lateral withdrawal.

[0200] This fractionation allows the recovery of at least one selected fraction from a naphtha fraction, a kerosene fraction, and a diesel fraction. This fractionation step can also allow the separation of condensable (propane, butane) and non-condensable (H2, methane, ethane) gaseous fractions, including unreacted dihydrogen, which can optionally be sent to the inlet of step c) or d).

[0201] The recovered naphtha fraction preferably has an initial boiling point of 30 °C and a final boiling point of 80 °C to 180 °C. This fraction can be used as fuel for internal combustion engines, particularly without the addition of other components such as esters. This fraction can be used as feedstock for a steam cracker, particularly for the production of olefins such as ethylene and propylene.

[0202] The recovered diesel fraction preferably has an initial boiling point of 80 to 180 °C and a final boiling point of 360 °C or less. This fraction can be used as diesel engine fuel, in particular without the addition of other components such as esters.

[0203] The recovered kerosene fraction preferably has a final boiling point below 300 °C, in particular as measured according to ASTM D86-12. The initial boiling point according to ASTM D86-12 may be from 120 to 185 °C. The kerosene fraction can be used as jet fuel, in particular without the addition of other components such as esters.

[0204] In particular, the cutting points of the recovered fractions can be adapted to obtain products meeting specific specifications, in particular without having to add other components such as esters.

[0205] In one embodiment, one of the separated fractions, in particular the diesel fraction, can be used to form all or part of the diluent.

[0206] Optional step of purification of the second effluent

[0207] The second effluent recovered in step b), before being sent to step e) of reforming, may advantageously be subjected to at least one purification treatment selected from (i) a step for removing solids such as gums, and (ii) a step for removing contaminants such as metals or other heteroatoms.

[0208] The solids removal step can, in particular, make it possible to remove any gums that may be present in the second effluent and that could clog downstream installations when the mixture is heated. It also makes it possible to remove of any solids (salts or other contaminants including metals) present in the second effluent.

[0209] This solids removal step is a liquid-solid separation that can be implemented by any gravity separation and / or filtration technique. Examples include filtration, decantation (possibly carried out under the action of an electric current), centrifugation, and hydrocyclones.

[0210] The contaminant removal step eliminates contaminants such as metals that could degrade the catalysts used in downstream processes. This removal step may employ purification techniques by adsorption, absorption, filtration, and / or electrochemical separation using ion-exchange membranes, preferably by electrochemical separation. Ion-exchange resins may be used, for example.

[0211] Step e) of reforming

[0212] During this step, implemented in a third reaction zone separate from the other two, the second effluent recovered in step b) is subjected to an aqueous phase reforming reaction in order to produce dihydrogen and carbon oxides (CO, CO2).

[0213] Preferably, the second effluent entering the reforming step e) may contain from 5 to 50% by mass of alcohols and in particular glycerol.

[0214] During this step, the alcohols contained in the second effluent, and in particular glycerol, are converted mainly into H2, and also into CO, CO2. The water-gas shift reaction (WGS), which converts CO in the presence of water into CO2 and H2, is generally facilitated under the conditions of implementation of this step, leading to the formation of a gas mixture with a low CO content while increasing the production of H2.

[0215] The gaseous mixture resulting from the reforming reaction may also include small proportions of methane and short-chain (C2-C3) alkanes. Oxygenated compounds (alcohols, carboxylic acids, aldehydes, diols) may also be formed during the reforming reaction and be found in the liquid phase.

[0216] This step can be carried out at temperatures of 180 to 300 °C, preferably 200 to 260 °C and a pressure of 0.1 to 6 MPa.

[0217] The alcohol / water molar ratio may be 1:3, preferably 1:9.

[0218] The mass hourly space velocity (WHSV) may be from 0.5 to 4 per hour, preferably from 0.5 to 3 per hour.

[0219] This step is generally carried out in the presence of a solid catalyst comprising a support and a catalytic active phase.

[0220] It is preferable that the support have a high specific surface area. In one embodiment, the specific surface area measured by the BET method can be adjusted by a person skilled in the art. The support can be carbon, aluminas, silicas, silica-aluminas, titanium oxides, cerium oxides, Ce-Zr oxides, magnesium oxides, magnesium-aluminum oxides, alone or in mixtures.

[0221] The carbon can be activated carbon, nanotubes, carbon black, mesoporous carbon, preferably with a high specific surface area, for example from 250 to 800 m2 / g.

[0222] The catalytic phase may include one or more elements selected from tin, cerium, boron, and a metal from groups 4, 7, 8, 9, 10 or 11 of the periodic table, cerium oxides, zinc oxides, cerium and zinc oxides, alone or in mixture.

[0223] By way of example, the catalytic phase can be chosen from Ni, Pt, Sn, Ce, Zr, Cu, CeZr, PtNi, PtCu, PtCo, PtFe, PtRe, PtRh, PtMo, RhRe, CuNi, PtNiCe, CeZrNi, CeZrNiCo, CePt.

[0224] By way of example, a Raney catalyst based on Ni may also be used, optionally in combination with tin (Sn) and / or boron (B).

[0225] The third reaction zone is separate from the other reaction zones. It may comprise one or more fixed-bed reactors.

[0226] Step f) of dihydrogen separation

[0227] During the reforming step, the gas mixture formed may contain, in addition to dihydrogen, other gases such as CO2, CO and possibly methane and light alkanes.

[0228] This step allows the gas mixture to be enriched in H2, by eliminating all or part of CO2 and CO, and possibly other gases.

[0229] This separation can be implemented via any suitable separation technique known in the prior art. It may consist of the separation of H2 and / or CO2.

[0230] It comprises, or consists of, at least one step selected from a membrane separation step, an adsorption separation step, in particular a pressure-modulated adsorption separation step, and a CO2 liquefaction step.

[0231] Separation by adsorption can be adsorption on amines.

[0232] The PSA is based on the selective adsorption of impurities (mainly CO, CO2, CH4) on a molecular sieve.

[0233] For example, dihydrogen can be separated by means of a membrane method (generally using membranes containing metals such as palladium) or of a pressure-modulated (Pressure Swing Adsorption or PSA) or temperature-modulated (Temperature Swing Adsorption or TSA) absorption method.

[0234] Alternatively or in combination, CO2 can be separated by liquefaction, typically by implementing a series of compression and cooling stages to condense the CO2. This liquefaction can be preceded by a purification step by passing through activated carbon.

[0235] The two types of separation can be combined into a single separation as a vacuum pressure-modulated absorption method.

[0236] Preferably, the separation step includes at least one pressure-modulated absorption step, possibly under vacuum.

[0237] Optional step g) of syngas production

[0238] Advantageously, the process according to the invention is integrated into a process for producing syngas, namely a synthesis gas containing dihydrogen, and generally CO2, CO, and methane. Other gases (H2O, N2, ...) may be present depending on the production process.

[0239] Such integration makes it possible to pool certain equipment and / or increase the production of dihydrogen.

[0240] Depending on its composition, the syngas produced during step g) is then sent to step e) of reforming or to the separation step f) of dihydrogen.

[0241] Preferably, the syngas produced during step g) is sent to the separation step f).

[0242] Syngas can be produced by gasification or pyrolysis of biomass and / or plastics.

[0243] Fischer-Tropsch type processes also make it possible to generate syngas.

[0244] Syngas can also be produced by steam methane reforming (or SMR for Steam methane Reforming in English).

[0245] Methane can be of fossil or renewable origin.

[0246] Thus, in one embodiment, step g) of syngas production comprises the following substeps:

[0247] a step in the production of biogas by methanation of biomass, the biogas containing at least methane and CO2,

[0248] an optional step for purifying the methane produced in step (i),

[0249] a steam reforming step of the methane produced in step (i) or of the purified methane in step (ii) to produce syngas.

[0250] The optional methane purification step may include a step for removing compounds containing sulfur, silicon and / or halogens, followed by a membrane or pressure-modulated absorption purification step.

[0251] In this embodiment, the solids, typically consisting mainly of gums, from the solids removal step during the purification treatment of the second effluent can be sent to the methanation step (i) to increase methane production.

[0252] Detailed description of the figures

[0253] Other features and advantages of the invention will become apparent from the following description of a particular embodiment of the invention, given by way of example but not limitation, with reference to the accompanying drawings in which:

[0254] Fig. 1 schematically represents a process for manufacturing hydrocarbon fluids according to an embodiment of the invention.

[0255] Fig. 2 schematically represents a process for manufacturing hydrocarbon fluids according to another embodiment of the invention.

[0256] In the figures, the same elements are designated by the same numerical references.

[0257] Fig. 1 represents a process for manufacturing hydrocarbon fluids 100 comprising a hydrolysis step carried out in a hydrolysis zone 10, a hydrolysis product recovery step, and a hydrotreatment step carried out in a hydrotreatment zone 20.

[0258] The hydrolysis zone 10 can be a co-current mixer reactor or a counter-current reactor. The feed to be treated enters the hydrolysis zone 10 through a first conduit 1. This feed is a naturally occurring hydrocarbon feed containing glycerides as previously described. This feed can be introduced at a temperature above 75 °C but preferably below 300 °C.

[0259] Via the same line 1 or another line 2, another feedstock can optionally be co-treated. This other feedstock is, for example, a liquefaction oil of a hydrocarbon feedstock, namely a biomass oil and / or a plastics oil.

[0260] Water, typically at a temperature of at least 100 °C, is introduced into the hydrolysis zone 10 via a conduit 3. In the example, an optional conduit 4 allows the introduction of steam superheated relative to the temperature recommended for hydrolysis.

[0261] At the outlet of the hydrolysis zone 10, a first effluent rich in free fatty acids formed during hydrolysis, and possibly containing fatty acid esters, is recovered via a line 5, and a second effluent, which is an aqueous phase containing the majority of the alcohols produced during hydrolysis, is recovered via a line 6. This aqueous phase also contains a majority of the pollutants initially contained in the naturally occurring hydrocarbon feedstock, and possibly some of the pollutants initially contained in the liquefaction oil. The phases are extracted separately and continuously in the upper and lower parts of the hydrolysis zone.

[0262] The organic phase is then sent to a hydrotreating zone 20 for hydrotreating and undergoing hydrodeoxygenation and / or decarboxylation and / or decarbonylation reactions, producing a hydrotreated effluent discharged through line 7. This hydrotreated effluent comprises a paraffin-rich liquid fraction forming a hydrotreated oil, and a fraction of non-condensable components. A portion of this hydrotreated oil can be conveyed via line 7b to a hydroisomerization and / or hydrocracking zone, or to a fractionation zone (not shown).

[0263] According to an optional embodiment of the invention, a portion of the hydrotreated oil is fed via a pipe 7a into the hydrolysis zone 10. As a result of this incorporation, the effluent rich in free fatty acids exiting the hydrolysis zone also contains hydrotreated natural oil. Thus, the addition of hydrotreated oil allows for the dilution of the natural hydrocarbon load in the hydrolysis zone, as well as the dilution of the free fatty acids produced during hydrolysis and discharged via the pipe 5. This second dilution can limit the flow rate, or even eliminate the need for the usual recycling of hydrotreatment products at the inlet of the hydrotreatment zone, thereby limiting the exothermicity of the reactions involved.Furthermore, the hydrotreated oil exiting the hydrotreatment zone 20, particularly directly without intermediate cooling, is at a temperature of at least 250 °C. Therefore, its introduction into the hydrolysis zone 10 provides some of the heating necessary for the hydrolysis reaction, improving the thermal integration of the unit. It should be noted that the hydrotreated oil can be sent directly to the hydrolysis zone 10 without prior degassing, meaning it contains unreacted dihydrogen that dissolves in the feedstock and is subsequently found in the first effluent 5 entering the hydrotreatment zone 20. This notably reduces the energy required to recycle the gaseous dihydrogen by compression in the hydrotreatment zone.

[0264] Typically, the hydrotreating zone 20 includes a hydrogen supply line 8 and one or more catalytic beds. A catalytic bed dedicated to demetallation (a guard bed) may be provided at the inlet of the hydrotreating zone 20 to remove chlorine, metals, and silicon. The hydrotreating zone 20 may include one or more reactors operated in series, in parallel, or both. Isolated, lead-lag, series, and / or parallel guard reactors may be considered depending on the nature and quantity of contaminants in the stream to be treated.

[0265] The aqueous phase 6 is then sent to a reforming step implemented in an aqueous phase reforming zone 80, optionally after one or more purification steps. The syngas exiting the reforming step is then sent to a dihydrogen separation step implemented in a separation zone 90, producing a gas enriched in H2 returned via a line 90a to the hydrotreating zone 20 and a purified syngas, depleted in H2, discharged via a line 90b.

[0266] In the example shown, the aqueous phase 6 first passes through a solids removal zone 70, for example by filtration, allowing solids, including gums, to be removed via a pipe 71, then through a contaminant removal zone 75 allowing contaminants, including metals, to be removed via a pipe 76, before being conveyed to the reforming zone 80.

[0267] Optionally, as shown, a syngas production step implemented in a syngas production unit 91 can be integrated into the process, the syngas produced is then conveyed via a conduit 92 to the dihydrogen separation zone 90.

[0268] Figure 2 represents a process for manufacturing hydrocarbon fluids 200, which differs from that shown in Figure 1 essentially by the presence, downstream of the hydrotreating zone 20, of a separation zone 30 and a hydroisomerization and / or hydrocracking zone 40. The hydrolysis and hydrotreating zones 10 and 20 can be as described with reference to Figure 1. The process also differs in the syngas production step.

[0269] In the embodiment shown [Fig. 2], the unit 200 also includes a separator 11 located on the discharge line 5 for the first effluent rich in free fatty acids. This separator condenses some of the water contained in the first effluent, as well as the alcohols and pollutants present in this water, which is discharged via a line 12. A first effluent rich in free fatty acids and with a reduced content of water, alcohols, and pollutants then enters the hydrotreatment zone 20 via the line 13. In the embodiment shown, this line has a demetallization guard bed 21. 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.

[0270] The separator tank 11 and / or the guard bed(s) 21 are part of an optional treatment zone 15 implementing the optional treatment step. This hydrotreatment zone may also include a contactor (not shown) for washing the effluent with water upstream of the separator tank 11.

[0271] At the outlet of the hydrotreatment zone 20, the hydrotreated effluent discharged through the pipe 7 comprises a liquid fraction rich in paraffins and a fraction of non-condensable components. In this embodiment, the hydrotreated effluent is sent to a separation zone 30 comprising a separator tank 31 and a stripping column 32. The separator tank 31 separates the water present in the effluent via a line 33 and the non-condensable gases (G) via a line 34. Note that the water recovered via the line 33 could be returned to the hydrolysis zone 10, optionally after undergoing treatment to reduce its acidity, and / or to the treatment zone 15, in particular to a contactor.

[0272] 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 forming a hydrotreated natural oil is recovered at the bottom of column 32 via the pipe 38.

[0273] Part of the hydrotreated natural oil is conveyed to the hydroisomerization and / or hydrocracking zone 40 via line 38b; another part can optionally be returned upstream of the hydrotreatment zone 20 via line 38a. This line 38a can optionally include a portion 38c which joins line 1, introducing the natural hydrocarbon feedstock into the hydrolysis zone. Note that this portion of line 38c could be directly connected to the hydrolysis zone 10.

[0274] In the embodiment shown, the conduit 38a also includes a portion 38d for returning some of the hydrotreated oil to the inlet of the hydrotreatment zone. This portion of the conduit 38d could, however, be omitted.

[0275] Depending on the desired objective, it is also possible to take part of the effluent flowing in pipes 7 or 35 and return it directly to the hydrolysis zone 10 (via pipes 7a or 35a) or upstream of it to be mixed with the hydrocarbon load flowing in pipe 1.

[0276] The hydroisomerization and / or hydrocracking zone 40 comprises a hydrogen supply line 41 and a discharge line 42 for the isomerized and / or hydrocracking effluent, rich in isoparaffins and forming a hydrotreated and hydroisomerized and / or hydrocracking natural oil. The hydroisomerization and / or hydrocracking zone 40 may comprise one or more reactors operated in series, in parallel, or both, each containing one or more catalytic beds. A portion of the hydroisomerized and / or hydrocracking effluent may optionally be returned to the hydrolysis zone 10 via line 43, to be mixed with the hydrocarbon feedstock either before or after its entry into the hydrolysis zone. Depending on the desired result, it may be possible to introduce into the hydrolysis zone only a portion of the hydroisomerized and / or hydrocracked effluent (pipe 38c is then omitted).

[0277] In certain embodiments, the manufacturing process according to the invention is devoid of a hydroisomerization and / or hydrocracking step. In this case, the diluent optionally used in the hydrolysis zone comes solely from a portion of one or more of the flows circulating in the pipes 7, 35 and 38.

[0278] Examples of circulating effluent temperatures and pressures are given in [Fig.2]. It can thus be seen that high-temperature flows are, in this embodiment, returned to the hydrolysis zone without having undergone any cooling other than that resulting from their passage through the existing equipment, for better thermal integration of the entire unit.

[0279] It should be noted that the effluent discharged by line 7 from the hydrotreatment zone of unit 100 or line 42 from the hydroisomerization and / or hydrocracking zone 40 can be sent to a fractionation zone 50 (not shown [Fig. 1]) to be separated into hydrocarbon streams such as a gaseous fraction, a naphtha fraction, a diesel fraction, and a kerosene fraction via lines 51, 52, 53, and 54, respectively. A recycle line 55 can then be provided to return a portion of the separated fraction, preferably the diesel fraction, to the hydrolysis zone 10 as a diluent.

[0280] Regardless of the embodiment, when a diluent is introduced into the hydrolysis zone, it can be introduced via the first inlet line 1, via the second inlet line 2, or via a dedicated inlet (not shown).

[0281] Furthermore, in this embodiment, the production of syngas is carried out by a methanation step implemented in a biomass digester 910. Optionally, as shown, the digester also receives solids, essentially gums, as input, which are removed via line 71. The biogas produced in the digester is discharged via line 911, can optionally be purified in a purification unit 912 before being sent to a steam reforming SMR unit 914. This SMR unit 914 produces syngas which is discharged via line 915 and can be sent to the aqueous phase reforming unit 80 or to the purification unit 90, preferably to the purification unit 90. Examples

[0282] Consider a process scheme as described with reference to [Fig.2].

[0283] It is assumed that the feedstock to be treated contains 0.25% by mass of phospholipids and that the hydrolysis is carried out under conditions of total conversion of triglycerides to fatty acids. The hydrotreatment step is a hydrodeoxygenation (HDO) step.

[0284] At the end of hydrolysis, the aqueous phase is subjected to centrifugation in unit 70 and then to membrane purification in unit 75.

[0285] Table 1 shows the mass balance of the fluxes SI to S9 circulating in the process and shown in [Fig. 2]. Table 2 shows the molar balance of the same fluxes, namely:

[0286] SI: hydrocarbon charge containing triglycerides entering the hydrolysis zone,

[0287] S2: water entering the hydrolysis zone,

[0288] S3: free fatty acids exiting the hydrolysis zone,

[0289] S4: aqueous phase exiting the hydrolysis zone (hypothesis: soluble glycerol) 100% in water),

[0290] S5: water / glycerol mixture exiting the centrifugation,

[0291] S6: gums exiting the centrifugation (hypothesis: gums + 5% water),

[0292] S7: water / glycerol mixture exiting membrane purification (assumption: 30%) (purified water comes out)

[0293] S8: metals / dirty water exiting membrane purification (assumption: contains 70% water),

[0294] S9: outgoing flow of aqueous phase reforming 80 (assumption: 80% of the glycerol is converted into H2 considering the reaction: C3H8O3 + 3H2O ->7H2 + 3CO2).

[0295] For the molar balance, it is assumed that the phospholipids are PC (phosphatidylcholines) with a molar mass of 734g / mol.

[0296] Table 3 specifies the H2 requirements of the hydrotreatment, and the production covered by the aqueous phase reforming of glycerol.

[0297] The H2 requirements of the hydrotreatment are estimated by taking into account the following reactions and favoring the hydrodeoxygenation reaction:

[0298] -1'hydrodeoxygenation of free fatty acids requiring 3 moles of H2 per mole of free fatty acids,

[0299] - the decarbonylation of free fatty acids requiring 1 mole of H2 per mole of fatty acids free fats,

[0300] - the decarboxylation of free fatty acids which does not consume H2.

[0301] [Table 1] Mass balance Flow (kg / h) SI S2 S3 S4 S5 S6 S7 S8 S9 Composition Water (kg / h) 30000 30000 28500 1500 8550 19950 2826 Free fatty acids (kg / h 90197 Glycerol (kg / h) 9802 9802 9802 9802 1950.4 Triglycerides (kg / h) 100000 H2 (kg / h) 1187.2 CO2 (kg / h) 11193.6 Phospholipids (kg / h) 250 250 250

[0302] [Table 2] Molar balance Flow (kmol / h) SI S2 S3 S4 S5 S6 S7 S8 S9 Composition Water (kmol / h) 1665 1665 1583 83 475 1108.3 157 Free fatty acids (k mol / / h 319 Glycerol (kmol / / h) 106 106 106 106 21.2 Triglycerides (kmol / h) 106 H2 (kmol / / h) 593.6 CO2 (kmol / / h) 254.4 Phospholipids (km ol / / h) 0.34 0.34 0.34

[0303] [Table 3] Dihydrogen requirement H2 requirement for hydrotreatment: Moles of H2 / mol of free fatty acids: 2.3. H2 requirement for hydrotreatment: kmol / h: 733.7. H2 requirement covered by the unit: 80-81%.

Claims

1.

2. Demands A process for manufacturing hydrocarbon fluids, in particular paraffins, from a hydrocarbon feedstock of natural origin containing at least 50% by mass of glycerides, said process comprising: a) a step of hydrolysis of the naturally occurring hydrocarbon feedstock in which said naturally occurring hydrocarbon feedstock is brought into contact with water in a first reaction zone under conditions of total hydrolysis to produce free fatty acids, alcohols including glycerol, and water, b) a step of recovery of the products of step a) in which a first effluent containing the free fatty acids and a second effluent containing the alcohols and water are extracted separately from the first reaction zone, c) a hydrotreating step, in which the first effluent recovered in step b) is contacted with dihydrogen in at least a second reaction zone in the presence of at least one catalyst under suitable conditions to transform the free fatty acids contained in the first effluent into paraffins and form a hydrotreated effluent containing paraffins, d) an optional hydroisomerization and / or hydrocracking step in which the hydrotreated effluent from step c) is subjected to a hydroisomerization and / or hydrocracking reaction in a hydroisomerization and / or hydrocracking zone in the presence of dihydrogen and at least one catalyst to produce an isomerized and / or hydrocracking effluent rich in isoparaffins, e) an aqueous phase reforming step of the second effluent recovered in step b) in a third reaction zone, in which at least some of the alcohols it contains are converted into dihydrogen, carbon dioxide and carbon monoxide, f) a step of separating the dihydrogen formed during step e), the dihydrogen thus separated being sent to step c) of hydrotreatment, and optionally to step d). A process according to claim 1, wherein, before being sent to reforming step e), the second effluent recovered in step b) is subjected to at least one purification treatment selected from (i) a solids removal step and (ii) a contaminant removal step such as metals.

3. A method according to any one of the preceding claims, wherein the dihydrogen separation step (f) comprises at least one step selected from a membrane separation step, an adsorption separation step, in particular a pressure- or temperature-modulated adsorption separation step, and a CO2 liquefaction step.

4. A process according to any one of the preceding claims, wherein the hydrolysis step a) 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 feed mass ratio of 0.1 to 2, preferably of 0.25 to 1.

5.

5. A process according to any one of the preceding claims, characterized in that the naturally sourced hydrocarbon filler is a naturally sourced oil selected from a vegetable oil, an animal oil or fat, a used oil, an oil produced by microorganisms, and mixtures thereof.

6. A process according to any one of the preceding claims, characterized in that at least one liquefaction oil of a hydrocarbon feed selected from a biomass oil and a plastics oil is further introduced into said first reaction zone, the at least one liquefaction oil of a hydrocarbon feed representing at most 10% by mass, preferably at most 5% by mass, more preferably at most 1% by mass, of the hydrocarbon feed of natural origin introduced into said first reaction zone.

7. A process according to any one of the preceding claims, characterized in that a diluent is introduced into said first reaction zone, said diluent being selected from a hydrocarbon feedstock of fossil origin, a part or fraction of the hydrotreated effluent produced in step c), a part or fraction of the isomerized and / or hydrocracking effluent produced in step d) of hydroisomerization and / or hydrocracking.

8. A method according to claim 7, characterized in that it comprises at least one of the following features: - the quantity of diluent introduced into said first reaction zone represents 0.5 to 50% by mass of the feed to be treated introduced into said zone, said feed to be treated consisting of the feed of natural origin, and optionally of the liquefaction oil, - the diluent is introduced into said first reaction zone at a temperature of 200 °C to 350 °C.

9. A process according to any one of the preceding claims, characterized in that a hydrocarbon feedstock of fossil origin is further introduced in step c) and / or in step d) where that step is present, and optionally the quantity of first effluent recovered in step b) and / or hydrotreated effluent from step c) where step d) is present, represents from 0.5 to 90% by mass, more preferably from 0.5 to 50% by mass, preferably from 5 to 25% by mass, of the total feedstock introduced in step c) and / or in step d) where that step is present.

10. A process according to any one of claims 1 to 9, characterized in that it further comprises a step g) of producing syngas containing dihydrogen and in that the syngas produced in step g) is sent to step e) of reforming or to step f) of separating dihydrogen.

11. A process according to claim 10, characterized in that step g) of syngas production comprises a steam methane reforming step.

12. A process according to claim 11, characterized in that step g) of syngas production comprises the following substeps: (i) a step of biogas production by methanization of biomass, the biogas containing at least methane and CO2, (ii) an optional step of purification of the methane produced in step (i), (iii) a step of steam reforming of the methane produced in step (i) or of the purified methane in step (ii).

13. A process according to claim 12, and comprising a purification step according to claim 2 comprising a solids removal step, characterized in that the solids from the removal step are sent to step (i) of biogas production.