PRETREATMENT PROCESS BY HYDROLYSIS OF A NATURALLY SOURCED HYDROCARBONATE FEED

Abstract

PROCESS FOR PRETREATING A NATURALLY SOURCED HYDROCARBONATE FEEDBACK BY HYDROLYSIS The invention relates to a process for pretreating a naturally sourced hydrocarbon feedstock containing fatty acid esters by hydrolysis, wherein said naturally sourced hydrocarbon feedstock is contacted with water in a hydrolysis zone (10) to produce a first effluent rich in free fatty acids and a second effluent rich in alcohol and water, characterized in that a diluent selected from a hydrotreated naturally sourced oil, a hydrotreated and isomerized naturally sourced oil, and mixtures thereof, is introduced into the hydrolysis zone to be hydrolyzed with said naturally sourced hydrocarbon feedstock. The invention also relates to a process and a unit for manufacturing hydrocarbon fluids incorporating the pretreatment according to the invention upstream of hydrotreatment, and optionally of hydroisomerization and / or hydrocracking.Abbreviated figure: figure 1.

Description

Title of the invention: METHOD FOR PRETREATING A NATURALLY SOURCED HYDROCARBONATED FEEDBACK BY HYDROLYSIS technical field

[0001] The present invention relates to the pretreatment by hydrolysis of naturally occurring hydrocarbon feedstocks and a process for manufacturing hydrocarbon fluids from complex mixtures of renewable hydrocarbons comprising this pretreatment. 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. Context 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. Previous 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 hydrogen consumption.

[0008] Corrosion phenomena are observed, however, during the preliminary hydrolysis stage due to the acidity of the vegetable and / or animal oils being treated, but also during hydrotreatment.

[0009] Document WO2021 / 028833 describes a pretreatment by hydrolysis in which crude used oil (which may be cooking oil, category 1 animal fats, or residual oils) is hydrolyzed in the presence of an effluent containing mono-, di-, and triglycerides of fatty acids free from impurities, exiting an esterification unit. The addition of this effluent dilutes the contaminants present in the used oil, improves the homogenization of the feedstock, and removes impurities. The free fatty acids produced during hydrolysis are then sent to a hydrotreating unit and subsequently to a hydroisomerization and cracking unit. The glycerol produced during hydrolysis is sent, along with a portion of the fatty acids produced by hydrolysis, to an esterification unit producing the effluent that is hydrolyzed with the crude oil.This process therefore requires the integration of an esterification unit in addition to the hydrotreating and hydroisomerization units.

[0010] Thus, there is always a need to improve existing processes.

[0011] The invention aims in particular to propose a pretreatment process by hydrolysis of a hydrocarbon feedstock of natural origin, intended in particular to be integrated into an existing hydrocarbon fluid manufacturing process without profound modification thereof. Description of the invention

[0012] The invention proposes a pretreatment process by hydrolysis of a naturally sourced hydrocarbon feed containing fatty acid esters, in which said naturally sourced hydrocarbon feed is brought into contact with water in a hydrolysis zone to produce a first effluent enriched in free fatty acids, optionally containing fatty acid esters, and a second effluent rich in alcohol and water, characterized in that a diluent selected from a hydrotreated naturally sourced oil, a hydrotreated and isomerized naturally sourced oil and mixtures thereof, is introduced into the hydrolysis zone.

[0013] 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.

[0014] The quantity of diluent introduced into the hydrolysis zone can advantageously represent 0.5 to 150% by mass of the total charge introduced into said zone.

[0015] Advantageously, the diluent can be introduced into the hydrolysis zone at a temperature of 200 °C to 350 °C. This can be achieved, in particular, without preheating the diluent when it is taken directly from the outlet of a hydrotreating or hydroisomerizing zone, without intermediate cooling. In this case, the naturally occurring hydrocarbon feedstock can be introduced into the hydrolysis zone at a temperature of 50 to 250 °C.

[0016] Advantageously, the naturally sourced hydrocarbon feed containing fatty acid esters used in the pretreatment process may comprise, or be composed of, a naturally sourced oil, an esterified naturally sourced oil, or mixtures thereof. This naturally sourced oil may, in particular, be selected from a vegetable oil, an animal oil or fat, a used oil, an oil produced by microorganisms, and mixtures thereof. Used oil is preferred.

[0017] In one embodiment, at least one liquefaction oil of a hydrocarbon feed selected from a biomass oil and a plastics oil may be introduced further into said hydrolysis zone, the at least one liquefaction oil of a hydrocarbon feed representing at most 10% by mass of the hydrocarbon feed of natural origin introduced into said hydrolysis zone.

[0018] Regardless of the embodiment, hydrolysis can be carried out under one or more of the following conditions:

[0019] - a temperature of 130 to 350 °C,

[0020] - a pressure of 7 to 100 barg,

[0021] - a water / natural hydrocarbon mass ratio of 0.1 to 2, preference of 0.25 to 1.5.

[0022] Another object of the invention relates to a process for manufacturing hydrocarbon fluids from a naturally sourced hydrocarbon feedstock containing fatty acid esters, the process comprising at least: a. a pretreatment step by hydrolysis of the naturally occurring hydrocarbon feedstock in which said naturally occurring hydrocarbon feedstock is brought into contact with water in a hydrolysis zone to produce a first effluent enriched in free fatty acids optionally containing fatty acid esters, and a second effluent rich in alcohol and water, b. an optional separation and / or purification step of the first effluent from step a) in which residual alcohols, inorganic impurities and / or water are removed from the first effluent to obtain a purified first effluent, c. a hydrotreating step, in which the first effluent from step a), optionally purified in step b), is contacted with dihydrogen in a hydrotreating zone in the presence of at least one catalyst under suitable conditions to transform the free fatty acids, and optionally the fatty acid esters, contained in the first effluent into paraffins, and to form a hydrotreated effluent comprising a liquid fraction rich in paraffins and a fraction of non-condensable components, the liquid fraction forming a hydrotreated natural oil, the liquid fraction forming a hydrotreated natural oil, d. a step of separating the hydrotreated effluent from step c) in which the fraction of non-condensable components is separated from the liquid fraction forming a hydrotreated natural oil, e. an optional hydroisomerization and / or hydrocracking step in which the hydrotreated natural oil separated in step d) 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 forming a hydrotreated and isomerized and / or hydrocracking natural oil,

[0023] said process being characterized in that step a) is carried out according to the pretreatment process of the invention, said diluent introduced into the hydrolysis zone being chosen from, in particular consisting of, (i) a portion of the hydrotreated effluent from step c), optionally directly from step c), without intermediate cooling, (ii) a portion of the hydrotreated natural oil from step d), optionally directly from step d), without intermediate cooling, or (iii) a mixture of (i) and (ii), and optionally mixed with a portion of the isomerized and / or hydrocracked effluent from step e) of hydroisomerization and / or hydrocracking, optionally directly from step e), without intermediate cooling.

[0024] Another object of the invention relates to a process for manufacturing hydrocarbon fluids from a naturally sourced hydrocarbon feedstock containing fatty acid esters comprising at least: a. a pretreatment step by hydrolysis of the naturally occurring hydrocarbon feedstock in which said naturally occurring hydrocarbon feedstock is brought into contact with water in a hydrolysis zone to produce a first effluent enriched in free fatty acids optionally containing fatty acid esters, and a second effluent rich in alcohol and water, b. an optional separation and / or purification step of the first effluent from step a) in which residual alcohols, inorganic impurities and / or water are removed from the first effluent to obtain a purified first effluent, c. a hydrotreating step, in which the first effluent from step a), optionally purified in step b), is contacted with dihydrogen in a hydrotreating zone in the presence of at least one catalyst under suitable conditions to transform the free fatty acids, and optionally the fatty acid esters, contained in the first effluent into paraffins and to form a hydrotreated effluent comprising a liquid fraction rich in paraffins and a fraction of non-condensable components, the liquid fraction forming a hydrotreated natural oil, d. a step of separating the hydrotreated effluent from step c) in which the fraction of non-condensable components is separated from the liquid fraction forming a hydrotreated natural oil, e. a hydroisomerization and / or hydrocracking step in which at least a portion of the hydrotreated natural oil from step d) 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 forming a hydrotreated and isomerized and / or hydrocracking natural oil,

[0025] said process being characterized in that step a) is carried out according to a pretreatment process according to the invention, said diluent introduced into the hydrolysis zone being made up of a part of the isomerized and / or hydrocracked effluent from step e), optionally directly from step e), without intermediate cooling.

[0026] Another object of the invention relates to a process for manufacturing hydrocarbon fluids from a naturally sourced hydrocarbon feedstock containing fatty acid esters comprising at least: a. a pretreatment step by hydrolysis of the naturally occurring hydrocarbon feedstock in which said naturally occurring hydrocarbon feedstock is brought into contact with water in a hydrolysis zone to produce a first effluent enriched in free fatty acids optionally containing fatty acid esters, and a second effluent rich in alcohol and water, b. an optional separation and / or purification step of the first effluent from step a) in which residual alcohols, inorganic impurities and / or water are removed from the first effluent to obtain a purified first effluent, c. a hydrotreating step, in which the first effluent from step a), optionally purified in step b), is contacted with dihydrogen in a hydrotreating zone in the presence of at least one catalyst under suitable conditions to transform the free fatty acids, and optionally the fatty acid esters, contained in the first effluent into paraffins and to form a hydrotreated effluent comprising a liquid fraction rich in paraffins and a fraction of non-condensable components, the liquid fraction forming a hydrotreated natural oil, d. a step of separating the hydrotreated effluent from step c) in which the fraction of non-condensable components is separated from the liquid fraction forming a hydrotreated natural oil, e. a hydrocracking step in which at least a portion of the hydrotreated natural oil from step d) is subjected to a hydrocracking reaction in a hydrocracking zone in the presence of dihydrogen and at least one catalyst to produce a hydrocracking effluent that is at least partially cracked and rich in isoparaffins of reduced molecular weight relative to the hydrotreated effluent and forming a hydrotreated and hydrocraced natural oil, f. a separation step in which at least a portion of the hydrotreated and hydrocracking natural oil from step e) is subjected to a separation into a gaseous fraction, a naphtha fraction, a kerosene fraction and a diesel fraction.

[0027] said process being characterized in that step a) is carried out according to a pretreatment process according to the invention, and said diluent introduced into the hydrolysis zone consists of:

[0028] of a portion of the hydrocracked effluent from step e), optionally directly from step e), without intermediate cooling.

[0029] and / or part of the effluent separated in step f), in particular the diesel fraction, optionally directly from step f), without intermediate cooling.

[0030] Another object of the invention relates to a process for manufacturing hydrocarbon fluids from a naturally sourced hydrocarbon feed containing fatty acid esters comprising using the water produced in the separation step d) of the hydrotreated effluent of step c) in the hydrolysis step a) and / or in the purification step b) and thus reducing the net water requirement to carry out this step a) and / or b).

[0031] For this purpose, during step d), the water produced during the hydrotreatment step c) and contained in the hydrotreated effluent of step c) can be separated and returned, in the hydrolysis step a) and / or in the separation and / or purification step b), in particular in a washing step of the latter.

[0032] The pretreatment process according to the invention can thus be easily integrated into one of the aforementioned conventional hydrocarbon fluid manufacturing processes in that it is sufficient to add recycling lines for the effluent exiting steps c), d), e) and / or f) to the hydrolysis step a), without having to add additional treatment units such as in particular an esterification unit.

[0033] In particular, the effluents from steps c), d), e) and / or f) can be sent directly, without intermediate cooling, to the hydrolysis step for better thermal integration. The temperature of the diluent, comprising a portion of one or more of the aforementioned effluents, can then be maintained at a temperature of 200 °C to 350 °C, which limits the heating of the naturally occurring hydrocarbon feedstock, the latter being able to be heated to a temperature sufficient to make it fluid, for example to a temperature of 50 °C to 250 °C.

[0034] Thus, advantageously, the temperature of the diluent introduced into the hydrolysis zone can be from 200 to 350 °C.

[0035] Step c) of hydrotreating the manufacturing processes according to the invention can be implemented under one or more of the following conditions:

[0036] - a temperature of 100 to 550 °C,

[0037] - in the presence of dihydrogen at pressures ranging from 0.01 to 10 MPa,

[0038] - in the presence of at least one catalyst selected from (i) oxides, phosphides or sulphides of Ni, Mo, W, Co or mixtures of NiW, NiMo, CoMo, NiCoW, NiCoMo, NiMoW and CoMoW, (ü) 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.

[0039] Step e) of hydroisomerization and / or hydrocracking of the manufacturing processes according to the invention can be carried out under at least one of the following conditions:

[0040] - a temperature of 150 °C to 500 °C,

[0041] - a pressure of 1 MPa to 15 MPa.

[0042] In the manufacturing processes according to the invention, at least a portion of the non-condensable components separated in step d) can be sent to the hydrolysis zone, optionally after removal of components other than di-hydrogen.

[0043] The invention also relates to hydrocarbon fluid manufacturing units adapted to implement the manufacturing processes according to the invention.

[0044] Thus, another object of the invention relates to a unit for manufacturing hydrocarbon fluids from a naturally sourced hydrocarbon feedstock containing fatty acid esters, comprising:

[0045] - a hydrolysis zone comprising at least one first inlet conduit for the a naturally sourced hydrocarbon charge containing fatty acid esters, a second water inlet pipe, a first outlet pipe for a first effluent and a second outlet pipe for a second effluent, and optionally an additional inlet pipe, - an optional separation and / or purification treatment zone connected to the first outlet pipe of the hydrolysis zone, - a hydrotreatment zone comprising at least one inlet connected to the first outlet pipe of the hydrolysis zone or to an outlet of the optional treatment zone, and an outlet pipe for hydrotreated effluent, - a separation zone connected to the outlet pipe of the hydrotreatment zone, - optionally a hydroisomerization and / or hydrocracking zone connected to an outlet pipe from the separation zone, characterized in that it comprises at least one recycle line connected on the one hand to the hydrolysis zone or to an inlet line of the hydrolysis zone and on the other hand to the outlet line of the hydrotreatment zone or to an outlet line of the separation zone, and optionally another recycle line connected on the one hand to the hydrolysis zone or to an inlet line of the hydrolysis zone and on the other hand to an outlet line of the hydroisomerization and / or hydrocracking zone.

[0046] Yet another object of the invention relates to a unit for manufacturing hydrocarbon fluids from a naturally sourced hydrocarbon feedstock containing fatty acid esters, comprising: - a hydrolysis zone comprising at least one first inlet pipe for naturally sourced hydrocarbon feed containing fatty acid esters, a second inlet pipe for water, a first outlet pipe for a first effluent and a second outlet pipe for a second effluent, and optionally an additional inlet pipe, - an optional separation and / or purification treatment zone connected to the first outlet pipe of the hydrolysis zone, - a hydrotreatment zone comprising at least one inlet connected to the first outlet pipe of the hydrolysis zone or to an outlet of the optional treatment zone, and an outlet pipe for hydrotreated effluent, - a separation zone connected to the outlet pipe of the hydrotreatment zone, - a hydroisomerization and / or hydrocracking zone connected to an outlet pipe from the separation zone, characterized in that it comprises at least one recycle line connected on the one hand to the hydrolysis zone or to the inlet of the hydrolysis zone and on the other hand to an outlet line of the hydroisomerization and / or hydrocracking zone.

[0047] In one embodiment, the units according to the invention may include a second separation zone connected to the outlet line of the hydroisomerization and / or hydrocracking zone, and comprising at least one discharge line for a naphtha fraction, one discharge line for a kerosene fraction, and one discharge line for a diesel fraction, and generally a gas discharge line. The unit then includes a recycle line connected on the one hand to the hydrolysis zone or to an inlet line of the hydrolysis zone and on the other hand to one of the discharge lines of the second separation zone, preferably to the discharge line for a diesel fraction.

[0048] Advantageously, the recycle lines of these units are connected directly to the elements they connect, without intermediate cooling equipment. Detailed description of the invention

[0049] 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.

[0050] The expressions % by weight and % by mass have equivalent meanings and are refer to the proportion of the mass of a product relative to 100g of a composition comprising it.

[0051] 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.

[0052] Naturally derived hydrocarbon filler containing fatty acid esters

[0053] By "hydrocarbon feed of natural origin", we mean a hydrocarbon feed not containing components of fossil origin.

[0054] The naturally sourced hydrocarbon filler containing fatty acid esters used in the present invention may comprise, or consist of, a naturally sourced oil, an esterified naturally sourced oil, or mixtures thereof.

[0055] 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.

[0056] The oil of natural origin may be chosen from a vegetable oil, an animal oil or fat, a used oil, an oil produced by microorganisms, as well as mixtures thereof.

[0057] A naturally sourced oil is defined as an oil that does not contain mineral oil of fossil origin.

[0058] Typically, an oil of natural origin may contain 50% or more, preferably 60% or more, preferably 70% or more, of fatty acids and / or fatty acid esters (mono-, di-, triglycerides).

[0059] In one embodiment, a naturally derived oil may contain fatty acid esters (mono-, di-, or triglycerides) and / or free fatty acids, containing one to three C8-C24 acyl groups, saturated or unsaturated. When several acyl groups are present, they may be identical or different.

[0060] The vegetable oil may be chosen from pine oil, rapeseed oil, sunflower oil, castor oil, peanut oil, linseed oil, babassu oil, oil of hemp, linola oil, jatropha oil, peanut oil, rice bran oil, mustard oil, carinata oil, coconut oil, copra oil, olive oil, palm oil, cottonseed oil, corn oil, palm kernel oil, soybean oil, pumpkin seed oil, grapeseed oil, argan oil, jojoba oil, sesame oil, walnut oil, hazelnut oil, tung oil, rice oil, safflower oil, seaweed oil, used oils, nut shell oil (including cashew nut shell oil), and any combination thereof.

[0061] 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 grease from the food industry, and used cooking oils which are animal by-products.

[0062] 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.

[0063] 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).

[0064] 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.

[0065] 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.

[0066] 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 using well-known mechanical or chemical extraction methods.

[0067] 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 numerous other organic and inorganic components, including phosphatides, sterols, tocopherols, toco- trynols, 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.

[0068] Preferably, the natural oils used in the present invention have not undergone pretreatment, such as the chemical and physical pretreatments usually carried out by a person skilled in the art, similar to those carried out for the treatment of food oils, such as degumming, neutralization with an alkaline solution (generally NaOH), bleaching, finishing or polishing, steam treatment, cavitation, etc.

[0069] 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 or ethyl esters of fatty acids, and comprising impurities from the oils, may also be part of the naturally sourced hydrocarbon fillers considered in the present invention.

[0070] The naturally derived hydrocarbon filler used in the present invention may thus contain 50% or more, preferably 60% or more, preferably 70% or more, of fatty acids and / or fatty acid esters (mono-, di-, triglycerides, alkyl esters of fatty acids, and in particular ethyl esters of fatty acids, methyl esters of fatty acids). In general, the naturally derived hydrocarbon filler comprises at most 99% of fatty acids and / or fatty acid esters.

[0071] 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.

[0072] 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.

[0073] 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. Liquefaction oil for a hydrocarbon feedstock

[0074] By "liquefaction oil", we mean 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.

[0075] 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, ...).

[0076] 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.

[0077] 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.

[0078] The term “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 mixtures, 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 mixtures.

[0079] 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 understood to mean materials composed of polymers and optionally of auxiliary components such as plasticizers, fillers, colorants, catalysts, flame retardants, stabilizers, etc. For example, these polymers may 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, etc. 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 and synthetic rubbers. They may be found in tire-type waste or any other household or industrial waste containing elastomers, natural and / or synthetic rubber, mixed or not with other components, such as plastics, plasticizers, fillers, vulcanizing agents, vulcanization accelerators, additives, etc.Examples of elastomeric polymers include ethylene-propylene copolymers, ethylene-propylene-diene terpolymer (EPDM), polyisoprene (natural or synthetic), polybutadiene, styrene-butadiene copolymers, isobutene-based polymers, isobutylene-isoprene copolymers, chlorinated or brominated, acrylonitrile butadiene copolymers (NBR), and polychlorinated polypropylenes (CR), polyurethanes, silicone elastomers, etc.

[0080] In general, any polymer or mixture of polymers capable of producing hydrocarbons by liquefaction may be used.

[0081] 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).

[0082] Plastic oils contain, in particular, paraffins, i-paraffins (iso-paraffins), dienes, alkynes, olefins, naphthenes, and aromatics. Plastic liquefaction oils also contain impurities containing heteroatoms, such as chlorinated, oxygenated, sulfurous, nitrogenous, and / or silylated organic compounds, metals, salts, and phosphorus compounds.

[0083] 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.

[0084] 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 number of 10 to 130 g Br2 / 100 g, as measured according to ASTM DI 159, and / or a maleic anhydride number (UOP326-82) of 1 to 55 mg maleic anhydride / lg.

[0085] 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 preferably at most 350°C, preferably 250°C (measured according to standard NF EN 15199-1 / 2).

[0086] A plastics oil typically comprises at least 20 ppm of heteroatoms, or even at least 30 ppm of heteroatoms.

[0087] A plastics oil may in particular comprise one or more of the following heteroatom contents: from 0 to 8%m of oxygen (measured according to ASTM D5622), from 1 to 13000 ppm of nitrogen (measured according to ASTM D4629), from 2 to 1000 ppm of sulfur (measured according to ISO 20846), from 1 to 1000 ppm of metals (measured by ICP), from 50 to 6000 ppm of chlorine (measured according to ASTM D7359-18), from 0 to 200 ppm of bromine (measured according to ASTM D7359-18), from 1 to 40 ppm of fluorine (measured according to ASTM D7359-18), 1 to 2000 ppm of silicon (measured by XRF).

[0088] The expression "biomass oil" refers to liquid hydrocarbon products obtained from the pyrolysis or hydrothermal liquefaction of one or more biomasses.

[0089] Biomass can be defined as an organic product of plant or animal origin.

[0090] 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.

[0091] 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.

[0092] 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 notably contain carboxylic acids, ketones, aldehydes, and phenols. Hydrotreated natural oil

[0093] The term "hydrotreated natural oil" means a natural oil, or a mixture of natural oils, that has undergone hydrotreatment. The natural oil is as defined above. It may, in particular, be chosen from among a vegetable oil, an animal oil or fat, a used oil, or an oil produced by microorganisms.

[0094] During hydrotreatment, hydrogenation of the unsaturates present in the aliphatic chains of fatty acids occurs and the elimination of oxygen atoms by hydrodeoxygenation and / or decarboxylation and / or decarbonylation, leading to the formation of paraffins, and in particular essentially n-paraffins.

[0095] The hydrotreatment can be as described below with reference to step hydrotreating of the process for manufacturing hydrocarbon fluids according to the invention.

[0096] The hydrotreated natural oil can be subjected to a further hydroisomerization treatment in order to transform at least some of the n-paraffins into isoparaffins. This is then referred to as a hydrotreated and isomerized natural oil.

[0097] The hydrotreated natural oil can be subjected to a further hydrocracking treatment in order to transform at least some of the n-paraffins into isoparaffins of reduced molecular weight. This is then referred to as a hydrotreated and hydrocracking natural oil.

[0098] The paraffin content of a hydrotreated natural oil, optionally isomerized and / or hydrocracked, may be at least 70% by mass, advantageously at least 80% by mass, typically at most 99% by mass.

[0099] The n-paraffin content of a hydrotreated natural oil may be at least 50% by mass, preferably at least 60% by mass, preferably at least 70% by mass, more preferably at least 80% by mass, typically at most 99% by mass.

[0100] The iso-paraffin content of a hydrotreated and isomerized and / or hydrocracked natural oil may be at least 50% by mass, preferably at least 60% by mass, preferably at least 70% by mass, more preferably at least 80% by mass, typically at most 99% by mass.

[0101] The chain length of the paraffins present in a hydrotreated, optionally isomerized and / or hydrocracking, natural oil varies depending on the natural oil used. Most often, these paraffins are C9-C24.

[0102] The chain length of the paraffins present in a hydrotreated and hydrocracking natural oil varies depending on the natural oil used and the severity of the hydrocracking step. Most often, these paraffins are C2-C24. A. Pretreatment process by hydrolysis

[0103] The pretreatment process according to the invention makes it possible to hydrolyze at least a portion of the esters present in the naturally occurring hydrocarbon feedstock in order to obtain free fatty acids and alcohols. It is therefore the reverse reaction of an esterification reaction.

[0104] During this step, the naturally occurring hydrocarbon charge reacts with water under suitable conditions to form free fatty acids and alcohols resulting from the dissociation of esters.

[0105] The hydrocarbon filler may contain mono-, di-, or triglycerides of fatty acids, and / or alkyl esters of fatty acids, and in particular ethyl esters of fatty acids and methyl esters of fatty acids. The alcohols formed thus include glycerol, alkyl alcohols, in particular ethanol and methanol, and other alcohols resulting from the partial or total hydrolysis of the fatty acid esters present. The fatty acids released depend on the nature of the natural oil used.

[0106] 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.

[0107] 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 percent 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).

[0108] 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 steam 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. Optionally, superheated steam may also be introduced to provide additional heat to further heat the feedstock, for example, steam at 300 to 500 °C at the hydrolysis pressure (typically 50 barg). This introduction may be carried out at one or more points in the hydrolysis zone. Alternatively, a combination of preheated water and steam may be used and introduced at one or more points in the hydrolysis zone.

[0109] Hydrolysis is typically carried out without a catalyst.

[0110] 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).

[0111] The hydrolysis zone may comprise one or more reactors operating in batch or continuous mode. For example, a countercurrent reactor or a cocurrent reactor equipped with a static mixer may be used. The hydrolysis zone may contain packing to improve contact between the different phases of the reactor.

[0112] Typically, the two phases of the biphasic mixture are extracted separately from the hydrolysis zone, the phase containing the fatty acids being extracted from an upper part of the first zone and forming a first effluent rich in free fatty acids and the denser aqueous phase being typically drawn from a lower part of the first zone and forming a second effluent rich in alcohol and water.

[0113] According to the invention, a diluent is also introduced into the hydrolysis zone. This diluent may be a hydrotreated natural oil, with or without non-condensable components, a hydrotreated, isomerized, and / or hydrocracking natural oil, or a mixture of these oils. Preferably, the diluent may contain at least some branched hydrocarbons. Preferably, the diluent may contain at least some hydrocarbons having the same number of carbon atoms in the chain.

[0114] 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.

[0115] Adding a diluent may allow: - Improved phase separation of polar products, such as glycerol, and inorganic impurities from non-polar products, such as free fatty acids; - reduced corrosion in the hydrolysis zone due to free fatty acids present in the naturally occurring hydrocarbon feedstock. - 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.

[0116] Furthermore, hydrolysis itself allows: - the removal of metals and heteroatoms present (especially P) in the naturally occurring hydrocarbon feedstock, these contaminants being found in the aqueous phase which is separated from the naturally occurring hydrocarbon charge, - a limitation of propane production during subsequent hydrotreatment of the first hydrotreated effluent rich in fatty acids, - a reduction in dihydrogen consumption during subsequent hydrotreatment of the first hydrotreated effluent rich in fatty acids.

[0117] 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.

[0118] Advantageously, the diluent can come directly from a hydrotreating step, a hydrocracking step and / or a hydroisomerization step, without intermediate cooling. It can then be at a temperature of 200 to 350 °C, typically 230 to 300 °C.

[0119] 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 can then be introduced into the hydrolysis reaction at a temperature sufficient to ensure its fluidity, for example, from 50 °C to 250 °C.

[0120] Advantageously, the amount of diluent introduced into the hydrolysis zone can represent 0.5 to 150% by mass, preferably 5 to 100% by mass, more preferably 5 to 40% by mass, even more preferably 10 to 20% by mass, of the total load introduced into the hydrolysis zone, or in any range defined by two of these limits.

[0121] In one embodiment of the invention, at least one liquefaction oil of a hydrocarbon feedstock selected from a biomass oil and a plastics oil may 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, more preferably from 0.5 to 5% by mass. This may allow for the incorporation of more components of renewable and / or natural origin, and possibly the addition of aromatic compounds.

[0122] The first effluent produced by the hydrolysis pretreatment process contains predominantly free fatty acids, typically at least 10% by mass of free fatty acids. It also generally contains esters of free fatty acids, typically in a content of at most 90% by mass.

[0123] Hydrolysis may be partial. In this case, the content of free fatty acids formed may then be limited, for example to a maximum of 20% by mass, the content of free fatty acid esters being, for example, a maximum of 80% by mass. Partial hydrolysis may can be obtained at moderate temperatures (temperatures close to the lower limit of the aforementioned ranges, and generally at low pressure) and / or by reducing the reaction time.

[0124] Hydrolysis can be complete. In this case, the content of free fatty acids formed can be high, for example, on the order of 60% by mass. 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.

[0125] Hydrolysis can also be carried out in the presence of a catalyst.

[0126] 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.

[0127] B. Process for manufacturing hydrocarbon fluids

[0128] The hydrolysis pretreatment process according to the invention is particularly advantageous when integrated into a process for manufacturing hydrocarbon fluids by hydrotreatment, and optionally hydroisomerization and / or hydrocracking.

[0129] Thus, the invention also relates to a process for manufacturing hydrocarbon fluids from a hydrocarbon feedstock of natural origin containing fatty acid esters as previously defined. Step a) of hydrolysis

[0130] According to the invention, the hydrolysis pretreatment step a) is carried out according to the hydrolysis pretreatment process of the present invention, the diluent introduced into the hydrolysis zone being formed from a portion of the effluent from step c) and / or a portion of the hydrotreated natural oil from step d) and / or a portion of the hydrotreated and isomerized natural oil from step e) and / or a portion of the hydrotreated and hydrocracked natural oil from step e) and / or a portion of the hydrotreated, hydrocracked and separated natural oil from step f) of the manufacturing process.In particular, these recycled parts can be taken directly from the output of the relevant stages and sent directly, notably without intermediate cooling, to the hydrolysis stage, in order to limit the heating required to the naturally occurring hydrocarbon feedstock before it enters stage a) and thus limit its degradation.

[0131] Optional step b) of separation and / or purification

[0132] The first effluent from the hydrolysis step may still contain alcohol residues, inorganic impurities and / or water.

[0133] The manufacturing process according to the invention may then include an optional step b) of treatment, in particular separation and / or purification, of the first effluent rich in free fatty acids produced during step a), during which the free fatty acids are separated from the alcohols, inorganic impurities and / or residual water present in this first effluent. This treatment step b) may be carried out in a treatment area comprising one or more separation and / or purification zones.

[0134] 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.

[0135] The treatment area may include a water washing area, preferably implemented in a contactor, typically upstream of the separation tank when present.

[0136] 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.

[0137] 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.

[0138] 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. Step c) of hydrotreatment

[0139] The first effluent from step a), or the first purified effluent from step b), is then subjected to hydrotreatment in a hydrotreatment zone in the presence of dihydrogen and at least one catalyst under suitable conditions to transform the free fatty acids, and optionally the fatty acid esters, contained in the first effluent into paraffins and form a paraffin-rich effluent.

[0140] This hydrotreatment step is typically carried out in the presence of dihydrogen and of 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.

[0141] 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.

[0142] The catalyst may have a supported or unsupported catalytic active phase.

[0143] 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.

[0144] It is also preferable that the support of the catalytic active phase has a low acidity, preferably neutral or basic, in order to avoid hydro-isomerization reactions which would give rise to branched paraffins and cracking at high temperature and pressure in the presence of dihydrogen.

[0145] Hydrotreating 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.

[0146] 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.

[0147] 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.

[0148] 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 keep the hydrogen present in the effluent in solution, thus limiting the amount of hydrogen that needs to be separated during the separation step d). This can promote the hydrotreatment reaction.

[0149] Alternatively or in combination, a 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 in dissolved form to be brought to the hydrotreating zone.

[0150] During this step c) of hydrotreating, different reactions can take place in the transformation of fatty acid esters and free fatty acids into paraffins: • 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 fatty 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; • a decarboxylation and / or a decarbonylation (DCOX), which leads to the formation of paraffins with one less carbon atom than the initial fat 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.

[0151] The implementation of the pretreatment step by hydrolysis of the present invention makes it possible to reduce the formation of propane.

[0152] 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. Hydrodeoxygenation

[0153] 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 C-O 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 large amount of dihydrogen.

[0154] By way of example, the equation for the hydrodeoxygenation of fatty acids is given:

[0155] R-CH2-CH2-COOH + 3 H2 to R-CH2-CH2-CH3 + 2 H2O.

[0156] 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, C0M0, NiCoW, NiCoMo, NiMoW and C0M0W as a catalytic phase, preferably supported on carbon, alumina, silica, titanium oxide or zirconia.

[0157] 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 bars), for example 6 MPa, and with a dihydrogen / hydrocarbon feed ratio of 100 to 2000, but preferably 350 to 1500, for example 800 NI H2 / l of hydrocarbon feed.

[0158] 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 compounds, and tetrahydrothiophenic compounds.

[0159] 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. Decarboxylation and / or decarbonylation

[0160] Under decarboxylation and / or decarbonylation conditions, the following reactions may occur:

[0161] Decarboxylation:

[0162] R-CH2-CH2-COOH to R-CH2-CH3 + CO2

[0163] [Ci8H33O]3C3H5O3 + 6 H2 → 3 Ci7H36 + 3 CO2 + C3H8

[0164] Decarbonylation:

[0165] R-CH2-CH2-COOH to R-CH=CH2 + CO + H2O

[0166] Other reactions that can occur under decarboxylation and / or decarbonylation conditions are:

[0167] - hydrogenation of unsaturated bonds:

[0168] R-CH=CH2 + H2 to R-CH2-CH3

[0169] - the hydrodeoxygenation of fatty acids:

[0170] R-CH2-CH2-COOH + 3 H2 to R-CH2-CH2-CH3 + 2 H2O

[0171] Further hydrogenation of the CO / CO2 produced can occur depending on the amount of dihydrogen available, the catalyst, and the reaction conditions:

[0172] CO + 3 H2 → CH4 + H2O

[0173] CO2 + 4 H2 à CH4 + 2 H2O

[0174] 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.

[0175] The catalyst can be selected from:

[0176] - the oxides, phosphides or sulphides 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

[0177] - 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

[0178] - basic oxides, such as alkali metal oxides (MgO, ZnO), the alkali-earth oxides, lanthanide oxides, zinc oxide, spinels (Mg 2Al2O4, 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).

[0179] 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.

[0180] 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. Separation step d)

[0181] The hydrotreated effluent from step c) is subjected, in part or in whole, before being sent to step e) or f), to a separation step d) in which non-condensable components such as propane, CO2, CO, methane, dihydrogen and vaporized water are separated from the liquid fraction.

[0182] 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 referred, in part or in whole, to the entry of step c).

[0183] In one embodiment, the effluent from step c) can thus be separated into: - a gaseous stream containing H2, H2S, CO2, and possibly small amounts of CO and NH3, - water, - a liquid fraction containing a mixture of paraffins.

[0184] The gas stream can undergo further treatment in order to separate the dihydrogen from the other gases for reuse in the process.

[0185] 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.

[0186] According to the invention, part of this liquid fraction can serve as a diluent during the hydrolysis step.

[0187] 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.

[0188] 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.

[0189] The water produced in the hydrotreatment can be used in step a) of hydrolysis or in step b) of purification and thus reduce the net need for water to carry out this step a) and / or b).

[0190] Step e) of hydroisomerization and / or hydrocracking

[0191] All or part of the hydrotreated natural oil from step d) 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 feedstock, forming a hydrotreated and isomerized and / or hydrocraced natural oil.

[0192] 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.

[0193] 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.

[0194] 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,

[0195] Hydrocracking catalysts possess a strong acid function, preferably sulfated zirconias, tungsten zirconias and zeolites or mixtures thereof.

[0196] 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.

[0197] The distance between the two functions, acidic and (de)hydrogenating, is one of the key parameters governing the activity and selectivity of the catalyst.

[0198] 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.

[0199] 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.

[0200] 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.

[0201] 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.

[0202] The catalysts and the conditions for hydroisomerization and / or hydrocracking are well known in the art.

[0203] 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.

[0204] 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.

[0205] 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.

[0206] 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 dihydrogen-containing gases in a downward flow mode, in an upward flow mode, or the liquid feed can flow in a downward flow while the di-containing gases... hydrogen flows in an upward flow mode through the catalyst beds.

[0207] 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 from about 0.1 to 20 h₁, more preferably 0.2 to 10 h₁, and most preferably 0.3 to 4 h₁. The supplied dihydrogen-containing gases can be introduced simultaneously with the feedstock at a ratio of 75 to 2500 NI (H₂) / L of feedstock, more preferably 150 to 1500 NI or more preferably 250 to 1000 NI.

[0208] 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. Step f) of separation

[0209] In one embodiment of the invention, the process for manufacturing hydrocarbon fluids may further include a separation step f) in which the effluent from step d) or the effluent from step e), preferably the effluent from step e), is separated into at least one fraction selected from a naphtha fraction, a kerosene fraction and a diesel fraction.

[0210] The effluent exiting step d) or e), preferably the effluent from step e), particularly under hydrocracking conditions, may undergo fractionation, for example by adding a separation column, for example a distillation column, or by lateral withdrawal.

[0211] 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 d) or e).

[0212] 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.

[0213] 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.

[0214] The recovered kerosene fraction preferably has a final boiling point below 300 °C, particularly 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, particularly without the addition of other components such as esters.

[0215] In particular, the cutting points of the recovered fractions can be adapted to obtain products meeting particular specifications, in particular without having to add other components such as esters.

[0216] In one embodiment, one of the separated fractions, in particular the diesel fraction, can be used to form all or part of the diluent. Detailed description of the figures

[0217] 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:

[0218] Fig. 1 schematically represents a hydrocarbon fluid manufacturing unit according to an embodiment of the invention.

[0219] Figure [Fig. 2] schematically represents a hydro fluid manufacturing unit carbonaceous according to another embodiment of the invention.

[0220] In the figures, the same elements are designated by the same numerical references.

[0221] Figure 1 represents a hydrocarbon fluid manufacturing unit 100 comprising a hydrolysis zone 10 and a hydrotreating zone 20. The hydrolysis zone 10 may be a co-current mixer reactor or a counter-current reactor. The feedstock to be treated enters the hydrolysis zone 10 through a first conduit 1. This feedstock is a naturally occurring hydrocarbon feedstock containing fatty acid esters as previously defined, and typically containing fatty acid triglycerides and / or alkyl fatty acid esters. This feedstock may be introduced at a temperature above 75 °C but preferably below 300 °C.

[0222] 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.

[0223] 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.

[0224] 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 via a line 6. This aqueous phase also contains a majority of the pollutants initially contained in the naturally occurring hydrocarbon feedstock.

[0225] 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 liquid fraction rich in paraffins, forming a hydrotreated oil, and a fraction of non-condensable components. A portion of this hydrotreated oil can be conveyed via a line 7b to a hydroisomerization and / or hydrocracking zone, or to a fractionation zone (not shown). According to the invention, a portion of the hydrotreated oil is conveyed via a line 7a to the hydrolysis zone 10. As a result of this incorporation, the effluent rich in free fatty acids exiting the hydrolysis zone also contains hydrotreated oil of natural origin.Thus, the addition of hydrotreated oil allows for the dilution of the naturally occurring hydrocarbon load in the hydrolysis zone, as well as the dilution of the free fatty acids produced during hydrolysis and discharged via line 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, in order to limit the exothermicity of the reactions involved.

[0226] Moreover, the hydrotreated oil exiting the hydrotreatment zone 20, in particular directly, without intermediate cooling, is at a temperature of at least 250 °C, so that its introduction into the hydrolysis zone 10 provides part of the heating required for the hydrolysis reaction, improving the thermal integration of the unit.

[0227] It should be noted that the hydrotreated oil can be sent directly to the hydrolysis zone 10, without having undergone prior degassing, so that it contains unreacted di-hydrogen which dissolves in the feed and is then found in the first effluent 5 which then enters the hydrotreatment zone 20. This makes it possible in particular to reduce the need for energy to recycle the gaseous di-hydrogen by compression in the hydrotreatment zone.

[0228] Typically, the hydrotreatment zone 20 includes a supply pipe 8 of the dihydrogen, and one or more catalytic beds. A catalytic bed dedicated to demetallation (guard bed) can be provided at the inlet of the hydrotreating zone to remove chlorine, metals, and silicon. The hydrotreating zone may include one or more reactors operated in series, in parallel, or both. Isolated, lead-lag, series, and / or parallel guard reactors can be considered depending on the nature and quantity of contaminants in the stream to be treated.

[0229] Fig. 2 represents a hydrocarbon fluid manufacturing unit 200, which differs from that shown in Fig. 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 Fig. 1.

[0230] 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 11 allows for the condensation of some of the water contained in the first effluent, as well as the alcohols and pollutants present in this water, which are 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 to omit the guard bed.

[0231] The separator tank 11 and / or the guard bed(s) 21 are part of an optional treatment zone 15 implementing the optional treatment step b). This hydrotreatment zone may also include a contactor (not shown) for washing the effluent with water upstream of the separator tank 11.

[0232] At the outlet of the hydrotreatment zone 20, the hydrotreated effluent discharged via the line 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.

[0233] The liquid organic phase leaves the flask 31 via a conduit 35 to enter the stripping column 32, into which steam is introduced via a conduit 36. The gases are evacuated from the stripping column 32 via a conduit 37 and the fraction liquid forming a hydrotreated natural oil is recovered at the bottom of column 32 via pipe 38.

[0234] Part of the hydrotreated natural oil is conveyed to the hydroisomerization and / or hydrocracking zone 40 via line 38b, while another part is returned upstream of the hydrotreatment zone 20 via line 38a. This line 38a thus includes a section 38c which joins line 1, introducing the natural hydrocarbon feedstock into the hydrolysis zone. It should be noted that this section of line 38c could be directly connected to the hydrolysis zone 10.

[0235] 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.

[0236] 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.

[0237] 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 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).

[0238] In some embodiments, the manufacturing unit according to the invention is devoid of a hydroisomerization and / or hydrocracking zone 40. In this case, the diluent used in the hydrolysis zone comes only from a part of one or more of the flows circulating in the pipes 7, 35 and 38.

[0239] Examples of circulating effluent temperatures and pressures are given in [Fig.2]. It can thus be seen that high-temperature flows are 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.

[0240] It should be noted that the effluent discharged by pipe 7 from the hydrotreatment zone of unit 100 or pipe 42 from the hydroisomerization and / or hydrocracking zone 40 can be sent to a fractionation zone 50 (not shown) 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.

[0241] Regardless of the embodiment, the diluent can be introduced into the hydrolysis zone via the first inlet line 1, via the second inlet line 2, or via a dedicated inlet (not shown).

Claims

Claims

1. A method of pretreatment by hydrolysis of a hydrocarbon feedstock of natural origin containing fatty acid esters, in which said hydrocarbon feedstock of natural origin is brought into contact with water in a hydrolysis zone (10) to produce a first effluent enriched in free fatty acids, optionally containing fatty acid esters, and a second effluent rich in alcohol and water, characterized in that a diluent chosen from a hydrotreated oil of natural origin, a hydrotreated and isomerized oil of natural origin and their mixtures, is introduced into the hydrolysis zone.

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

3. Pretreatment method according to claim 1 or 2, characterized in that the diluent is introduced into the hydrolysis zone at a temperature of 200°C to 350°C.

4. A method of pretreating any one of claims 1 to 3, characterized in that the hydrocarbon feedstock of natural origin containing fatty acid esters comprises an oil of natural origin, an esterified oil of natural origin or mixtures thereof.

5. Pretreatment method according to any one of claims 1 to 4, characterized in that at least one liquefaction oil of a hydrocarbon feedstock chosen from a biomass oil and a plastics oil is also introduced into said hydrolysis zone, the at least one liquefaction oil of a hydrocarbon feedstock representing at most 10% by mass of the hydrocarbon feedstock of natural origin introduced into said hydrolysis zone.

6. Pretreatment process according to any one of claims 1 to 5, characterized in that the hydrolysis is carried out under one or more of the following conditions: - a temperature of 130 to 350 °C, - a pressure of 7 to 100 barg, - a water / natural hydrocarbon feedstock mass ratio of 0.1 to 2, preferably of 0.25 to 1.

5.

7. Process for manufacturing hydrocarbon fluids from a hydrocarbon feedstock of natural origin containing fatty acid esters comprising at least: a) a pretreatment step by hydrolysis of the hydrocarbon feedstock of natural origin in which said hydrocarbon feedstock of natural origin is brought into contact with water in a hydrolysis zone (10) to produce a first effluent enriched in free fatty acids optionally containing fatty acid esters, and a second effluent rich in alcohol and water, b) an optional step of separation and / or purification of the first effluent from step a) during which residual alcohols, inorganic impurities and / or water are removed from the first effluent to obtain a first purified effluent, c) a hydrotreatment step, in which the first effluent from step a), optionally purified in step b), is brought into contact with dihydrogen in a hydrotreatment zone (20) in the presence of at least one catalyst under conditions suitable for transforming the free fatty acids, and optionally the fatty acid esters, contained in the first effluent into paraffins and forming a hydrotreated effluent comprising a liquid fraction rich in paraffins and a fraction of incondensable components, the liquid fraction forming a hydrotreated oil of natural origin, d) a step of separating the hydrotreated effluent from step c) during which the fraction of incondensable components is separated from the liquid fraction forming a hydrotreated oil of natural origin, e) an optional hydroisomerization and / or hydrocracking step during which the hydrotreated oil of natural origin separated in step d) is subjected to a hydroisomerization and / or hydrocracking reaction in a hydroisomerization and / or hydrocracking zone (40) in the presence of dihydrogen and at least one catalyst to produce an iso-paraffin-rich isomerized and / or hydrocracked effluent forming a hydrotreated and isomerized and / or hydrocracked oil of natural origin, said process being characterized in that step a) is carried out according to the pretreatment process of any one of claims 1 to 6, said diluent introduced into the hydrolysis zone being chosen from (i) a portion of the hydrotreated effluent from step c), optionally originating directly from step c), without intermediate cooling, (ii) a portion of the hydrotreated oil of natural origin from step d), optionally originating directly from step d), without intermediate cooling, or (iii) a mixture of (i) and (ii), and optionally-

8. clearly mixed with a portion of the isomerized and / or hydrocracked effluent from step e) of hydroisomerization and / or hydrocracking, optionally coming directly from step e), without intermediate cooling. Process for manufacturing hydrocarbon fluids from a hydrocarbon feedstock of natural origin containing fatty acid esters, comprising at least: a) a pretreatment step by hydrolysis of the hydrocarbon feedstock of natural origin in which said hydrocarbon feedstock of natural origin is brought into contact with water in a hydrolysis zone (10) to produce a first effluent enriched in free fatty acids optionally containing fatty acid esters, and a second effluent rich in alcohol and water, b) an optional step of separation and / or purification of the first effluent from step a) during which residual alcohols, inorganic impurities and / or water are removed from the first effluent to obtain a first purified effluent, c) a hydrotreatment step, in which the first effluent from step a), optionally purified in step b), is brought into contact with dihydrogen in a hydrotreatment zone (20) in the presence of at least one catalyst under conditions suitable for transforming the free fatty acids, and optionally the fatty acid esters, contained in the first effluent into paraffins and forming a hydrotreated effluent comprising a liquid fraction rich in paraffins and a fraction of incondensable components, the liquid fraction forming a hydrotreated oil of natural origin, d) a step of separating the hydrotreated effluent from step c) during which the fraction of incondensable components is separated from the liquid fraction forming a hydrotreated oil of natural origin, e) a hydroisomerization and / or hydrocracking step during which at least part of the hydrotreated oil of natural origin from step d) is subjected to a hydroisomerization and / or hydrocracking reaction in a hydroisomerization and / or hydrocracking zone (30) in the presence of dihydrogen and at least one catalyst to produce an iso-paraffin-rich isomerized and / or hydrocracked effluent forming a hydrotreated and isomerized and / or hydrocracked oil of natural origin, said method being characterized in that step a) is implemented

9. according to a pretreatment process according to any one of claims 1 to 6, said diluent introduced into the hydrolysis zone consisting of a part of the isomerized and / or hydrocracked effluent from step e), optionally leaving directly from step e), without intermediate cooling. Process for manufacturing hydrocarbon fluids from a hydrocarbon feedstock of natural origin containing fatty acid esters, comprising at least: a) a pretreatment step by hydrolysis of the hydrocarbon feedstock of natural origin in which said hydrocarbon feedstock of natural origin is brought into contact with water in a hydrolysis zone (10) to produce a first effluent enriched in free fatty acids optionally containing fatty acid esters, and a second effluent rich in alcohol and water, b) an optional step of separation and / or purification of the first effluent from step a) during which residual alcohols, inorganic impurities and / or water are removed from the first effluent to obtain a first purified effluent, c) a hydrotreatment step, in which the first effluent from step a), optionally purified in step b), is brought into contact with dihydrogen in a hydrotreatment zone (20) in the presence of at least one catalyst under conditions suitable for transforming the free fatty acids, and optionally the fatty acid esters, contained in the first effluent into paraffins and forming a hydrotreated effluent comprising a liquid fraction rich in paraffins and a fraction of incondensable components, the liquid fraction forming a hydrotreated oil of natural origin, d) a step of separating the hydrotreated effluent from step c) during which the fraction of incondensable components is separated from the liquid fraction forming a hydrotreated oil of natural origin, e) a hydrocracking step during which at least part of the hydrotreated oil of natural origin from step d) is subjected to a hydrocracking reaction in a hydrocracking zone in the presence of dihydrogen and at least one catalyst to produce a hydrocracking effluent at least partially cracked and rich in isoparaffins of reduced molecular mass compared to the hydrotreated effluent and forming a hydrotreated and hydrocracked oil of natural origin, f) a separation step during which at least a portion of the hydrocracking effluent from step e) is subjected to separation into a gaseous fraction n, a naphtha fraction, a diesel fraction and a kerosene fraction, said process being characterized in that step a) is carried out according to a pretreatment process according to any one of claims 1 to 6, said diluent introduced into the hydrolysis zone consisting of a portion of the hydrocracking effluent separated in step f), in particular the diesel fraction, optionally originating directly from step f), without intermediate cooling, optionally mixed with a portion of the hydrocracked effluent from step e), optionally originating directly from step e), without intermediate cooling.

10. Manufacturing process according to any one of claims 7 to 9, wherein the hydrotreatment step c) is carried out under one or more of the following conditions: - a temperature of 100 to 550°C - in the presence of dihydrogen at pressures ranging from 0.01 to 10 MPa, - in the presence of at least one catalyst chosen from (i) oxides, phosphides or sulfides of Ni, Mo, W, Co or mixtures of NiW, NiMo, CoMo, NiCoW, NiCoMo, NiMoW and CoMoW, (ii) metals or mixtures of metal alloys from group 10 and group 11 of the periodic table, (iii) basic oxides such as alkali metal oxides, alkaline earth oxides, lanthanide oxides, zinc oxide, spinels, perovskites, calcium silicates.

11. Manufacturing process according to any one of claims 7 to 10, in which step e) of hydroisomerization and / or hydrocracking is carried out under at least one of the following conditions: - a temperature of 150°C to 500°C, - a pressure of 1 MPa to 15 MPa.

12. Manufacturing process according to any one of claims 7 to 11, characterized in that at least a part of the incondensable components separated in step d) are sent to the hydrolysis zone, optionally after removal of the components other than dihydrogen.

13. Manufacturing process according to any one of claims 7 to 12, characterized in that, during step d), the water produced during hydrotreatment step c) and contained in the hydrotreated effluent from step c) is separated and returned, in hydrolysis step a) and / or in separation and / or purification step b).

14. Manufacturing unit (100, 200) of hydrocarbon fluids from a hydrocarbon feedstock of natural origin containing fatty acid esters, comprising: - a hydrolysis zone (10) comprising at least a first inlet pipe (1) for the hydrocarbon feedstock of natural origin containing fatty acid esters, a second inlet pipe (3, 4) for water, a first outlet pipe (5) for a first effluent and a second outlet pipe (6) for a second effluent, and optionally an additional inlet pipe (2), - an optional separation and / or purification treatment zone (15) connected to the first outlet pipe (5) of the hydrolysis zone, - a hydrotreatment zone (20) comprising at least one inlet connected to the first outlet pipe (5) of the hydrolysis zone or to an outlet of the optional treatment zone (15), and an outlet pipe (7) for a hydrotreated effluent, - a separation zone (30) connected to the outlet pipe (7) of the hydrotreatment zone, - optionally a hydroisomerization and / or hydrocracking zone (40) connected to an outlet pipe (38) of the separation zone (30), characterized in that it comprises at least one recycle pipe (38a, 38c; 7a) connected on the one hand to the hydrolysis zone (10) or to an inlet pipe (1) of the hydrolysis zone and on the other hand to the outlet pipe (7) of the hydrotreatment zone or to an outlet pipe (38) of the separation zone (30), and optionally another recycle pipe (43) connected on the one hand to the hydrolysis zone (10) or to an inlet pipe of the hydrolysis zone and on the other hand to an outlet pipe (42) of the hydroisomerization and / or hydrocracking zone (40).

15. Manufacturing unit (200) of hydrocarbon fluids from a hydrocarbon feedstock of natural origin containing fatty acid esters, comprising: - a hydrolysis zone (10) comprising at least a first inlet pipe (1) for the hydrocarbon feedstock of natural origin containing fatty acid esters, a second inlet pipe (3, 4) for water, a first outlet pipe (5) for a first effluent and a second outlet pipe (6) for a second effluent, and optionally an additional inlet pipe (2), - an optional separation and / or purification treatment zone (15) connected to the first outlet pipe (5) of the hydrolysis zone, - a hydrotreatment zone (20) comprising at least one inlet connected to the first outlet pipe (5) of the hydrolysis zone or to an outlet (38) of the optional treatment zone, and an outlet pipe (7) for a hydrotreated effluent, - a separation zone (30) connected to the outlet pipe (7) of the hydrotreatment zone, - a hydroisomerization and / or hydrocracking zone (40) connected to an outlet pipe (38) of the separation zone (30), characterized in that it comprises at least one recycle pipe (43) connected on the one hand to the hydrolysis zone (10) or to an inlet pipe (1) of the hydrolysis zone and on the other hand to an outlet pipe (42) of the hydroisomerization and / or hydrocracking zone.

16. Manufacturing unit (200) according to claim 14 or 15, characterized in that it comprises a second separation zone (50) connected to the outlet pipe (42) of the hydroisomerization and / or hydrocracking zone, and comprising at least one discharge pipe (52) for a naphtha fraction, one discharge pipe (63) for a kerosene fraction and one discharge pipe (54) for a diesel fraction, and in that it further comprises a recycle pipe (55) connected on the one hand to the hydrolysis zone (10) or to an inlet pipe (1) of the hydrolysis zone and on the other hand to one of the discharge pipes of the second separation zone, preferably to the discharge pipe (54) for a diesel fraction.

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