FR3034099A1 - OPTIMIZED BIO-OIL CONVERSION PROCESS WITH LOAD STABILIZATION - Google Patents

Abstract

The present invention relates to a process for producing hydrocarbons comprising at least one hydroreforming step from a feedstock comprising at least one bio-oil, said feedstock being stabilized by contacting said feedstock, in the presence of a reducing agent, with a so-called stabilizing catalyst in the zones where the temperature is sufficient to initiate the formation of polymers and / or solids, that is to say in which the temperature is at least greater than 80 ° C., said catalyst said stabilization being either integrated in said zone, or dispersed in said load.

Description

Dornr. The present invention relates to the conversion of bio-oils by a catalytic process in which the thermal stabilization of the feed is improved by the addition of a so-called stabilization catalyst. The so-called stabilizing catalyst is placed or injected, in the presence of a reducing agent, into the areas of the process where the bmp. Is suitable for the formation of solids thus making it possible to provide an increased catalytic contribution and to avoid clogging or clogging of process equipment. This invention relates to the treatment of liquids from biomass and in particular liquefied biomass from pyrolysis (also called bio-oil) for the production of hydrocarbon products, in particular chemicals and / or ready-to-use hydrocarbon jets. liquid fuels called biofuels. technique Bio-oils are liquid products obtained by thermochemical liquefaction of cellulosic biomass. Thermochemical processes generally convert biomass into liquid, gaseous and solid products. Among these processes, so-called rapid pyrolysis methods tend to maximize the liquid yield. During rapid pyrolysis, the temperature of the biomass, optionally finely divided, is rapidly raised to values above about 300 ° C. and preferably between 300 and 900 ° C. and the effluent is condensed in the form of biocompounds. oil. Ringer et al. (LargeScale Pyrolysis Oit Production: A Technology Assessment and Economic Analysis, M. Ringer, V. Putsche, and J. Scahill, NREL Technical Report NREL / TP-510-37779, November 2006) have studied the different achnologies implemented for the rapid pyrolysis of biomass on a large scale. They include bubbling fluid beds, circulating fluidized beds, ablative pyrolysis reactors, vacuum pyrolysis and rotary cone pyrolysis. At first glance, bio-oils derived from the rapid pyrolysis of biomass could in principle provide low-cost renewable liquid fuels; indeed, their use as fuel for boilers, stationary gas turbines and diesels has been described. In addition, rapid pyrolysis has been developed at a relatively large scale, on the order of several hundred tons per day. However, this technology has not yet attracted much commercial interest. Indeed, a bio-oil and a particular bio-oil resulting from the rapid pyrolysis of the biome: a complex mixture of highly oxygenated polar hydrocarbon products obtained from the rupture of biopolymers, having physical and chemical properties limiting its direct use as a biofuel. Pyrolysis bio-oils have undesirable properties such as: (1) corrosivity due to their high water and organic acid content; (2) a low specific calorific value due to the high oxygen content, typically of the order of 40% by weight; (3) chemical instability due to the abundance of reactive functional groups such as the carbonyl group, which can lead to polymerization during storage and hence phase separation; (4) a relatively high viscosity and phase separation tendency under high shear conditions, in an injector for example; (5) an incompatibility with conventional hydrocarbon fuels because of their insolubility therein; (6) solid particles of coal resulting from pyrolysis, which will always be present in unfiltered bio-oils to a greater or lesser degree, may cause clogging of injectors and pipes, 7) thermal instability due to their propensity to polymerize at temperatures above 100 ° C. All of these aspects combine to make the handling, transportation, storage and processing of bio-oils difficult, and costly, thereby integrating them into existing heat and energy systems and technologies. problematic. The economic viability of the production of bio-oils for energy applications thus depends on the discovery of suitable methods for their recovery into a liquid fuel of higher quality, at a sufficiently low cost. Indeed, considerable efforts have been made in recent years to seek practical technologies that can overcome all or some of the disadvantages mentioned above. Over the last twenty years, the approach of direct hydrotreatment of the bio-oil for conversion to stable hydrocarbons or oxygenated liquids has been intensively studied. Elliott has published a detailed study of three historical developments, including the work with model compounds known to be present in bio-oils (Historical Developments Hydroprocessing Bioils, DC Elliott, Energy & Fuels 2007, 21, 1792 One of the major obstacles to the direct catalytic hydrotreatment of bio-oils is their propensity to polymerize when subjected to temperatures above about 100 ° C, which gives rise to formation of solids at temperatures above about 100 ° C, with consequences such as clogging of charge lines, furnaces and reactors, as well as the rapid deactivation of the catalyst, or even clogging of the reactor inlet. partially overcome by hydrotreating only the thermally resistant portion of the bio-oil, thus, by adding water to the bio-oil, it can be separated e into an aqueous phase and a viscous phase of higher density, General lies between 20 and 30% by weight of bio-oil, called pyrolytic lignin as amply derived from the woody portion of the charge pyrolysis of biomass. Since pyrolytic lignin is rich in phenolic material, it has a much greater thermal stability than that of the carbohydrate-derived portion of the bio-oil, and is therefore easier to catalytically hydrotreat without formation of solids. . This is the approach followed by Piskorz and a /. (Conversion of Lignins to Hydrocarbon Fuels, Piskorz, Majerski, D. Radlein, and D.S. Scott, Energy & Fuels, Vol 3, 723-726, 1989) and, more recently, by Marker and Petri in US Pat. No. 7,578,927. This method has the disadvantage of carrying out a step of separating the bio-oil upstream of the catalytic hydrotreating stage and the obligation to treat the two fractions separately. The resulting process is complex and its implementation leads to losses in mass and energy yield, as well as a higher operating cost. The hydrotreatment of the complete bio-oil, that is to say having not undergone any prior separation step was considered. US Pat. No. 4,795,841 proposes a process for the hydrotreatment of the complete bio-oil in two stages, the bio-oil being used alone, ie not mixed with other streams, in the first step of which the thermal stability The overall bio-oil is improved by catalytic hydrogenation at a temperature of about 250 ° C. However, this two-stage hydrotreating process results in solid formation and rapid deactivation of the catalyst. Hydroprocessing of bio-oils is also difficult because of the formation of multiple organic phases, in addition to the aqueous phase. Furthermore, the kinetics of hydrogenation is slow, especially at the relatively low temperatures required for the thermal stabilization of bio-oils. US-2009 / 0,253,948 discloses a method of converting biomass-derived pyrolysis oil into a liquid fuel by means of a two-stage deoxygenation of the pyrolysis oil and separation of the products, in wherein the final hydrocarbon product as well as the fractions resulting from the final distillation and boiling at boiling temperatures corresponding to the recoverable fractions in the gasoline, kerosene and diesel fuel pools can be recycled. However, it does not teach the degree of dispersion or solubilization of the pyrolysis oil in a hydrocarbon medium. The patent application (VVO 2012/035410 A2) relates to a two-step process for the production of a stable hydrocarbon effluent that can be incorporated into the fuel pool, from a feedstock comprising at least one bio-oil that has not been subjected to no preprocessing stage. In this invention the catalyst contemplated is an additional unducted catalyst. This requires the use of a catalyst supported on particles of large size (0.9 - 2 mm) to avoid training. The use of the supported catalysts can lead to an early deactivation of the catalytic activity by clogging the pores making the active phase inaccessible to the reagents; large support dimensions and small pore diameters may also impose infusional limitations on the higher molecular weight reagents. All of these aspects make 3034099 4 reactions:, f. polymerization can take place impacting the stability of the effluent and / or the load even before injection into the reactor. The same constraints are found in the application W02012 / 140335A, which describes a process for converting solid lignocellulosic biomass, optionally mixed with a lignocellulosic pyrolytic oil, the process comprising a step of setting the stage. pnnsion the biomass particles in a solvent, then a bubbling bed hydroconversion stage in the presence of a non-driven supported catalyst and a second hydroconversion stage in a slurry reactor containing a dispersed catalyst and trained, said catalyst being kept in suspension in said reactor and circulating from bottom to top with the feedstock and discharged with the product effluent. In this case, it is a question of successive hydroconversion stages, the order in which they are carried out being indifferent. This type of sequence allows to take advantage of this type of reactor called slurry reactor, upstream or downstream of the reactor operating in bubbling bed. The patent application US2012 / 0285079 describes a method for stabilizing the pyrolysis oil comprising a step of hydrogenation of the bio-oil in the presence of a ruthenium catalyst at a temperature of at least greater than 70 ° C. and must be preferably kept below 100 ° C so as not to degrade the bio-oil, and at a pressure of at least 600 psig (4.1 MPa) to produce a hydrogenated bio-oil. However, this document does not describe any step of recycling any of the effluents resulting from the process. On the other hand, the catalyst for the stabilization of the oil must be supported and the noble metal content must be relatively high because of the low hydrogenation kinetics encountered in the temperature range envisaged. The patent application WO2008 / 151792 describes a process for hydroconversion of heavy oils and in particular heavy oils of petroleum origin comprising a hydroconversion step by passing said oil over at least one bubbling bed and in the presence of a heterogeneous and supported hydroconversion catalyst and a nano-dispersed hydrogenation catalyst in said oil, said nano-dispersed catalyst circulating through the reactors and being evacuated with the produced effluent which is then separated to produce a a liquid fraction containing said nano-dispersed catalyst, said fraction being subsequently recycled to the hydroconversion stage. The heterogeneous and supported hydroconversion catalyst comprises at least one Group VIII metal and at least one Group VIB metal deposited on an oxide support which is then converted to a transition metal sulfide, a zeolite or possibly clay. to be added to the medium. The nano-dispersed hydrogenation catalyst comprises molybdenum or tungsten sulfide may be formed in situ or ex situ. The process operates at a temperature between 360 and 130 ° C and a pressure of 10 to 20 MPa. The difficulties encountered in the treatment of bio-oils have their origin in the rapid thermal polymerization of the bio-oil, which leads to line blockages and reaction equipment as well as to rapid deactivation of the hydrotreatment catalyst. classic. In fact, at the temperatures typically required, for the hydrotreatment of the bio-oils, the polymerization reactions are substantially faster than the hydrotreatment reactions, which ultimately leads to the formation of solids or gums. There is therefore a need for an improved bio-oil hydrotreatment process that minimizes solids formation, deactivation of the catalyst, and maximizes the yield of hydrocarbons produced. It is also desirable to maximize the hydrocarbon fraction whose boiling point is in the boiling range of fuels such as gasoline, kerou'Te or diesel. The present invention constitutes in this sense an improvement of the process described in application VV02012 / 140335A. SUMMARY OF THE INVENTION The present invention relates to a process for producing hydrocarbons comprising at least one hydroreforming step from a feedstock comprising at least one bio-oil, said feedstock being thermally stabilized by contacting said feedstock. charge, in the presence of a reducing agent, with a so-called stabilizing catalyst in areas where the temperature is sufficient to initiate the formation of polymers and / or solids, ie in which the temperature is at least higher at 80 ° C, preferably upstream of the reactor or reactors in which the hydroreforming step is carried out, or directly in the said reactor or said reactor, said stabilization catalyst being either integrated in said zone or dispersed in the charge prior to introduction of said feed into the first hydroreforming step. Thus, the polymerization and solids formation reactions resulting from the heating of said feedstock to temperatures at least greater than 80 ° C are minimized in hot areas such as equipment and convoy lines located between the heating equipment and the ( s) hydroreforming reactor (s), heating equipment and reactor (s) included.

In particular, the present invention relates to a process for producing hydrocarbon products from a filler comprising at least one bicool oil, said process comprising the steps of introducing said filler into a first hydroreforming stage comprising at least one least one reactor, in the presence of hydrogen and a hydroreforming catalyst comprising at least one transition metal chosen from the elements of groups 3 to 12 of the periodic table and at least one support selected from activated carbons, silicon carbides, silicas, transition aluminas, alumina silicas, zirconium oxide, cerium oxide, titanium oxide and transition metal aluminates, taken alone or as a mixture, for obtaining at least one liquid effluent comprising at least one aqueous phase and at least one organic phase, said first hydroreforming stage operating at a temperature of between 250 and 450 ° C., at an absolute pressure of between 3 and 30 MPa, at a hourly space velocity per ra: at the bio-oil level greater than 0.2 h -1, and with a quantity of hydrogen introduced such that the ratio volume hydrogen on a bio-oil is between 50 and 2000 Nm3 / m3, and wherein at least a portion of the organic phase of the effluent from said first hydroreforming stage is recycled in mixture with said feedstock comprising at least one biomass oil, with a recycling rate equal to the ratio of the mass flow rate of said organic phase to the mass flow rate of the bio-oil of between 0.05 and 5, a second hydrotreating and / or hydrocracking stage of at least one part of the organic phase of the effluent from the first hydroreforming step to obtain a hydrocarbon effluent, in which a so-called stabilization catalyst is brought into contact with said feedstock, in the presence of an agent. reducer in at least one area of the process wherein the temperature at least greater than 80 ° C, said catalyst being either integrated in said zone, or dispersed in said charge. Throughout the rest of the text, the term catalyst integrated in said zone, a solid catalyst, shaped to adapt to the internal geometry of the area in which it is placed, so as to occupy the entire section of passage of the said charge while minimizing the losses of loads in the equipment. Throughout the remainder of the text, dispersed catalyst is understood to mean a catalyst having a particle size and a density adapted to its entrainment, that is to say to its circulation in the three-phase reactor (s) by the liquid flows, said dispersed catalyst circulating from bottom to top, with the feedstock, in the said three-phase reactor (s), and being withdrawn from the said triphasic reactor (s) with the liquid effluent produced. An advantage of the present invention is to prevent the formation of polymers and solids that can lead to fouling or clogging in hot zones, in which the temperature is at least greater than 80 ° C. upstream of the reactor (s) such as the equipment and lines used for heating and transporting the feedstock to the hydroreforming reactor (s) by integrating or injecting into said zones a catalyst or catalytic precursor, and thus improving the thermal stability of said chard d ~ ,, ns said hot zones and eliminate the risk of frequent blockages.

Another advantage of the process is to improve the performance of the process according to the invention by enabling the production of a stable hydrocarbon effluent that can be incorporated into the fuel pool, from a feedstock comprising at least one bio-oil, comprising an oxygen content of less than 5% and preferred. less than 1% by weight and a water content of less than 0.1% by weight relative to the total mass of said hydrocarbon effluent, without significant formation of coke or bio-oil polymers, with low deactivation rates of the first one. hydroreforming catalyst, improved conversion rates and reduced hydrogen consumption. In the case of the use of hydroreforming reactor (s) driven or bubbling bed and dispersed stabilizing catalyst, another advantage of the present invention is the increase of the catalytic contribution to the thermal contribution for the same volume of reactor which allows to have a better control on the selectivity of the reactions. Even at the inter-equipment lines and in the high-temperature separators located downstream of the hydroreforming reactor or reactors, the use of a so-called stabilization catalyst, dispersed in addition to the first conventional catalyst used in the step of hydroreforming, allows a gain in stability of the products obtained and an increase in catalytic performance. These advantages will make it possible to obtain greater hydrogenation and stabilization of the products. The operating cost of the process according to the invention is therefore reduced. Another advantage of the present invention is to provide a process having a great flexibility with respect to the nature of the liquids derived from the biomass that can be used as feedstock comprising at least one bio-oil, in particular liquids resulting from the pyrolysis of the biomass, which can have wide ranges of viscosity, water content and degree of polymerization, depending on the origin of the biomass and the pyrolysis process used. Another advantage of the present invention is to avoid thermal reactions outside the reaction zone containing the supported catalyst, which allows a better operability of the unit, especially in the separation zone. Detailed description of the invention. Charge The feedstock treated in the process according to the invention is a feedstock comprising at least one bio-oil.

The bio-oil of the filler treated in the process according to the invention may advantageously be a pretreated or non-pretreated biofilter.

Preferably, the bio-oil of the filler treated in the process according to the invention is unpretreated, that is to say that said bio-oil has not undergone any pretreatment step after the pyrolysis. In particular, said bio-oil has not undergone any pretreatment step intended to reduce its metal content, its solids content, its water content or its acid content.

A bio-oil is a complex mixture of oxygenated compounds obtained from breaking biopolymers present in the original biomass. In the case of organic, lignocellulosic, bio-oil contains compounds derived from cellulose, hemicellulose and lignin (structure present in lignocellulosic biomass). In particular, a bio-oil is a highly oxygenated polar hydrocarbon product which generally comprises at least 10% by weight of oxygen, preferably from 10 to 60% by weight, and preferably from 20 to 50% by weight of oxygen relative to the total weight of said In general, the oxygenated compounds are alcohols, aldehydes, esters, ethers, organic acids, aromatic oxygen compounds and free water, the free water being at least 5% by weight, preferably at least 10% wt and preferably at least 20 wt% of the bio-oil.These properties make the bio-oil totally immiscible with hydrocarbons, even with aromatic hydrocarbons, Bio-oils are advantageously outcome s of biomass preferably selected from plants, grasses, trees, wood chips, seeds, fibers, seed husks, aquatic plants, hay and other sources of lignocellulosic material, such as by For example, those from municipal waste, agro-food waste, forest waste, slaughter residues, agricultural and industrial wastes (such as, for example, sugar cane bagasse, dehydrated canes, etc.). oil palm, sawdust or straws). Bio-oils may be derived from paper pulp and by-products of recycled or non-recycled paper or by-products of paper mills. The bio-oils are advantageously obtained by thermochemical liquefaction of the biomass, preferably by pyrolysis, and preferably by rapid, slow pyrolysis with or without a catalyst (in the presence of a catalyst, this is known as catalytic pyrolysis). Pyrolysis is a thermal decomposition in the absence of oxygen, with thermal cracking of the gas, liquid and solid feedstocks. A catalyst may advantageously be added to enhance the conversion during so-called catalytic pyrolysis. Catalytic pyrolysis generally gives a bio-oil having a lower oxygen content than the bio-oil obtained by thermal decomposition, but the yield of bio-oil is generally lower. The selectivity between the gas, the liquid and the solid is related to the reaction temperature and the residence time of the vapor. Biomass pyrolysis processes, including rapid pyrolysis, are well described in the literature such as, for example, A.V. Bridgwater, H. Hofbauer and S. van Loo, Thermal Biomass Conversion, CPL Press, 2009, 37-78.

The slow pyrolysis is advantageously carried out at a temperature of between 350 and 450 ° C. and preferably of the order of 400 ° C. and with a residence time of a few minutes to a few hours which favors the production of a solid product also called carbonization product or charcoal. In particular, slow pyrolysis generally allows; production of 35% by weight of gas, 30% by weight of liquid and 35% by weight of char. Gasification processes operating at very high temperatures, preferably above 800 ° C, promote the production of gas, and in particular more than 85% by weight of gas. The intermediate pyrolysis is advantageously carried out at a temperature generally of between 450 and 550 ° C. and with a residence time of the short vapor, preferably between 10 and 10 seconds, which favors the liquid yield. In particular, the intermediate pyrolysis generally allows the production of 30% weight of gas, 50% by weight of liquid and 20% by weight of char. The rapid pyrolysis is advantageously carried out at a temperature generally of between 450 and 550 ° C. and with a residence time of the very short vapor, preferably between 0.5 and 2 seconds, which maximizes the liquid yield: in particular, rapid pyrolysis generally allows the production of 10-20% by weight of gas, 60-75% by weight of liquid and 10-20% by weight of carhanation product. High liquid yields are thus obtained in fast pyrolysis processes with a liquid yield of up to 75% by weight.

Preferably, the bio-oils used in the process according to the present invention are obtained by rapid pyrolysis of the biomass. The filler treated in the process according to the invention preferably comprises a bio-oil content of between 10 and 100% by weight relative to the total weight of said filler. Preferably, the treated feedstock consists of 100% bio-oil.

The filler comprising at least one bio-oil used in the process according to the invention may also advantageously contain another. compounds derived from biomass, said compounds being advantageously chosen from vegetable oils, algal or algal oils, fish oils, fats of vegetable or animal origin, and alcohols derived from fermentation of biomass sugars , or mixtures of such fillers, pretreated or not. Vegetable oils or oils derived from animal fats essentially comprise chemical structures of the triglyceride type which the person skilled in the art also knows under the name tri-ester of fatty acid: 3 as well as free fatty acids, whose fatty chains contain a number of carbon atoms of between 9 and 25.

The said vegetable oils may advantageously be crude or refined, wholly or in part, and derived from plants selected from rapeseed, sunflower, soybean, palm, olive, coconut, copra, castor, cotton, peanut, flax and crambe oils and all oils derived for example from sunflower or rapeseed by genetic modification or hybridization, this list not being limiting. Said animal fats are advantageously chosen from bacon and fats composed of residues from the food industry or from the food service industries. Fried oils, animal oils; N.Kings such as fish oils, tallow, lard can also be used. Said feed comprising at least one bio-oil may also advantageously be treated in admixture with at least one hydrocarbon feedstock derived from petroleum and / or coal. The hydrocarbon feedstock derived from petroleum can advantageously be chosen from direct distillation distillates under vacuum, vacuum distillates obtained from a conversion process, such as coking, fixed-bed hydroconversion and hydrotreatment of heavy fractions by distillation. bubbling bed, the products resulting from catalytic cracking in fluidized bed, such as for example the light cycle oil (LCO), the heavy cycle oil (HCO) and any distillate from catalytic cracking fluidized bed generally having a distillation range d The aromatic extracts and paraffins obtained in the preparation of lubricating oils and the solvent deasphalted oils, alone or in admixture, are used at about 150 ° C. to about 370 ° C. The hydrocarbon feedstock derived from coal may advantageously be selected from the products resulting from the liquefaction of coal and the aromatic fractions from the pyrolysis or gasification of coal and shale oils or products derived from shale oils, alone or mixed, pretreated or not. Preferably, said filler comprising at least one bio-oil may advantageously be a mixture of any of the abovementioned fillers, said fillers possibly being pretreated or not.

Prior to the hydroreforming step, said liquid feedstock comprising at least one bio-oil may advantageously undergo at least one pretreatment step for separating at least one fraction comprising solid impurities from said liquid feedstock and / or reducing the amount of acidic and / or highly reactive compounds which can polymerize. Said pretreatment step may be, without being exhaustive, a step of physically separating liquids and solids, by any means whatsoever (filtration, centrifugation, magnetic separation, extraction, treatments in basic or acid medium ,. ...,), a chemical reaction step (such as, for example, esterification, acetalization, etc.) making it possible to transform the oxygenated molecules responsible for the thermal instability of the bio-oil at low temperature, for example less than 100 ° C, or the mixture with an ad-hoc solvent for better bio-oil, ...

Said pretreatment step allowing the elimination of at least a portion of said solid impurities and / or oxygen molecules responsible for the thermal instability of the bio-oil, such as certain carbonyl and carboxylic species, for example can be done by any solid / liquid separation techniques or any chemical reaction known to those skilled in the art. Preferably, said pretreatment step is carried out on said feedstock comprising at least one bio-oil mixed or not with a liquid flow of the process or outside the process, for example a solvent. Preferably, said step of pretreatment by physical separation of liquids and solids is carried out by filtration, centrifugation, electrostatic precipitation, or decantation, said techniques being used alone or in combination, in any order, some being able to operate cyclically to ensure continuous operation of the entire process. Implementation of the stabilization of the charge According to the invention, said charge is thermally stabilized by bringing said charge into contact with a so-called stabilizing catalyst in the presence of a reducing agent in at least one zone of the process wherein the temperature is at least greater than 80 ° C, said catalyst being either integrated in said zone or dispersed in said charge. Preferably, the reducing agent is hydrogen. Preferably, hydrogen is recycle hydrogen from the process or fresh hydrogen. Preferably, the reducing agent is advantageously introduced in an amount such that the ratio of feed reducing agent introduced is between 50 and 2000 Nm3 / m3 and preferably between 100 and 1000 Nm3 / m3. Preferably, bringing said charge into contact with a so-called stabilizing catalyst in the presence of a reducing agent in at least one zone of the process in which the temperature is at least greater than 80 ° C. is carried out in the presence of at least at least a portion of the organic phase of the effluent 25 from the first hydroreforming step. The zones in which temperatures are at least greater than 80 ° C. are advantageously the heating equipment, the transport lines of the said feedstock up to the hydroreforming reactor (s), the preheating exchangers, the furnaces , the convoy lines between the equipment, the injection lines or any equipment located upstream of the reactor (s) of the hydroreforming stage. The hydroreforming reactor or reactors are also advantageously one or more zones in which the temperature is at least greater than 80 ° C.

Preferably, the so-called stabilizing catalyst is placed in areas where the temperature is at least greater than 80 ° C, and preferably at least greater than 100 ° C. According to a first variant, the so-called stabilization catalyst is brought into contact with said charge prior to the introduction of said charge. in the first hydroreforming stage, in the presence of a reducing agent, upstream of the reactor (s) of the hydroreforming stage, in at least one zone in which the temperature is at least greater than 80 ° C. In the case where the catalyst is brought into contact with the feedstock prior to the introduction of said feedstock in the first hydroreforming stage, the so-called stabilization catalyst is placed in the presence of hydrogen and of said feedstock to be stabilized, before introduction into the or; in one or more sections of the process in which the thermal reaction reactions resulting in the formation of polymers and / or solids are high3. In this case, the zones in which the temperature is at least greater than 80 ° C. are advantageously the heating equipment, the transport lines of the said chain, up to the hydroreforming reactor (s), the preheating exchangers, furnaces, convoy lines between equipment, injection lines or any equipment located upstream of the reactor (s) of the hydroreforming stage. According to a second variant, the so-called stabilization catalyst is brought into contact with said feedstock directly in said hydroreforming reactor (s). In this configuration, triplexic slurry or bubbling bed reactor technology is preferred. According to a third variant, at least a portion of the catalyst may advantageously be dispersed in the feedstock prior to the introduction of said feedstock into the first hydroreforming stage and introduced continuously with the feedstock into the said reactor (s) and the other part can be introduced directly into the said three-phase reactor (s) of the first hydroreforming step. According to the invention, said so-called stabilization catalyst is either integrated in said zone or dispersed in said charge when it is brought into contact with said charge prior to introduction of said charge into the first hydroreforming step . The so-called stabilization catalyst, whether integrated or injected, is a shaped metal, said metal being chosen from transition metals chosen from nickel, cobalt, platinum, palladium, copper and aluminum. iron, alone or in alloy, said catalyst possibly also containing at least one support selected from metal oxides, preferably silicas, transition aluminas, silica aluminas, zirconium oxide, cerium oxide, titanium oxide, activated carbons, silicon carbides and transition metal aluminates alone or as a mixture.

In the case where the metal is chosen from noble metals, preferably platinum and palladium, the metal content is advantageously between 0.1 and 10% by weight relative to the total mass of the catalyst and preferably between 0.5 and 8% wt. In the case where the metal is chosen from non-noble metals, preferably from nickel, cobalt, copper and iron, the metal content is advantageously between 1 and 95% by weight relative to the total weight of said catalyst and preferably between 5 and 95% by weight. The term catalyst integrated in said zone, a catalyst shaped to adapt to the internal geometry of the area in which it is placed, so as to occupy the entire passage section of said load while minimizing losses of loads in the equipment.

It can advantageously be placed in one or more sections of the process prior to introduction into the hydroreforming reactor. Said integrated catalyst can advantageously be fixed or mobile in the equipment or line in which it is placed. Advantageously, the integrated catalyst is integral with the equipment in which it is integrated but can be easily removed and replaced by a so-called fresh or regenerated catalytic system. In another configuration, the so-called structured stabilization catalyst is mobile and circulates in circles in the lines and equipment where stabilization is necessary by training with said load and via a system for recycling the catalytic system. It is also possible to remove it from the process for generating, or to replace it with, a new so-called fresh or regenerated catalytic system According to another embodiment, the so-called stabilization catalyst is deposited by methods known to those skilled in the art, on the inner surface d2S areas where the temperature is above 80 ° C and preferably at least sw :: - .. sieure 100 ° C. Preferably, the integrated catalyst can be in form foam, grid, greasing, porous monolith, or any shape to occupy the entire cross-section of said filler, preferably said integrated catalyst is a solid catalyst, elme and containing at least one element capable of activating hydrogen and optionally at least one support selected from metal oxides, preferably silicas, transition aluminas, silica aluminas, zirconium oxide, cerium, titanium oxide, Ch. Abonaacfifa. silicon carbides and transition metal aluminates alone or in admixture.

According to a first variant, the integrated catalyst is a shaped metal, said metal being chosen from transition metals chosen from nickel, cobalt, platinum, palladium, copper and iron, alone or in alloy . Preferably, the integrated catalyst is chosen from Raney Ni in the form of metal foam, grid or lining.

In the case where the integrated catalytic catalyst or precursor is a shaped metal, said integrated catalyst may advantageously be a metal or a metal alloy shaped to fit the internal geometry of the equipment in which said catalyst or integrated catalytic precursor is placed. According to a second variant, the integrated catalyst is a shaped metal, said metal being chosen from among the transition metals chosen from nickel, cobalt, platinum, palladium, copper and iron, alone or in alloy, said catalyst being also supported and containing at least one support selected from metal oxides, preferably silicas, transition aluminas, silica aluminas, zirconium oxide, cerium oxide, titanium oxide, activated carbons, silicon carbides and transition metal aluminates alone or as a mixture.

In the case where the integrated catalyst is a supported catalyst, said integrated catalyst can advantageously be obtained by impregnation of at least one active phase precursor on a support having a structure adapted to the internal geometry of the equipment in which said catalyst Stabilization is integrated.

In the case where the catalyst is dispersed in said feed, it has a particle size and a density adapted to its drive. The term "entrainment" of the dispersed catalyst is understood to mean its circulation in the equipment and transport lines upstream of the hydroreforming reactor (s) by the liquid streams. The dispersed catalyst can be separated, by a technique known to those skilled in the art, before the introduction of said feed into the hydroreforming reactor (s) or entrained in the hydroreforming reactor (s) in the menu where the technology reactor allows it. In this configuration, a slurry or bubbling bed reactor technology is preferred, said dispersed stabilization catalyst circulating with the feedstock in the said three-phase reactor (s), and being discharged from the said triphasic reactor (s) with the liquid effluent produced.

In this case, said catalyst is introduced continuously with the feed in one or more sections of the process where the temperature is above 80 ° C, and preferably above 100 ° C. This embodiment allows a gain in stability of the load, the polymerization reactions being avoided, during the preheating of the charge and its transport to (x) reactor (s) hydroreforming.

Preferably, the dispersed catalyst has a size of from 0.001 to 100 μm and can be supported or unsupported. Preferably, the dispersed catalyst has a size of between 0.5 μm and 100 μm. In the case where the dispersed catalyst is a dispersed supported catalyst, said stabilization catalyst can advantageously be obtained by grinding the supported catalyst used in the hydroreforming step or the pre-hydrotreating step, preferably by grinding the catalyst. supported by hydroreforming or pre-hydrotreating fresh or spent or by grinding a mixture of fresh and spent catalysts, or - by impregnation of at least one active phase precursor on a support having a granulometry ad: i7tée (obtained by grinding) and preferably a size of between 0.001 and 100 μm and preferably between 0.5 μm and 100 μm. In the case where the dispersed catalyst is an unsupported catalyst, said dispersed catalyst can advantageously be obtained by injection of at least one active phase precursor directly in the feed prior to introduction of said feedstock into the first hydrorefornna step and / or introduced continuously with the charge in the said reactor (s) and / or in the triphasic reactor (s). The dispersed catalyst can therefore advantageously be formed and / or activated in situ under the heating conditions of the charge and / or reaction of the hydroreforming step or ex-situ, outside the reactor, and then injected continuously with load. Preferably, said dispersed catalyst is a solid, shaped catalyst having a suitable particle size and preferably a size of between 0.001 and 100 μm and preferably between 0.5 μm and 100 μm and containing at least one element capable of activating the hydrogen and optionally at least one support selected from metal oxides, preferably silicas, aluminas, silicas aluminas, zirconium oxide, cerium oxide, oxide titanium, coals, silicon carbides and aluminates of tris yisition taken alone or in mixture. Preferably, the dispersed catalyst is Raney Ni. The amount of stabilization catalyst inserted or injected into the so-called hot zones depends on the composition of the charge and the hot volumes (T> 80 ° C) of the installation to be filled. Preferably, the amount of catalyst inserted or injected into the so-called hot zones is such that the vvh is between 0.1 and 10 h -1 and preferably between 0.5 and 5 h -1.

According to the invention, said feedstock comprising at least one bio-oil, optionally at least one hydrocarbon feedstock derived from petroleum and / or coal, optionally other compounds derived from biomass, mixed with at least one part of the organic phase of the effluent from the hydroreforming stage which is recycled with a recycle rate equal to the mass flow rate of said organic phase on the mass flow rate of the bio-oil of between 0.05 and 5, is introduced in said hydroreforming step. The reaction is referred to herein as "hydroreforming" since it brings about a characteristic change in the molecular weight distribution of the feed comprising at least one bio-oil. Preferably, the hydroreforming step is considered as a hydrotreating step. During said strut of hydroreforming, the bio-oil is partially deoxygenated and partially hydroconverted with a partial production of hydrogen internal to the reaction. During said first hydroreforming step, the bio-oil is converted to stabilize the product, to render it miscible with the hydrocarbons, to cause an easy phase separation of the water in the bio-oil, lowering its viscosity, lowering its corrosivity, significantly converting high molecular weight fractions to smaller molecules and lowering its oxygen content from about 50% by weight to less than 15% by weight. Catalysts According to the invention, the catalyst used in said hydroreforming step 20 preferably comprises at least one transition metal chosen from the elements of groups 3 to 12 of the periodic table and at least one support chosen from coals. silicon carbides, silicas, transition aluminas, alumina silicas, zirconium oxide, cerium oxide, titanium oxide and transition metal aluminates, alone or as a mixture.

In the present invention, reference is made to the new notation of the Periodic Table of Elements: Handbook of Chemistry and Physics, 76th Edition, 1995-1996. Preferably, said supported hydroreforming catalyst comprises a Group 10 metal, alone or in combination with at least one Group 3 to 12 metal and preferably a Group 10 metal, alone or in combination with at least one metal of Group 10 Groups 5, 6, 7, 8, 9, 10, 11 of the Periodic Table. Very preferably, said supported hydroreforming catalyst comprises nickel, alone or in combination with at least one metal selected from chromium (Cr), molybdenum (Mo), manganese (Mn), tungsten (W), iron (Fe), cobalt (Co) and copper (Cu).

Preferably, the support of said hydroreformed supported catalyst is selected from silicas, transition aluminas, silica aluminas, porous carbon and transition metal aluminates. These supports can be taken alone or in mixture. Their shaping can be carried out in the form of extrusions, tri / quadrilobes, or balls. Preferably, said supported hydroreforming catalyst is a catalyst selected from catalysts comprising nickel (Ni), nickel and chromium (NiCr) or nickel and manganese (NiMn) on porous carbon and the catalysts compy nant nickel and molybdenum (NiMo) on alumina or nickel aluminate. Preferably, said hydroreformed supported catalyst comprises a group 10 and preferably nickel metal content of between 1 and 80% by weight, preferably between 5 and 70% by weight and more preferably between 10 and 65% by weight. , expressed as a percentage by weight of group 10 metal oxide relative to the total mass of said catalyst. In the case where said Group 10 metal is used in combination with at least one Group 3 to 12 metal, said hydroreformed supported catalyst comprises a Group 3 to 12 metal content of from 1 to 20 wt. percentage weight of metal oxide groups 3 to 12 relative to the total mass of said catalyst. In the case where the metal of the group 10 is chosen from Pt and Pd, said metal is used alone and the content of said group 10 metal, expressed as a weight percentage of metal oxide group 10 is advantageously between 0 , 2 and 10% by weight, preferably between 0.5 and 5% by weight relative to the total weight of said catalyst. The hydroreforming catalyst may also advantageously comprise a doping element such as, for example, phosphorus, boron, silicon or platinum at contents of between 0.1 and 5% by weight relative to the total weight of said catalyst. According to the invention, said supported hydrorefornage catalyst has a size of between 0.1 and 5 mm and preferably between 0.2 and 4 mm. Preferably, said supported hydroreforming catalyst is prepared according to key methods such as co-kneading or impregnation followed by one or more heat treatments. It is preferably used in the form of cylinders, balls or extrudates. The transition metals chosen from the elements of Groups 3 to 12 of the Periodic Table 30 constitute the active phase of said hydroreforming catalyst, a. Said hydroreforming catalyst is advantageously used in the hydroreforming step after undergoing an activation, reduction or sulphurization step. Said hydroreforming catalyst may advantageously be activated by reduction or by in situ sulphidation, under the reaction conditions of the first hydroreforming step, or ex-situ. In the case where said hydroreforming catalyst is activated ex situ, that is to say before being introduced into said hydroreforming step, the reduction or sulphurization step carried out under the conventional conditions of reduction and sulfurization, known to those skilled in the art, for example in the reactor (in situ) or ex situ, by contacting the catalyst, at high temperature, in the presence of hydrogen for the reduction or hydrogen with a source of hydrogen sulfide, such as dinethylethyl disulfide (DMDS) for the sulfidation activation mode. The non-hydroreformed supported catalyst is fluidized in the catalytic zone but remains within the three-phase reactor. Said supported catalyst can advantageously be removed from the reactor and renewed by adding fresh catalyst without stopping the process. Said spent supported catalyst may advantageously be partly replaced by fresh catalyst by withdrawal at the bottom of the reactor and introduction, either at the top of the reactor (s) or downstream, at a regular time interval, that is to say for example by puff or almost continuously. In conventional cases of bubbling bed operation, for example, fresh catalyst can be introduced every day. The replacement rate of the spent catalyst by fresh cost can be, for example, from about 0.01 kilograms to about 10 kilograms per cubic meter of charge. This withdrawal and replacement are performed using devices for the continuous operation of the hydroreforming step.

The three-phase reactor or reactors used in said hydroreforming step advantageously comprise a recirculation pump for maintaining said hydroreforming supported catalyst in a bubbling bed by continuous recycling of at least a portion of the liquid effluent fed to the bottom of the reactor. i C., ctors. Said spent catalyst withdrawn from the reactor can advantageously be sent to a regeneration zone in which the carbon it contains is removed, and then to return the regenerated catalyst to the hydroreforming step. Said spent catalyst withdrawn from the reactor can also advantageously be sent to a rejuvenation zone in which at least a part of the deposited metals is removed before regenerating the catalyst by removing the carbon and sulfur contained therein, and then returning the catalyst rejuvenated and regenerated in the hydroreforming step.

The supported or unsupported stabilizing catalyst is finely dispersed in the liquid phases throughout the reactor (s) and / or in the charge injection line, in the case where said catalyst for stabilization is introduced continuously with the feedstock. Said stabilization catalyst is thus driven by the liquid effluent produced and by the recirculation flow of the bubbling bed reactor (s). Said stabilizing catalyst thus circulates from bottom to top with the feed in the said reaction (s) and is removed from the reactor (s) with the liquid effluent produced.

FIG. 1 schematically represents a reactor used in the hydroreforming step with the circulation of the different streams. According to the invention, said hydroreforming stage operates at a temperature of between 250 and 450.degree. C., preferably between 250 and 400.degree. C., and preferably between 270 and 360.degree. an absolute pressure of between 3 and 30 MPa, preferably between 3.5 and 25 MPa, and preferably between 5 and 20 MPa and more preferably between 10 and 20 MPa, and at a high space velocity with respect to the organic oil, preferably greater than 0.2 h -1, more preferably between 0.5 h -1 and 5 h -1, more preferably between 1 h -1 and 5 h -1 and 10 the amount of hydrogen introduced such that the volume ratio hydrogen on hydrocarbons is between 50 and 2000 Nm3 / m 3 and preferably between 100 and 1000 Nm 3 / m 3 According to one embodiment, the feedstock comprising at least the bio-oil In another embodiment, said charge is preheated. at a temperature below 80 ° C before contact with the stabilizing catalyst or before being introduced into the hydroreforming step. Indeed, prolonged heating or storage at high temperature without the presence of a catalyst can cause a deterioration of the load. There are no limitations on the apparatus for carrying out the process. This can be conducted in batch or continuous mode. Nevertheless, for large-scale industrial applications, it will be preferable to operate continuously.

The first hydroreforming stage may advantageously be carried out in any reactor which facilitates the efficient dispersion of the bio-oil in the reaction mixture. A simple continuous stirred continuous reaction (CSTR) is suitable in batch mode. For continuous applications, downflow, moving bed, bubbling bed or slurry reactors will be more suitable. While keeping the catalyst in the reactor, bubbling bed reactor technologies have the advantage of allowing easy catalyst replacement during continuous operations, which provides greater flexibility in the operation of the reactor. unit, increases the duty cycle and maintains an activity as a function of time almost constant. These technologies also accept charges containing a few solids or producing solids during the course of reactions, which is not the case for fixed bed reactor technology, except for the use of reactive guards reactors, for example. The slurry reactor technology, in the English terminology, has the same advantages as the moving bed and bubbling bed reactor technologies and the added advantage of operating with a cooler, therefore with an activity maximum, but the disadvantage of greatly complicating the recovery of catalyst leaving the reactor with the effluents. Other reactors meeting the principles set forth herein are within the scope of those skilled in the art of chemical reactor technology and are within the scope of the present invention. In accordance with the invention, said hydroreforming step enables the production of at least one liquid effluent comprising at least one aqueous phase and at least one organic phase. A gaseous phase is also advantageously obtained at the end of said hydroreforming step. Said gaseous phase containing predominantly CO2, H 2 S and light C 1 -C 4 gases such as, for example, methane, said gas phase may advantageously be separated from said aqueous and organic phases in any separator known to those skilled in the art.

The analysis of the liquid effluent by the Micro Conradson Carbon Residue Test (MCCRT) method defined by standard NF EN ISO 10370 or ASTM D4530 shows no sign of polymerization. According to an embodiment in which the stabilization of the charge before introduction into the hydroreforming reactor (s) is performed with a catalyst integrated in the hot zone or deposited on the inner surface of said hot zone; said aqueous phase and said organic phase are free of said stabilization catalyst and can be advantageously separated by decantation. According to another embodiment in which a supported or unsupported catalytic catalyst or precursor is dispersed in the feedstock prior to the introduction of said feedstock into the hydroreforming reactor (s), said stabilizing cat.3lyseur can be recovered by any method known to those skilled in the art, such as preferably chosen from decantation, filtration and / or centrifugation of at least a portion and preferably all of each aqueous and organic phase. It can then be advantageously regenerated, and at least partly recycled and reused upstream of said hydroreforming step. According to another embodiment in which a supported or unsupported stabilization catalyst is dispersed in the feed and / or directly introduced into the three-phase hydroreforming reactor (s) operating in bubbling bed or slurry said stabilizing catalyst circulating with the feedstock in said reactor (s) is withdrawn from said reactor (s) with the liquid effluent produced, the liquid effluent thus also produced comprises at least said spent stabilization catalyst. spent stabilization is advantageously distributed in the various phases, aqueous and organic, depending on their viscosity and their density.

Said aqueous phase and said organic phase of the produced liquid effluent, also containing said used stabilization catalyst, are advantageously separated by decantation.

Said spent stabilization catalyst can then advantageously be recovered by at least one solid / liquid separation step by any method known to those skilled in the art, such as preferably chosen from decantation, filtration and / or centrifugation. at least a portion and preferably the total of each aqueous and organic phase, it can then be advantageously regenerated, and at least partly recycled and reused in said hydroreforming step and / or upstream. at least a part of said organic phase may advantageously be recycled in said hydroreforming step, before or after the solid / liquid separation step Thus, at least a part of said organic phase recycled in the first hydroreformation step may whether or not to include said spent stabilization catalyst, said aqueous phase comprises water and may also include organic carriers, main acetic acid and methanol (case of crude pyrolysis bio-oil), mixed in said aqueous phase, the aqueous phase contains essentially water formed by hydrodeoxygenation and water contained in the bio-oil no pretreated which has not been converted and generally less than about 20% by weight of dissolved organic matter. For the pyrolysis bio-oils, the aqueous phase separated during the first reforming step typically contains about 10% by weight of acetic acid and a lower proportion of methanol. Preferably, acetic acid and methanol are recovered in the aqueous phase because they constitute valuable by-products. The acetic acid may advantageously be recovered by various known means such as distillation or evaporalon, crystallization in the form of a salt, for example an alkaline earth, or by solvent extraction, by means of liquid ion exchangers for example. Because of its low boiling point and the absence of azeotropic formation with water, the methanol is simply recovered by distillation. Preferably, acetic acid and methanol taken together comprise at least 80% by weight of the organic components in the aqueous phase.

The organic phase contains partially deoxygenated bio-oil and hydrocarbons. The term "partially deoxygenated bio-oil" means a bio-oil containing less than 25% by weight of oxygen and preferably less than 15% by weight of oxygen relative to the total weight of said organic phase, and having a qu: the amount of carbon residue, otherwise called CCR in acronym, less than 12% by weight, preferably less than 8% by weight, more preferably less than 3% by weight relative to the weight of said organic phase. The organic phase therefore comprises less than 25% by weight of oxygen, preferably less than 15% by weight of oxygen, and preferably less than 10% by weight of oxygen relative to the total weight of said organic phase.

Thus, said organic phase is deoxygenated to a degree sufficient to render it miscible with hydrocarbon feeds such as those used in petroleum refining at high concentrations. In general, said organic phase can mix freely with most hydrocarbon products at concentrations up to at least 50% by weight. Moreover, since the oxygen content is substantially reduced and the bio-oil is already partially converted, the hydrogen requirements during hydrotreatment / hydrocracking stages in the refinery are greatly minimized. In addition, said organic phase is stabilized so that it can be hydrotreated / hydrocracked in a refinery without the risk of large formation of solids. The organic phase preferably contains less than 25% by weight of oxygen and preferably less than 15% by weight of oxygen and less than 5% by weight of water, preferably less than 2% by weight of water relative to total mass of said organic phase. The consumption of hydrogen during said first hydroreforming step is preferably less than about 2% by weight of the bio-oil. Preferably, the total acid number (TAN) is less than about 100 KOH / g oil. The total acid number is expressed in mg KOH / g of oil. This is the amount of potassium hydroxide in milligrams needed to neutralize the acids in one gram of oil. There are standard methods for determining the acid number, such as ASTM D 974 and DIN 51558 (for mineral oils, biodiesels), or methods specific to biodiesels using European standard EN 14104 and ASTM D664, widely used worldwide. The higher heating value (PCS) is greater than about 35 MJ / kg in the organic phase resulting from said first hydroreforming step. Without being exhaustive, said organic phase may for example be used in refining processes such as hydrocracking, hydrotreatment or catalytic cracking feedstock or as an industrial fuel. Said organic phase can also be used directly as a fuel-grade hydrocarbon product for road, air or sea transport. In the case where said organic phase is directly used for maritime transport, the quality of the fuels is fairly or very different according to the grades considered (distillate type fuels DMX, DMA, DMZ, DMB or residual fuels type RMA, RMB, RMD, RME, RMG or RMK according to ISO 8217) and the specifications peculiar to this type of fuels mean that the second hydrocracking step of the process according to the invention is generally not necessary. On the other hand, a second hydrotreating step operating under mild conditions, that is to say at high VVH, and under moderate hydrogen pressure, can advantageously be carried out. Preferably, said hydrotreating step advantageously operates at a temperature Between 300 and 380 ° C, at a pressure of between 3 and 8 MPa and at a VVH of between 1 and 3 hours -1.

Typically, during the first hydroreforming step, the yields in the organic phase with respect to the dry biomass, that is to say comprising 0% humidity, introduced into the pyrolysis step, are between 15 and 15%. 45% by weight, and preferably between 15 and 40% by weight. The yields in aqueous phase relative to dry biomass are between 10 and 50% by weight, and preferably between 10 and 40% by weight. The gas phase yields relative to the dry biomass are between 5 and 30% by weight. The conversion of the organic fraction of the bio-oil into a partially deoxygenated bio-oil is at least 70% by weight. The partially deoxygenated bio-oil and more particularly the organic phase comprising at least said partially deoxygenated bio-oil produced by hydroreforming can be easily converted into fully deoxygenated hydrocarbons, compatible with the carburizing pools, by means of processes using conventional refinery, such as hydrotreating or hydrocracking. At least a portion of the organic phase of the effluent from the first hydroreforming stage is recycled in said first hydroreforming step with a recycle ratio equal to the mass flow rate of said organic phase on the mass flow rate of the non-pretreated bio-oil of between 0.05 and 5. The said portion of recycled organic phase may optionally have undergone a separation step, solid / liquid aion preferably by decomposition, filtration and / or centrifugation, beforehand. In the first hydroreforming step, it is preferable to recycle the recycle rate from 0.05 to 2, preferably from 0.05 to 1.5, more preferably from 0.2 to 1 , 3 and very preferably (.: 3, between 0.3 and 1. The recycle rates used make it possible to have a load sufficiently thermally stable enough to be introduced into the preheating furnace as well as into the reactor of hydrorefomage without risk of clogging, to facilitate the reactions of conversion and deoxygenation of the bio-oil on the catalyst, to improve the dissolution of hydrogen gas in the recycled organic phase from the first step of hydroreforming and better manage the exothermicity lost by the reactions, while minimizing the recycling of all or part of the organic phase resulting from the hydroreforming in order to minimize the investment costs as well as the operating costs.

The organic phase recycled in said first hydroreforming step, and resulting from this step, also serves to lower the density of the partially deoxygenated bio-oil produced during this first step, which facilitates the phase clearance of the partially deoxygenated bio-oil and the aqueous phase at the hydroreforming outlet. This separation which is easily effected during the cooling of the reaction mixture is another advantage provided by the presence of recycled organic pha in the reaction mixture of the first hydroreforming step. The presence of the organic phase recycled in the optional mixture tends to expel water from said organic phase, thus reducing the water content as much as possible, which is favorable to the use of said organic phase. as an industrial fuel or as a feedstock for subsequent hydrotreatment / hydrocracking steps. Thus, said organic phase resulting from the first hydroreforming step contains less than 5% by weight of water, preferably less than 2%. Hydropene Consumption During said hydroreforming step, an internal bio-oil reforming of carbon oxides and hydrogen is carried out with a relatively high hydrocarbon yield and a low relative hydrogen consumption. The hydrogen consumption is therefore moderate during said hydroreforming step and the internal production of hydrogen by hydroreforming makes it possible to operate the process with a very limited external hydrogen consumption. Part of the hydrogen required for the reaction in said hydroreforming step is generated internally, a priori from the water present in the bio-oil, by hydroreforming a proportion of the bio-oil, in such a way that a significant portion of the oxygen is released under carbon dioxide, and the net hydrogen requirement is much lower than in the case of the direct hydrodeoxygenation process. The other part of the hydrogen necessary for the reaction is of external origin. Typically, the hydrogen consumption during the first hydroreforming step is less than about 2% by weight of the bio-oil mass in the reactor, and the corresponding CO2 emission to produce it. is much less than in the case of processes of the hydrodeoxygenation (HDO) type, with a consumption of at least 4 or 5% by weight of external hydrogen (depending on the oxygen content of the feedstock). The hydrogen of external origin can advantageously be supplied from fossil resources, by gasification / partial oxidation or by steam reforming, by steam reforming of the bio-oil itself (although this implies a loss of of carbon energy efficiency), by steam reforming methane produced and light gas fractions and / or fractions comprising light oxygen compounds from the first hydroreforming step or the subsequent step of hydrotreatment / hydrocracking, It is also possible to react the recovered CO with the water produced to obtain hydrogen by means of a known reaction of conversion of gas to water by "water gas shift" according to the English terminology. Saxon (WGS). Thus, the overall process, from the biomass to the final hydrocarbon product, could be self-sufficient in hydrogen. The implementation of said hydroreforming step under the conditions claimed and in particular by the integration of a complementary stabilization catalyst supported or unsupported, integrated or dispersed in the so-called hot zones of the process and with the conditions used, therefore has the following advantages: - the bio-oil is stabilized during preheating, heating and transport operations upstream of the hydroreforming step so that it can then be refined without risk of polymer formation or / and solids in the equipment before introduction into the hydroreforming reactor (s), it is desoneni; to a degree sufficient to render it miscible with typical hydrotreatylate feedstocks from petroleum cuttings, the catalytic supply is increased by the presence in so-called hot zones of the process and / or in the reactor (s) ) of hydroreforming, a stabilization catalyst integrated or dispersed in addition to the hydroreforming supported catalyst and improves the performance of the process according to the invention by allowing the production of a stable hydrocarbon effluent and incorporable fuel pool from a filler comprising at least one non-pretreated bio-oil, comprising an oxygen content of less than 5% and preferably less than 1% w / w and a water content of less than 0.1 () / 0 weight relative to the total mass of said hydrocarbon effluent, without significant formation of coke or bio-oil polymers, with low rates of deactivation of the first hydroref catalyst and, improved conversion rates and reduced hydrogen consumption, all non-accessible liquid volume by the mere use of a conventional undrained hydroreforming catalyst and also any intergranular volume of the catalyst bed is used using a dispersed and driven stabilizing catalyst introduced with the feedstock or directly into the three-phase hydroreforming reactor (s), in the latter configuration the problem of diffusional limitations is avoided by the use of a second catalyst said trained, complementary, of reduced particle size with respect to the first hydrorefornage catalyst said undrained. Furthermore, the oxygen content in the bio-oil is reduced, so that the hydrogen requirements during a hydrotreatment in the refinery are greatly reduced, at a level adapted to conventional hydrotreating / hydrocracking processes. petroleum products - hydrogen is generated internally from the water present by hydroreforming a portion of the bio-oil, so that most of the oxygen is released preferentially in the form of carbon dioxide and that the net external hydrogen requirements are limited - the product is essentially water-free, the residual water forming a separate phase - the corrosivity of the product is greatly reduced since most of the organic acids are converted or pass in the aqueous phase light carboxylic acids such as acetic acid present in the crude bio-oil can be recovered in the In the aqueous phase, and as valuable by-products, only a moderate amount of gaseous hydrocarbons, mainly methane, is formed if necessary. This methane fraction can be reformed by the so-called methane reforming process. steam (Steam Methane Reforming SMR) for producing bio-hydrogen for hydroreforming or hydrotreatment / hydrocracking processes - it is also possible to use the bio-coal from the pyrolysis step as a feedstock for the gasification reactor to produce synthesis gas (CO + H2). This synthesis gas can also be used to produce bio-hydrogen for the pre-hydrotreatment, hydroreforming and / or hydrotreatment / hydrocracking stages, thus using the SMR process and / or the The biofuel conversion process can be self-sufficient in hydrogen, without the need for fossil fuel hydrogen - the hydrocarbon weight yield is higher than that of the bio-coal gasification process. direct deoxygenation to that obtained by hydro- - the operating conditions are relatively moderate and the hourly space velocity is high (shorter residence time compared to conventional hydro-deoxygenation processes) in continuous mode. In addition to increasing hydrocarbon yield and reduced hydrogen requirements, the goal is to reduce both capital and operating costs for upgrading bio-oils to produce a renewable source of chemicals. . and fuels for transport from whole lignocellulosic biomass.

An organic separation step resulting from said hydroreforming step may optionally be carried out between said hydroreforming step and said hydrotreating and / or hydrocracking step. Said separation step may advantageously be carried out by methods well known to those skilled in the art such as flash, distillation, stripping, liquid / liquid extraction etc.

The fractionation zone preferably comprises a fractionation section which incorporates a high temperature high pressure separator (HPHT). Optionally, at least a portion of said organic phase from the hydroreforming step is fractionated in a fractionation zone, for example by distillation, into at least a light fraction having an initial boiling point of less than 250 ° C. C and at least one heavy fraction having an initial boiling point greater than 250 ° C. In this variant, said heavy fraction having an initial boiling point of greater than 250 ° C. can be recycled in said hydroreforming step of the process according to the invention and said light fraction can be recycled in the optional step of pre-treatment. hydrotreating. recycling the heavy fraction makes it possible to increase the yield of the hydro-reforming step and recycling the light fraction having a low viscosity in the optional pre-hydrotreatment stage allows a better operability of the bio-oil filler. Hydrotreating and / or hydrocracking step Said organic phase comprising at least said partially deoxygenated bio-oil of the effluent resulting from said hydroforming step still contains a high oxygen content. It is therefore not a pure hydrocarbon and therefore requires further processing if the goal is to convert it into a hydrocarbon product of fuel quality for road, air or sea transport. In the case of recovery for maritime transport, only a hydrotreatment step 15 under mild conditions can advantageously be implemented. According to one variant, at least a part of said organic phase, preferably freed from said second catalyst by at least one liquid / solid separation step, and at least partially deoxygenated bio-oil of the effluent from the first hydroreforming step is subjected to a second hydrotreatment and / or hydrocracking step. Said hydrotreatment and / or hydrocracking step advantageously operates in the presence of hydrogen and a hydrotreatment and / or hydrocracking catalyst, at a temperature above 200 ° C., at a pressure of between 2 MPa and 25 MPa and at a space velocity of between 0.1 hr-1 and 2011-1. Said hydrotreatment and / or hydrocracking step enables the production of a hydrocarbon effluent. At least a portion of said organic phua of the effluent from the first hydroreforming step may optionally be introduced into said hydrotreating and / or hydrocracking step in mixture with a charge of fossil origin. Said filler of fossil origin preferably comprises at least 20% by volume of compounds whose boiling point is greater than 250 ° C. and, preferably, less than 50% by volume of compounds whose boiling point is greater than 350 ° C. Said charge of fossil origin is advantageously chosen from atmospheric distillates, vacuum distillates, such as, for example, distillates derived from the direct distillation of crude or conversion units such as fluid catalytic cracking units, from 3034099 These feedstocks are used for the extraction of base aromatics or base-dressing oils or solvent dewaxing of base lubricating oils, distillates from processes for the hydrotreatment and / or hydroconversion of residues resulting from the hydroconversion to a fixed bed or a moving bed or to a bubbling bed or to a suspension bed of atmospheric residues and / or of 5 residues under vacuum and / or oils deasphalted from any solvent deasphalting process using light solvents, and deasphalted oils, or any mixture of the above-mentioned fillers The above list is not limiting. The n-C7 insolubles of the overall charge is generally less than 5000 ppm, preferably less than 1000 ppm and more preferably less than 200 ppm.

Hydrotreating In a preferred embodiment, said step is a hydrotreatment step operating in the presence of a heterogeneous catalyst and hydrogen at a temperature of between 250 and 450 ° C, preferably between 300 and 400 ° C, preferred manner between 320 and 380 ° C, at a pressure of between 2 MPa and 25 MPa, preferably between 5 MPa and 20 MPa and at a space velocity of between 0.1 h-1 and 20 h-1 and preferably between 0.5 h-1 and 5 h-1 and with a total amount of hydrogen mixed with the feed (including the chemical consumption and the recycled amount) such that the hydrogen / hydrocarbon volume ratio is between 100 and 3000 Nm3 / m3 and preferably between 100 and 1000 Nm3 / m3. Said hydrotreatment catalyst advantageously comprises an active phase comprising at least one group 6 metal chosen from molybdenum and tungsten alone or as a mixture, preferably combined with a group 8 to 10 metal chosen from nickel and cobalt, alone or in admixture and a support selected from the group consisting of alumina, silica, silica-alumina, magnesia, clays and mixtures of two or more of these minerals. Said support may further contain other compounds such as, for example, oxides selected from the group consisting of boron oxide, zirconia, titania, phosphoric anhydride. Preferably, said support consists of alumina, and more preferably alumina [eta], [theta], [delta] or [gamma]. The total quantity of metal oxides of group 6 and groups 8 to 10 in the catalyst used is advantageously between 5 and 40% by weight, preferably between 6 and 30% by weight relative to total mass of catalyst. In the case where said catalyst comprises nickel, the nickel oxide content is advantageously between 0.5 and 12% by weight and preferably between 1 and 10% by weight. In the case where the catalyst comprises molybdenum, the content of molybdenum oxide is advantageously between 1 and 35% by weight of molybdenum oxide (MoO 3) and preferably between 5 and 30% by weight of molybdn oxide, J, these percentages being expressed in% by weight relative to the total mass of catalyst. A NiMo, NiVV or CoMo catalyst is preferably used.

Said catalyst used in the hydrotreating step can also advantageously contain at least one doping element chosen from phosphorus and / or boron. Said element may advantageously be introduced into the matrix or, preferably, deposited on the support. It is also possible to deposit silicon on the support, alone or with phosphorus and / or boron.

The oxide content in said element is advantageously less than 20%, preferably less than 10%, based on the total mass of catalyst. The metals of the catalysts used in the second hydrotreatment step of the method according to the invention may be metals or sulphurized metal phases. Hydrocracking: mild hydrocracking and high pressure hydrocracking In another preferred embodiment, said step is a hydrocracking step advantageously operating at a pressure of between 2 MPa and 25 MPa, at a temperature of between 250 and 480 ° C. an hourly space velocity of between 0.1 hr-1 and 20 hr-1, and with a total amount of hydrogen mixed with the feed (including the chemical consumption and the amount recycled) such that the hydrogen / hydrocarbon volume ratio is between 80 and 5000 Nm3 / m3. Preferably, at least a portion of said organic phase of the effluent from the first hydroreforming step is subjected to a second hydrocracking step in the presence of a heterogeneous catalyst and hydrogen. Said hydrocracking step may advantageously be carried out in one or two stages according to the methods known to those skilled in the art.

According to a preferred embodiment, said hydrocracking step is a mild hydrocracking. In this case, said second hydrocracking step gives a net conversion of products whose boiling point is less than 375 ° C is advantageously between 5 and 50% by weight, advantageously between 10 and 45% by weight. Said mild hydrocracking step advantageously operates at a pressure of between 2 MPa 25 and 12 MPa (290-1740 psi), preferably between 2 and 10 MPa (290-1450 psi), more preferably between 4 and 9 MPa (580 psig). -1305 psi) and more preferably between 3 and 7 MPa (435-1015 psi), at a temperature between 350 and 450 ° C, at a space velocity of between 0.2 hr-1 and about 5 hr. 1 and with a total amount of hydrogen mixed with the feedstock (including the chemical consumption and the recycled amount) such that the hydrogen / hydrocarbon volume ratio is between 100 and 2000 Nm3 / m3, preferably between 200 and 1500 Nm3 / m3, According to a preferred embodiment, said hydroclimation step is a so-called high pressure hydrocracking. In this case, the operating conditions used in the process according to the invention 3034099 30 make it possible to achieve conversions of products whose boiling point e.-1 less than 340 ° C., preferably less than 370 ° C. ° C, greater than 10% and more, preferably between 20 and 95 ° / 0, more preferably between 50 and 95%. Said hydrocracking step, said high pressure, advantageously operates in the presence of hydrogen at a temperature of between 250 and 480.degree. C., preferably between 320 and 450.degree. C., more preferably between 330 and 435.degree. a pressure of between 5 MPa and 20 02a (725-2900 psi), the hourly space velocity being between 0.1 hr-1 and 6 hr -1, preferably. between 0.2 h -1 and 3 h -1, and with a quantity of hydrogen introduced is such that the volume ratio hydrogen / hydrocarbon is between 100 and 2000 Nms / m3.

According to a very preferred embodiment, said step is a hydrotreating step followed by a step of hydrocracking at least a portion of the organic phase of the effluent from the first hydroreforming step. The hydrotreating step upstream of the hydrocracking step makes it possible to reduce the heteroatoms potentially harmful for the hydrocracking catalyst (s). The hydrotreatment test step 15 carried out in the presence of a conventional hydrorefining catalyst known to those skilled in the art. Said hydrotreating step and / or hydrocracking may advantageously be carried out in a fixed bed reactor or in a so-called driven bed: moving bed reactor, bubbling bed reactor or suspension reactor. It is possible to use a single catalyst or several different catalysts, simultaneously or successively, in the case of a fixed bed reactor.

The hydrocracking catalysts employed in the second hydrocracking step are conventional hydrocracking catalysts and are known to those skilled in the art. The hydrocracking catalyst preferably comprises at least one metal of groups 8 to 10 chosen from Ni and / or Co, and at least one metal of group 6 chosen from Mo and / or W, on a silica support -alumine and / or zeolite.

Other conventional catalysts include FAU type zeolite Y, an amorphous support (usually alumina) and at least one metal or metal compound having a hydrodehydrogenating function (usually at least one Group 6 metal and grcn). ipcs 3 to 10, preferably at least one Group 6 metal and at least one Group 8 to 10 non-noble metal. Before the injection of the feedstock, the catalysts used in the process according to the present invention are preferably subjected to a preliminary sulphurization treatment in order to transform, at least in part, the oxide species into sulphides before they are brought into contact. with the load to be treated.

The sulphidation activation treatment is known to those skilled in the art and can be carried out using any method already described in the literature, either in situ, ie in the reactor. , ie ex situ. The hydrocarbon effluent obtained at the end of said hydrotreatment and / or hydrocracking step is a completely deoxygenated liquid hydrocarbon effluent. Said hydrocarbon liquid effluent 5 comprises a content of hydrocarbon compounds advantageously greater than 98% by weight and preferably greater than 98.9% by weight. Said effluent also advantageously comprises less than 1% by weight of oxygen and less than 0.1% by weight of water relative to the total mass of said effluent. The higher heating value (PCS) of said hydrocarbon liquid effluent is about 45 MJ / kg, which is comparable to that of diesel. The boiling point of said hydrocarbon liquid effluent, measured by simulated distillation by gas chromatography, according to the ASTM D2887 method, for example, is less than about 500 ° C, preferably less than 450 ° C. The overall yield of hydrocarbon liquid effluent obtained at the end of the second hydrotreatment and / or hydrocracking step relative to the dry biomass is advantageously between 10 and 48% by weight and preferably between 10 and 40% by weight. The hydrogen consumption during the second step is preferably less than 2% by weight based on the mass of bio-oil introduced. This equates to a hydrogen consumption during the second stage is preferably less than 4 96 weight relative to the mass of organic effluent sent to said second step. Said hydrocarbon liquid effluent from the second stage of hydrotreating and / or hydrocracking is advantageously subjected to a distillation stage to obtain at least one section boiling at a temperature of between 150 and 370.degree. Said cup can be incorporated into the diesel and kerosene fuel bases. Preferably, said hydrocarbon liquid effluent from the second hydrotreatment and / or hydrocracking step is not recycled in said first hydroreforming step.

DESCRIPTION OF THE FIGURE FIG. 1 schematically represents the process according to the invention in the case where the stabilizing catalyst is distilled. previously in the feed comprising at least the bio-oil before being introduced into the first hydroreforming step. Figure 1 also illustrates the case where the effluent from the hydroreforming step is sent to a second hydrotreatment and / or hydrocracking step to produce middle distillates.

The stabilization catalyst is introduced via the pipe (2) and dispersed in a zone (A) in the feed comprising at least the bio-oil resulting from the rapid pyrolysis of the IOMPSSE which is introduced via the pipe. (1). The feed comprising said catalytic catalyst or precursor is then fed via line (3) into the first hydroreforming step (B) which produces at least one effluent (4) which is fed into a gas / liquid separation step (C). ) at the end of which a gaseous phase is separated via the pipe (5) and a liquid effluent (6). Said liquid effluent contains an aqueous phase and an organic phase and also said stabilization catalyst distributed in one and the other of the aqueous and organic phases. The aqueous and organic phases are then separated in a decantation step (D). The aqueous solution also comprising said stabilization catalyst is recovered in line (7) and an organic phase also containing said stabilization catalyst is recovered in line (9). The aqueous phase (7) and an organic phase (9) both containing the stabilization catalyst are respectively separately sent to liquid / solid separation zones (E) and (F) so as to recover respectively in the pipes (8). and (10) said spent stabilization catalyst which is collected in a mixing zone (G) of said spent catalyst. At least a portion of said spent stabilization catalyst is recycled via the lines (11) and (13) in the hydroreforming step (A) and the other portion is purged via the line (12). An organic phase still containing said stabilization catalyst is also recycled via the line (16) to the hydroreforming step (A), an aqueous phase and an organic phase which is discharged from the catalyst. stabilization are respectively recovered at the end of the separation zones (E) and (F) in the lines (14) and (15). At least a part of the organic phase freed from the spent stabilization catalyst is recycled via line (17) in the hydroreforming step (A). The other part of the said organic phase freed from the t.rA stabilizing catalyst is sent to the second hydrotreatment and / or hydrocracking step (H) to obtain a hydrocarbon effluent in the pipe (18). Said hydrocarbon effluent is then sent to a separation zone (I) to recover at least one boiling point cut between 150 and 370 ° C in the pipe (19). The examples below illustrate the invention without limiting its scope. Examples The experiments were conducted with a bio-oil obtained by rapid pyrolysis of hardwood mixtures. The operating conditions of the rapid pyrolysis are: a temperature of 500 ° C. and a residence time of the vapors of the order of one second. Table 1 below presents the data obtained following the analysis of this bio-oil.

3034099 33 Table 1: Analysis of bio-oil esse volume at 20 ° C, g / cm 1.21 Cynematous viscosity at 20 ° C, mm2 / s 182.6 PH 2.5 Higher heating value, MJ / kg at 18 , 03 Lower heating value, MJ / kg 16.46 Water content,% by mass 20.7 Pyrolytic lignin,% by mass 19.0 Carbon, by mass | 43.9 Hydrogen,% mass 7.39 Nitrogen,% mass <0.05 Oxygen, mass% 47.3 Sulfur (ppm) 92 MCCRT,% mass 21 a The Higher Calorific Heat cures a calori bomb, the Heat Power Lower is calculated using the following equation: LHV (J / g) = HHV (J / g) - 2181 3 * H 96 (`) / 0 wt.) The stabilization catalyst used in the experiments is a Ni of Commercial Raney powder in water containing at least 92% Ni. Example 1 (non-compliant): Formation of solid thermal treatment at 280 ° C of: unstabilized non-pretreated bio-oil mixed with an organic liquid phase issw. The hydroreforming step This example illustrates the formation of solids during a heat treatment, which may represent prolonged heating of the feed before introduction into the hydroreforming reactor, from a bio-oil feedstock. non-pretreated non-stabilized with the characteristics described in Table 1 mixed with a ph ,,,; e organic liquid from the hydroreforming step at a 1: 1 ratio (organic liquid phase: bio-oil) simulating a recycle rate 1. 140 g of filler (bio-oil / organic liquid phase mixture) is introduced into an autoclave reactor. The reactor is pressurized with nitrogen to a pressure of about 100 bar at the test temperature, and then gradually heated with stirring at 500 rpm to 280 ° C and maintained at that temperature for 6 hours. The reactor is then rapidly cooled and cooled to room temperature.

Two phases, an aqueous and organic phase, are obtained at the end of the test. Both phases are filtered on a 1 μm porosity fiberglass filter. The reactor and the stirrer are washed with acetone to recover the solids present on the surface. Wash acetone containing the solids is also filtered. The filtered solid is washed several times with acetone and dried in an oven at 80 ° C for 1 night. 0.8 g of solid is weighed or 1.14% by weight of the bio-oil feed introduced. Example 2 (according to the imu = ntion): Stabilization of a non-pre-treated bio-oil charae mixed with an orriani-eu liquid phase from the hydroreformaqe stage This example illustrates the stabilization of a bio charge oil not pre-treated with the characteristics described in Table 1 in admixture with an organic liquid phase resulting from the hydroreforming step in a 1: 1 ratio (organic liquid phase: double-oil) simulating a recycle rate of 1, in equipment and lines before introduction into the hydroreforming reactor. 2 g of a commercial Raney Ni powder catalyst is introduced with 80 g of filler (bio-oil / organic liquid phase mixture) into an autoclave reactor. The reactor is pressurized with hydrogen to reach the target of 13 MPa at the test temperature, then gradually heated with stirring to 175 ° C and maintained at this temperature for 3 hours. The reactor is then rapidly cooled and cooled to room temperature. The effluent gas is collected and accounted for. A single liquid phase is recovered and filtered to separate the catalyst. The catalyst is washed with acetone, dried, neutralized and then subjected to programmed temperature oxidation to estimate the amount of residual carbon residue. The density of the liquid phase obtained is 0.954 at 20 ° C. and the MCCRT of the liquid phase is 7.9% by weight. The liquid phase contains 14% by weight of dissolved water determined by Karl-Fischer assay. The hydrogen consumption is 0.65% by weight relative to the feed, which represents 1.3% by weight relative to the bio-oil.

EXAMPLE 3 (according to the invention): heat treatment at 280 ° C. of an unreprocessed bio-oil strut stabilized in melana with an uide phase of the droreforma o This example illustrates the the result of a heat treatment, which may involve prolonged heating of the bio-oil filler mixed with a liquid phase derived from the hydroreforming stage and according to Example 2 before introduction into the reactor 30 d 'hydroreforming. 140 g of stabilized charge (bio-oil / organic liquid phase mixture) is introduced into a reactor. The reactor is vented with nitrogen to a pressure of about 100 bar at the test temperature and then gradually heated with stirring at 500 rpm to 280 ° C and maintained at this temperature for 6 hours. h. The reactor is then rapidly cooled and cooled to room temperature. Two phases, an aqueous and organic phase, are obtained at the end of the test. Both phases are filtered on a 1 μm porosity fiberglass filter. The reactor and the stirrer are washed with acetone. Wash acetone is also filtered. The filter is then washed several times with acetone and dried in an oven at 80 ° C for 1 night and weighed. 0.05 g of solid is weighed, ie 0.12 wt. Of the introduced bio-oil filler. This example shows that by contacting the feedstock (bio-oil mixed with an organic liquid phase resulting from the hydroreforming step) with a stabilization catalyst, for example of Raney Ni type, and hydrogen before the hydroreforming reactor in the zones of temperatures higher than 80 ° C., the formation of solids by purely thermal reactions is greatly reduced, which makes it possible to reduce or even to avoid the problems of clogging or fouling of the equipment in question. upstream of the reactors and between the reactors.

Claims (10)

REVENDICATIONS1. A process for producing hydrocarbons from a feedstock comprising at least one bio-oil, said process comprising the steps of: introducing said feedstock into a hydroreforming first comprising at least one reactor, in the presence of hydrogen and a hydroreforming catalyst comprising at least one transition metal chosen from the elements of groups 3 to 12 of the periodic table and at least one support chosen from active carbons, silicon carbides, silicas, aluminum aluminas and transition, alumina silicas, zirconium oxide, cerium oxide, titanium oxide and transition metal aluminates, taken alone or as a mixture, to obtain at least one liquid effluent comprising at least one aqueous phase and at least one organic phase, said first hydroreforming stage operating at a temperature of between 250 and 450 ° C., at an absolute pressure of between 3 and 30 MPa, at a space velocity of the time relative to the bio oil greater than 0.2 h-1, and with a quantity of hydrogen introduced such that the volume ratio hydrogen on bio-oil is between 50 and 2000 Nm3 / m3, and in which at least a part of the organic pharr3 of the effluent from said first hydroreforming step is recycled mixture with said feedstock comprising at least one bio-oil, with a recycling rate equal to the ratio of the mass flow rate of said organic phase to the flow rate mass of the bio-oil between 0.05 and 5, a second step of hydrotreating and / or hydrocracking at least a portion of the organic phase of the effluent from the first hydroreforming step to obtain a hydrocarbon effluent, wherein a stabilizing catalyst is contacted with said feedstock, in the presence of a reducing agent, in at least one zone of the process in which the temperature is at least greater than 80 ° C, said catalyst eta nt is integrated in said zone, or dispersed in said load. The process of claim 1, wherein the reducing agent is hydrogen. 3. Method according to one of claims 1 or 2, wherein the areas in which the temperature is at least greater than 80 ° C are the heating equipment, the transport lines of said load to the (x) reactor ( s) hydroreforming, preheating exchangers, furnaces, convoy lines between equipment, injection lines or any equipment located upstream of the hydroreforming stage reactor (s) or reactor (s); hydroreforming 3034099 37 4. Method according to one of claims 1 to 3, wherein the so-called stabilization catalyst is contacted with said charge prior to the introduction of said charge in the first hydroreforming step, upstream of the reactor or reactors. the hydroreforming step, 5. Method according to one of claims 1 to 3, wherein the so-called stabilizing catalyst is brought into contact with said feed directly into said hydroreforming reactor (s). 6. Method according to one of claims 1 to 5 wherein the so-called stabilization catalyst, whether integrated or injected, is a shaped metal, said metal being selected from transition metals selected from nickel, cobalt, platinum, palladium, copper and iron, alone or in alloy, said catalyst possibly also possibly containing at least one support selected from among metal oxides, activated carbons, silicon carbides and aluminates of transition taken alone or in mixture. 7. Method according to one of claims 1 to 6 wherein said integrated catalyst is selected from Raney Ni in the form of metal foam, grid or lining. The process according to one of claims 1 to 6 wherein said dispersed catalyst is Raney Ni having a size of from 0.001 to 100 μm. 9. Method according to one of claims 1 to 8, wherein the contacting of said charge with a so-called stabilization catalyst in the presence of a reducing agent, in at least one zone of the process in which the temperature is at least above 80 ° C is carried out in the presence of at least a portion of the orunicilie phase of the effluent from the first hydroreforming step. 10. Method according to one of claims 1 to 9 wherein at least a portion of said organic phase of the liquid effluent from the first hydroreforming step is subjected to a second hydrotreating step and / or hydrocracking operating advantageously in the presence of hydrogen and of a hydrotreatment and / or hydrocracking catalyst, at a temperature greater than 200 ° C., at a pressure of between 2 MPa and 25 MPa and at a space velocity of 1 hour inclusive; between 0.1 hr and 20 hr-1 to produce a hydrocarbon effluent.