FR3041359A1 - OPTIMIZED PROCESS FOR THE VALORISATION OF BIO-OILS IN AROMATIC AND OLEFINIC BASES - Google Patents

Abstract

The invention describes a method for converting a liquid feed comprising at least one bio-oil, said process comprising one or more hydroreforming step (s), in the presence of hydrogen and one or more catalysts of hydroreforming process 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, transition aluminas, silica aluminas, 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, followed by a step of catalytic cracking of at least a portion of the effluent from the hydroreforming stage (s) in at least one reactor operating in upward or downward flow containing a cracking catalyst catalytic converter, operating with a catalyst on charge ratio of between 4 and 15 and with an outlet temperature of the reactor (s) of between 450 and 600 ° C.

Description

FIELD OF THE INVENTION

The present invention relates to a process for converting a liquid feed comprising at least one bio-oil, said bio-oil being derived from biomass and in particular from liquefied biomass resulting from the pyrolysis of biomass. More specifically, the invention relates to a process for converting bio-oil into aromatic compounds, olefinic compounds and fraction that can be incorporated into the fuel pool, in particular to the gasoline, kerosene and diesel fuel pools, said process comprising one or more step (s). hydroreforming, followed by a step of catalytic cracking of the effluent from the hydroreforming step.

STATE OF THE ART

Given the abundant and renewable reserves of biomass, an attractive alternative for the production of petrochemical and fuel-based intermediates is the use of liquids from biomass, usually also called bio-oil or biobrud.

Bio-oils are liquid products obtained by thermochemical liquefaction of cellulosic biomass. The method for thermochemical liquefaction of biomass can for example be carried out in the presence or absence of catalyst, in the presence of an inert gas or a gas containing hydrogen and water. Thermochemical processes generally convert biomass into liquid, gaseous and solid products. Among these methods, so-called rapid pyrolysis methods tend to maximize the liquid yield. During rapid pyrolysis, the temperature of the biomass, possibly divided, is rapidly raised to values above about 300 ° C. and preferably between 450 and 600 ° C. and preferably between 450 ° and 550 ° C. and the products liquids are condensed as a bio-oil. Ringer et al. (Large-Scale Pyrolysis Oil Production: A Technology Assessment and Economics Analysis, M. Ringer, V. Putsche, and J. Scahill, NREL Technical Report NREL / TP-510-37779, November 2006) studied the various technologies implemented for 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.

Bio-oils and in particular bio-oils resulting from the rapid pyrolysis of biomass are complex mixtures of highly oxygenated polar hydrocarbon products obtained from the breaking of biopolymers, and having physical and chemical properties limiting their direct use.

Pyrolysis bio-oils have undesirable properties such as: (1) corrosivity due to their high content of water and organic acids; (2) a low specific calorific value due to the high oxygen content, typically of the order of 40% by weight; (3) chemical instability, both storage and thermal, due to the abundance of reactive oxygen functional groups such as the carbonyl group, which can lead to polymerization during storage and hence phase separation; (4) a viscosity and a tendency to separate relatively high phases under high shear conditions, in an injector for example; (5) solid particles of coal resulting from pyrolysis, which will always be present in unfiltered bio-oils in a small quantity such that the bio-oil / coal particles ratio is greater than 10: 1 and preferably greater than 50 1. However, said particles can cause plugging of stationary internal combustion engines or poison post-treatment catalysts.

All these aspects combine to make the handling, transportation, storage and implementation of bio-oils difficult and expensive, thus making their integration into current heat and energy systems and technologies very problematic.

Over the last 20 years, the approach of direct hydrotreatment of bio-oil to stable hydrocarbons or oxygenated liquids has been intensively studied. Elliott has published a detailed study of these many historical developments, including work with model compounds known to be present in bio-oils (Historical Developments in BioOils Hydroprocessing, DC Elliott, Energy & Fuels 2007, 21, 1792- 1815).

Another approach is to convert the bio-oil alone or with conventional hydrocarbons into FCC-type catalytic cracking processes. Al-Sabawi et al. (Fluid Catalytic Cracking of Biomass-Derived Oils and Their Blends with Petroleum Feedstocks: A Review, M. Al-Sabawi et al., Energy & Fuels 2012, 26, 5355-5372) published a synthesis of research and development in this field by evaluating the effects of the introduction of liquid feeds from biomass, including bio-oils, on the operability of conventional FCC processes, catalysts, yields and product qualities. One of the major obstacles to direct hydrotreating or catalytic cracking of bio-oils is their propensity to polymerize when subjected to temperatures above about 100 ° C, resulting in the formation of temperatures above about 140 ° C, with consequences such as clogging charging lines, furnaces and reactors and the rapid deactivation of the catalyst, or even clogging of the reactor inlet and injectors.

US2014034550, US2014034552, US201403554 disclose a FCC type conversion process of a non-hydrotreated bio-oil co-processing with a hydrocarbon feed using separate injection modes. These modes are presented as advantageous for treating unstable bio-oils with immiscible hydrocarbons. However, there is no mention of the products formed and their quality.

It remains to find an efficient conversion process. The difficulties encountered have their origin in the rapid thermal polymerization of the bio-oil, which leads to line blockages and reaction equipment as well as a rapid deactivation of the catalyst and a loss of carbon yield of the products of interest by the In other words, at the temperatures typically required for the hydrotreatment of bio-oils, the polymerization reactions are substantially faster than the hydrotreatment reactions, which ultimately results in the formation of coke and dry gas. solid in equipment in reaction conditions. In FCC-type processes, the formation of polymers can cause clogging of the injectors and the presence of a high concentration of coke to be burned in the regeneration section with the consequence of reducing the catalyst life by regeneration temperatures. too high.

Al-Sabawi et al. (Fluid Catalytic Cracking of Biomass-Derived Oils and Their Blends with Petroleum Feedstocks: A Review, M. Al-Sabawi et al., Energy & Fuels 2012, 26, 5355-5372) concludes their study with the need to hydrotreat the bio-oils before sending them in an FCC-type process. Nevertheless, no information is given on the means to be used, the operating conditions of the hydrotreatment and the level of hydrotreatment necessary for an effective conversion of bio-oils into FCC.

There is therefore a need for an improved bio-oil conversion process that minimizes solids formation, catalyst deactivation and hydrogen consumption, and maximizes the deoxygenated oil yield produced.

The present invention aims at producing aromatic and olefinic compounds and fractions that can be incorporated in the fuel pool, in particular at the gasoline, kerosene and diesel fuel pool, from a liquid feedstock comprising at least one bio-oil using a process comprising one or more several hydroreforming step (s), followed by a step of catalytic cracking of the effluent from the hydroreforming step (s). Summary of the invention

The present invention relates to a process for converting a liquid feedstock comprising at least one bio-oil, said feedstock being introduced in at least the following stages: one or more hydroreforming stage (s), possibly preceded by pretreatment of the bio-oil in particular to improve the thermal stability, in the presence of hydrogen and one or more hydroreforming catalysts comprising at least one transition metal selected from the group of elements 3 to 12 of the periodic classification and at least one support selected from activated carbons, silicon carbides, silicas, transition aluminas, alumina silicas, zirconium oxide, cerium oxide, titanium oxide and aluminates of transition metals, 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, operating at a temperature of between 100 and 450 ° C., at an absolute pressure of between 3 and 30 MPa, at a space hourly velocity with respect to the bio-oil greater than 0.2 h -1, and with a quantity of hydrogen introduced such as the volume ratio of hydrogen. on hydrocarbons is between 50 and 2000 Nm3 / m3, a step of catalytic cracking of at least a portion of the effluent from the hydroreforming stage (s) in at least one reactor operating in updraft or downstream containing a catalytic cracking catalyst, operating with a catalyst on charge ratio of between 4 and 15 and with an outlet temperature of the reactor (s) of between 450 and 600 ° C., a separation of the effluent obtained at the end of the catalytic cracking step.

An advantage of the present invention is to provide a process for converting a liquid feedstock comprising at least one bio-oil, comprising one or more hydroreforming step (s), possibly preceded by a pretreatment of the bio-oil in particular. to improve the thermal stability, followed by a catalytic decarcing step to obtain, after separation, aromatic compounds, olefinic and fractions that can be incorporated into the fuel pool, in particular the gasoline and diesel fuel pool.

The present invention, with respect to the direct catalytic cracking of the bio-oil, has the main advantage of having a partially purified feedstock and with a molecular weight distribution more narrow to lower molecular weights (for example less than 1000), which promotes catalytic cracking of products of interest, increases the yield of said products, and decreases the inevitable conversion of the heavier compounds and / or the more refractory coke which is deposited on the catalytic cracking catalyst. This induces a lower coke production allowing a significantly more favorable liquid product energy efficiency and easier operation of the catalytic cracking unit. In addition, the partial purification / conversion of the bio-oil makes it possible to envisage mixing it, at least partially, with conventional oil charges, which greatly reduces the operating cost (reduces for example the consumption of catalyst), simplifies the injection system since it is thus possible in this case to have one (and not two different systems as in the case of an unconverted bio-oil) and therefore reduces the investment while facilitating the driving of the unit.

DETAILED DESCRIPTION OF THE INVENTION

According to the invention, the filler comprising at least one bio-oil treated in the process according to the invention is a liquid filler.

Throughout the rest of the text, the term "liquid filler" is understood to mean a filler comprising less than 2% by weight and preferably less than 1% by weight relative to the bio-oil, of solid particles dispersed in a liquid. This corresponds to a bio-oil / solid particles ratio greater than 50: 1 and preferably greater than 100: 1 Said charge is not a suspension.

A bio-oil is a complex mixture of oxygenates, obtained from breaking biopolymers present in the original biomass. In the case of lignocellulosic biomass, the structures from these three main components, cellulose, hemicellulose and lignin, are well represented by the components of the bio-oil.

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 of oxygen relative to the total weight of said bio-oil. In general, the oxygenated compounds are alcohols, aldehydes, esters, ethers, organic acids and aromatic oxygen compounds. In the case where the bio-oil is derived from the rapid pyrolysis, part of the oxygen is present in the form of free water representing at least 5% by weight, preferably at least 10% by weight and preferably at least 20% by weight. % weight of the bio-oil. These properties make the bio-oil totally immiscible with hydrocarbons, even with aromatic hydrocarbons that typically contain very little or no oxygen.

The bio-oils are preferably derived from biomass preferably selected from plants, herbs, trees, wood chips, seeds, fibers, seed husks, aquatic plants, hay and other sources of lignocellulosic materials, such as those from municipal waste, agro-food waste, forest waste, slaughter residues, agricultural and industrial waste (such as sugar cane bagasse, waste from oil palm cultivation, sawdust or straws). Bio-oils can also come from paper pulp and by-products of recycled or non-recycled paper or by-products from 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, with or without hydrogen (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. Bridgewater, 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 the 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 20 seconds, which favors the liquid yield. In particular, the intermediate pyrolysis generally allows the production of 30% by 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, the Fast pyrolysis generally allows the production of 10-20% weight of gas, 60-75% weight of liquid and 10-20% weight of char. The highest liquid yields are therefore obtained in the context of rapid wood pyrolysis processes, with a liquid yield of up to 75% by weight. Part of the oxygen is present in the form of free water representing at least 5% by weight, preferably at least 10% by weight and preferably at least 20% by weight of the bio-oil.

Preferably, the bio-oils used in the process according to the present invention are obtained by rapid pyrolysis of the biomass.

The bio-oils can also advantageously be obtained by thermochemical liquefaction of the biomass such as for example by hydropyrolysis of the biomass.

The treated liquid feedstock in the process according to the invention preferably comprises a bio-oil content of between 1 and 100% by weight relative to the total weight of said feedstock.

The liquid feedstock comprising at least one bio-oil used in the process according to the invention may also advantageously contain other liquid feedstocks derived from biomass, said liquid feeds being advantageously chosen from vegetable oils, algae or algal oils. , fish oils, fats of vegetable or animal origin, and alcohols derived from the fermentation of the sugars of biomass, or mixtures of such fillers, whether pre-treated or not. Vegetable oils or oils derived from animal fats essentially comprise chemical structures of the triglyceride type which are also known to those skilled in the art as tri-ester of fatty acids as well as free fatty acids, the fatty chains of which contain a fatty acid. number of carbon atoms between 9 and 25.

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 oils, flax and crambe and all oils from eg sunflower or rapeseed by genetic modification or hybridization, this list is not limiting. Said animal fats are advantageously chosen from fats composed of residues from the food industry or from the catering industries. Fried oils, various animal oils such as fish oils, tallow, lard can also be used.

Said liquid feed comprising at least one bio-oil may also advantageously be treated in admixture with at least one hydrocarbon liquid feed derived from petroleum and / or coal. The petroleum hydrocarbon feedstock can advantageously be selected from the direct distillation distillates under vacuum, vacuum distillates from a conversion process, such as those resulting from coking processes, fixed bed hydroconversion or hydrotreating of ebullated bed heavy fractions, products from fluid catalytic cracking units, such as, for example, light catalytic cracked gasoil (LCO) of different origins, heavy catalytic cracked gasoil (HCO) of different origins and any fluid catalytic cracked distillate fraction generally having a distillation range of about 150 ° C to about 370 ° C, the aromatic extracts and paraffins obtained in the preparation of lubricating oils and the solvent deasphalted oils, alone or in mixed. The hydrocarbon feedstock derived from coal may advantageously be chosen from products resulting from the liquefaction of coal and aromatic fractions originating from the pyrolysis or gasification of coal and shale oils or products derived from shale oils, alone or mixed, pretreated or not.

Preferably, said liquid feed comprising at least one bio-oil may advantageously be a mixture of any of the abovementioned fillers, said feeds possibly being pretreated or not.

In a preferred variant, said liquid feed treated in the process according to the invention consists entirely of bio-oil.

Prior to the hydroreforming step, said liquid feedstock comprising at least one bio-oil may advantageously undergo at least one pretreatment step making it possible to separate at least one fraction comprising solid impurities from said liquid feedstock and / or to reduce the amount of highly reactive compounds that can polymerize.

Said pretreatment stage may be, without being exhaustive, a step of physical separation of 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, catalytic hydrogenation, etc.) making it possible to transform the oxygenated molecules responsible for the thermal instability of the bio-oil at low temperature, for example lower at 100 ° C, or the mixture with an ad-hoc solvent to better stabilize the bio-oil, ...

Said pretreatment step allowing the elimination of at least a portion of said solid impurities and / or oxygenated molecules responsible for the thermal instability of the bio-oil, such as certain carbonyl and carboxylic species, for example, can be done by any of the techniques. solid / liquid separation 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 an indifferent order, some being able to operate in a controlled manner. cyclic to ensure continuous operation of the entire process. The advantage of this optional pretreatment step is to allow certain bio-oils particularly thermally unstable / evolutive and / or containing significant amounts of solids and / or optionally having several separate phases an easier injection of the input charge. of the first hydroreforming step by limiting the risks of corking by polymerization and / or thermal solidification, as well as limiting the risk of production of insoluble particles in the reactor that may limit the stability of the catalyst and its lifetime and / or the clogging of the reactor (s) or equipment downstream of said reactors.

Hvdroreformaae

According to the invention, said liquid feedstock having optionally undergone at least one pretreatment stage, possibly with at least one liquid hydrocarbonaceous feedstock derived from oil and / or coal, optionally other liquid feedstocks derived from the biomass, optionally in a mixture with at least a portion of the organic phase of the effluent from the hydroreforming stage which is recycled, is introduced into 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 a hydrotreatment / hydro-conversion step in which the liquid feedstock comprising at least the bio-oil and preferably in which the bio-oil is partially deoxygenated and partially hydroconverted. Said hydroreforming step is carried out with a partial production of hydrogen internal to the reaction.

Preferably, said hydroreforming step is a partial deoxygenation and partial hydroconversion step. Partial deoxygenation and partial hydroconversion are understood to mean a reaction in which the oxygen content in the organic phase is reduced to a content of between 5 and 25% by weight and makes it possible to obtain less than 20% by weight of a fraction boiling at a temperature greater than 600 ° C.

During said hydroreforming step, the bio-oil is converted to stabilize the product, to render it at least partially miscible with the hydrocarbons, to cause an easy phase separation of the water in the bio-oil , lowering its viscosity, lowering its corrosivity, converting high molecular weight fractions significantly to smaller molecules and lowering its oxygen content.

Said hydroreforming step may be carried out in one or more stages at increasing temperatures, with the same catalyst or different catalysts and whose activation form may be similar or different.

According to the invention, the catalyst used in the hydroreforming stage preferably comprises at least one transition metal chosen from the elements from groups 3 to 12 of the periodic table and at least one support chosen from activated carbons. silicon carbides, silicas, transition aluminas, alumina silicas, zirconium oxide, cerium oxide, titanium oxide and transition metal aluminates, alone or as a mixture.

Preferably, the catalyst comprises a group 10 metal, alone or in combination with at least one metal of groups 3 to 12 and preferably at least one metal of groups 4 to 11. Preferably, the catalyst comprises Ni, alone or in combination with at least one metal of groups 4 to 11 and preferably selected from chromium (Cr), molybdenum (Mo), manganese (Mn), tungsten (W), iron (Fe), cobalt (Co) and copper (Cu).

The metal content of group 10, expressed as a percentage by weight of metal oxide of group 10 is advantageously between 1 and 80% by weight, preferably between 5 and 70% by weight and preferably between 10 and 65% by weight relative to to the total mass of said catalyst.

In the case where the Ni is used alone, the Ni content, expressed as a weight percentage of Ni oxide, is advantageously between 1 and 80% by weight, preferably between 5 and 70% by weight and preferably between 10 and 65% by weight. % by weight relative to the total mass of said catalyst.

In the case where the metal of group 10 is chosen from Pt and Pd, said metal is used alone and the content of said metal of group 10, expressed as a percentage by weight of metal oxide of 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.

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% by weight expressed as a percentage Group 3 to 12 metal oxide weight relative to the total mass of said catalyst.

The hydroreforming catalyst may also advantageously comprise a doping element such as, for example, phosphorus, boron or platinum at contents of between 0.1 and 1% by weight relative to the total weight of said catalyst.

Preferably, the support is chosen 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

Preferred hydroreforming catalysts are advantageously chosen from catalysts comprising nickel (Ni), nickel and chromium (NiCr) or nickel and manganese (NiMn) on porous carbon and catalysts comprising nickel and molybdenum ( NiMo) on an alumina or a nickel aluminate. Preferably, said catalyst is prepared according to conventional methods such as co-mixing or impregnation of molecular precursors followed by one or more heat treatments.

Said catalyst is advantageously used in the first step of pre-hydrotreatment under reduced or sulfurized farm.

Operating conditions

According to the invention, said hydroforming step is carried out at a temperature between 100 and 450 ° C, preferably between 250 and 400 ° C, and preferably between 270 and 360 ° C, and at an absolute pressure 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, at a space velocity with respect to the bio oil greater than 0, 2 h -1, preferably between 0.5 h -1 and 5 h -1, and more preferably between 1 h -1 and 5 h -1, and with an amount of hydrogen introduced such that the hydrogen volume ratio on hydrocarbons is between 50 and 2000 Nm3 / m3 and preferably between 100 and 1000 Nm3 / m3.

Preferably, the liquid feed comprising at least the bio-oil is not preheated, or only preheated to a temperature below 80 ° C before being introduced into the hydroreforming process. Indeed, prolonged heating or storage at high temperature can cause deterioration.

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 hydroreforming reaction can be carried out in any reactor which facilitates the efficient dispersion of the bio-oil in the reaction mixture. A simple continuous stirred reactor (CSTR) is suitable in batch mode. For continuous applications, downflow co-flowed bed reactors (fixed bed, moving bed, bubbling bed or slurry reactors will be more suitable.) While keeping the catalyst in the reactor, the Mobile bed and ebullated bed reactor technologies have the advantage of allowing easy catalyst replacement during continuous operations, which provides greater flexibility in unit operation, increases the duty cycle, and maintains a steady state of operation. These technologies also accept charges containing a few solids or producing solids during the reaction, which is not the case for fixed bed reactor technology, except for the use of reactors. permutable guards for example.The technology of the slurry reactor, according to the English terminology, has the same advantages as the technologies of reactors with mo The additional advantage of operating with a fresh catalyst is that with maximum activity, but the disadvantage of greatly complicating the recovery of the catalyst leaving the reactor with the effluents. The addition of a limited amount of catalysts in the form of a dispersion can also be envisaged in a moving or bubbling bed. Other reactors meeting the principles set forth herein are within the abilities of those skilled in the art of chemical reactor technology and are within the scope of the present invention.

The product of the hvdroreformaae stage

According to the invention, said hydroreforming step makes it possible to obtain at least one liquid effluent comprising at least one organic phase.

Said liquid effluent may also optionally contain at least one aqueous phase.

A gaseous phase is also advantageously obtained. Said gaseous phase mainly containing CO 2, CO 3 and light C 1 -C 4 gases such as, for example, methane. Said gaseous phase may advantageously be separated from said aqueous and organic phases in any separator known to those skilled in the art.

At least one step of separating at least one organic phase, at least one aqueous phase and at least one gaseous phase can be implemented between said hydroreforming step and said catalytic cracking step.

Said gaseous phase is advantageously separated from said liquid effluent by a gas / liquid separation step. Said gas-liquid separation step is advantageously implemented in any separator known to those skilled in the art.

Said aqueous phase and said organic phase are advantageously separated by decantation. The analysis of the liquid effluent shows no sign of polymerization.

Said aqueous phase comprises water and may also comprise organic materials, mainly acetic acid and methanol (case of fast pyrolysis bio-oil), dissolved in said aqueous phase. The aqueous phase essentially contains water formed by hydrodeoxygenation and water contained in the unprocessed bio-oil which has not been converted and in general less than about 20% by weight of dissolved organic matter.

The organic phase contains partially deoxygenated bio-oil and hydrocarbons. The term "partially deoxygenated bio-oil" means a bio-oil containing less than 20% by weight of oxygen and preferably less than 15% by weight of oxygen relative to the total mass of said organic phase. The organic phase therefore comprises less than 20% by weight of oxygen, preferably less than 15% by weight of oxygen, 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 sufficient degree to make 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 of up to at least 30% by weight. Moreover, said organic phase is stabilized so that it can be subsequently treated in a refinery without the risk of formation of hydrocarbons. solids by polymerization or polycondensation.

The organic phase preferably contains less than 20% 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 the mass. total of said organic phase.

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 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.

Preferably, the Conradson Carbon (CCR) is less than 10% by weight, preferably less than 7% by weight, more preferably less than 5% by weight. Conradson Carbon is expressed in% by weight.

Typically, during the hydroreforming step, the yields in the organic phase relative to the dry biomass, that is to say comprising 0% moisture, introduced into the pyrolysis step, is between 15 and 45.degree. % by weight, and preferably between 15 and 40% by weight. The yields in aqueous phase relative to the 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 partially deoxygenated bio-oil represents at least 70% by weight.

According to a variant, at least a portion of the organic phase of the effluent from the hydroreforming step is recycled in said hydroreforming step. Preferably, the recycle ratio equal to the ratio of the mass flow rate of said organic phase to the mass flow rate of the non-pretreated bio-oil is between 0.05 and 10, preferably between 0.05 and 5, and very preferably preferred, between 0.05 and 1.

The recycle rates used make it possible to have a sufficiently thermally stable charge overall so that it can be introduced into the preheating furnace as well as into the hydrorefaction reactor without any risk of clogging, to facilitate the conversion and deoxygenation reactions of the biofuel. oil on the catalyst, to improve the dissolution of hydrogen gas in the recycled organic phase from the first hydroreforming step and to better manage the exothermicity generated 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 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 bio-oil. partially deoxygenated and the aqueous phase at the hydroreforming outlet. This separation which occurs easily during the cooling of the reaction mixture is another advantage that provides the presence of the organic phase recycled in the reaction mixture of the hydroreforming step.

Hydrogen consumption Hydrogen 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 efficiency carbon dioxide), by steam reforming methane produced and light gas fractions and / or fractions comprising light oxygen compounds from the hydroreforming step or the optional hydrotreatment step and the subsequent step of catalytic cracking. It is also possible to react the CO recovered with the water produced to obtain hydrogen by means of the known reaction of gas to water conversion by "water gas shift" according to the English terminology (WGS) . Thus, the overall process, from the biomass to the final hydrocarbon product, could be self-sufficient in hydrogen.

During the hydroreforming step, a moderate amount of gaseous hydrocarbon, essentially methane, is formed. This methane fraction can advantageously be reformed using the so-called steam methane reforming (SMR) process in order to produce bio-hydrogen for the hydroreforming steps or the optional hydrotreatment step.

It is also possible to use the bio-coal from the pyrolysis step as feed for the gasification reactor to produce synthesis gas (CO + H2). This synthesis gas can also be used to produce bio-hydrogen for the hydroreforming steps or the optional hydrotreating step.

Thus, by implementing the SMR process and / or the gasification of bio-coal, the process of conversion and upgrading of the bio-oil can be self-sufficient in hydrogen, without requiring the addition of hydrogen of origin fossil

We have also discovered that the partially deoxygenated bio-oil and more particularly the organic phase comprising at least said partially deoxygenated bio-oil produced by hydroreforming can be converted into aromatic and olefinic compounds and fractions that can be incorporated in the fuel pool and in particular gasoline, kerosene and diesel fuel, with better liquid yields than on non or insufficiently hydroconverted bio-oil, with a lower coke yield and can also be treated optionally in co-processing with a single injection.

Optional prehydroaénation.

A pre-hydrogenation step may advantageously be carried out upstream of said hydroreforming step, and preferably between said optional pre-treatment step and said hydroreforming step.

Preferably, said pre-hydrogenation step is carried out at low temperature.

Preferably, said pre-hydrogenation step is carried out at a temperature between 70 and 250 ° C., preferably between 70 and 200 ° C. and very preferably between 100 and 200 ° C., at an absolute pressure of between 3 and 30 ° C. MPa, at a space hourly velocity with respect to said 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 .

Said pre-hydrogenation step is advantageously carried out in the same type of reactor as the hydroreforming step.

Preferably, said pre-hydrogenation step is carried out in the presence of a catalyst that is identical to or different from the catalyst used in said hydroreforming step and preferably different. Said catalyst used in said pre-hydrogenation step has the same definition as the catalyst used in said hydroreforming step. Optional hydrotreatment step

According to a preferred embodiment, at least a part, and preferably all, of the organic phase of the effluent resulting from the hydroreforming step is sent to a hydrotreatment step in the presence of hydrogen in at least one reactor containing a hydrotreating catalyst, operating at a temperature between 250 and 400 ° C, preferably between 320 and 380 ° C, at a pressure of between 2 MPa and 25MPa, preferably between 5 MPa and 20 MPa and at a pressure of hourly space velocity of between 0.1 hr -1 and 20 hr -1 and preferably between 0.5 hr -1 and 5 hr -1 and with a total amount of hydrogen mixed with the feedstock (including chemical consumption and the amount recycled) such that the volume ratio hydrogen / hydrocarbon 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 metal of group 6 chosen from molybdenum and tungsten alone or as a mixture, preferably associated with at least one metal of groups 8 to 10, preferably 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, titanium oxide, phosphoric anhydride. Preferably, said support is made of alumina, and more preferably alumina [eta], [theta], [delta] or [gamma].

The total amount of metal oxides of group 6 and groups 8 to 10 in the hydrotreatment catalyst used is advantageously between 5 and 40% by weight, preferably between 6 and 35% by weight relative to the 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 relative to the total mass of catalyst. 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 molybdenum oxide, these percentages being expressed in% by weight relative to the total mass of catalyst. A preferred catalyst is advantageously chosen from NiMo, NiW or CoMo catalysts on an alumina support.

Said catalyst used in the hydrotreating step may also advantageously contain at least one doping element chosen from phosphorus and 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% relative to the total mass of catalyst.

The metals of the catalysts used in the hydrotreatment step of the method according to the invention may be metals or sulphurized metal phases. For maximum efficiency, these metal oxide catalysts are usually converted at least partially to metal sulfides. The catalysts based on metal oxides can be sulphurated by any technique known in the prior art, for example in the reactor (in situ) or ex situ, by contacting the catalyst, at elevated temperature, with a source. of hydrogen sulfide, such as dimethyl disulfide (DMDS).

Since biomass normally contains only a very small amount of sulfur, the use of non-sulphurized catalysts should avoid any risk of sulfur contamination in the fuels produced. Among the other catalysts based on metal oxides adapted to the hydrotreatment stage, mention may be made of the metal phases obtained by reduction in hydrogen. The reduction is generally carried out at temperatures of from about 150 ° C to about 650 ° C, at a hydrogen pressure of from about 0.1 to about 25 MPa (14.5-3625 psi). Optional separation

A step of separating at least one organic phase, at least one aqueous phase and at least one gaseous phase may optionally be implemented between said hydrotreating step and said catalytic cracking 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 organic phase resulting from the hydrotreating step and optionally separated is freed from nitrogen, oxygen and sulfur impurities.

The fractionation zone preferably comprises a fractionation section which incorporates a high temperature high pressure separator (HPHT) and then an atmospheric distillation. Catalytic cracking stage

According to the invention, at least a portion of the effluent from the hydroreforming step, and preferably at least a portion, preferably the entire organic phase of the effluent from said step of hydroreforming having optionally undergone the hydrotreatment step and optionally separated, is sent in said catalytic cracking step in at least one reactor operating in upward or downward flow containing a catalytic cracking catalyst, operating with a catalyst to charge ratio of between 4 and 15, preferably between 6 and 12 and with an outlet temperature of the reactor (s) of between 450 and 600 ° C, preferably between 480 and 580 ° C.

Preferably, the feedstock of said catalytic cracking step is the organic phase of the effluent resulting from the hydroreforming step, having optionally undergone the hydrotreating step and optionally separated and / or fractionated.

According to a preferred embodiment, at least one hydrocarbon liquid feed derived from petroleum and / or coal is sent in said catalytic cracking step mixed with at least a portion of the liquid effluent from the hydroreforming step, and preferably at least a portion, preferably all of the organic phase of the effluent from said hydroreforming step having optionally undergone the hydrotreating step and optionally separated.

In the case where at least one hydrocarbon liquid feed derived from petroleum and / or coal is sent in said catalytic cracking step mixed with at least a part of the effluent from the hydroreforming stage, the proportion of effluent from the hydroreforming stage represents at least 1%, preferably 5% by weight relative to the total mass of said mixture consisting of the hydrocarbon liquid feedstock and the effluent from the hydroreforming step. Preferably, the proportion of the effluent from the hydroreforming step represents at most 50%, preferably at most 30% by weight relative to the total mass of said mixture.

The liquid hydrocarbonaceous feedstock derived from petroleum and / or coal to be cracked contains more than 50% by weight of hydrocarbons having a boiling point greater than 340.degree. Generally the charge consists of a vacuum distillate, or optionally an atmospheric residue. The overall cracked feed may contain up to 100% by weight of hydrocarbons having a boiling point above 340 ° C. Among them, and in a non-exhaustive manner, there may be mentioned: distillates of direct distillation under vacuum, vacuum distillates resulting from a conversion process, such as those resulting from coking processes, hydroconversion to a fixed bed , hydrocracking or hydrotreating of heavy fractions in a bubbling bed, a moving bed or a slurry bed, - aromatic extracts and paraffins obtained during the preparation of lubricating oils - deasphalted oils extracted with a solvent, alone or in mixture.

In a catalytic cracking unit, the thermal balance is ensured by the combustion of the coke deposited on the catalyst during the reaction step. This combustion takes place in the regeneration zone by air injection via a compressor called the main air compressor (abbreviated MAB, abbreviation of the English terminology of "main air blower").

Typically, the catalyst enters the regeneration zone with a coke content (defined as the mass of coke on the mass of catalyst) of between 0.5% and 1%, and comes out of said zone with a coke content of less than 0.01%. During this step, combustion fumes are generated and leave the regeneration zone at temperatures between 640 ° C and 800 ° C. These fumes will then, depending on the configurations of the unit, undergo a number of post treatments.

The Conradson carbon content of the feedstock (abbreviated as CCR and defined for example by ASTM D 482) provides an evaluation of coke production during catalytic cracking. Depending on the Conradson carbon content of the feed, the coke yield requires a specific sizing of the unit to satisfy the heat balance.

Thus, when the load has a CCR leading to a higher coke content than that required to ensure the thermal balance, the excess heat must be removed. This can be done for example, and non-exhaustively, by the installation of a "catcooler", well known to those skilled in the art, which is an external cooling of a regenerator catalyst section by exchange with water, leading to the production of high-pressure steam.

The catalyst of the FCC reactor is typically composed of particles of average diameter generally between 40 and 140 micrometers, and most often between 50 and 120 micrometers.

The catalytic cracking catalyst contains at least one suitable matrix such as alumina, silica or silica-alumina with or without the presence of a Y-type zeolite dispersed in this matrix.

The catalyst may further comprise at least one zeolite having a shape selectivity of one of the following structural types: MEL (for example ZSM-11), MFI (for example ZSM-5), NES, EUO, FER, CHA ( for example SAPO-34), MFS, MWW. It may also comprise one of the following zeolites: NU-85, NU-86, NU-88 and IM-5, which also have a shape selectivity. The advantage of these zeolites having a shape selectivity is to obtain a better selectivity propylene / isobutene, ie a higher propylene / isobutene ratio in the cracking effluents.

The proportion of zeolite having a shape selectivity with respect to the total amount of zeolite may vary depending on the charges used and the structure of the desired products. Often, from 0.1% to 60%, preferably from 0.1% to 40% and in particular from 0.1% to 30% by weight of zeolite having a shape selectivity are used.

The zeolite (s) may be dispersed in a matrix based on silica, alumina or silica-alumina, the proportion of zeolite (all zeolites combined) relative to the weight of the catalyst being often between 0.7% and 80% by weight. preferably between 1% and 50% by weight, and more preferably between 5% and 40% by weight.

In the case where several zeolites are used, they can be incorporated in a single matrix or in several different matrices. The zeolite content having a shape selectivity in the total inventory is less than 30% by weight.

The catalyst used in the catalytic cracking reactor may consist of an ultra-stable type Y zeolite dispersed in a matrix of alumina, silica, or silica-alumina, to which is added a zeolite additive ZSM5, the amount of ZSM5 crystals in the total inventory being less than 30% by weight.

Said catalytic cracking step operates both in FCC units using an upflow reactor (called "riser" in English terminology), and in units using a downflow reactor (called "downer" in the terminology). Anglo-Saxon).

Said catalytic cracking step advantageously operates in an FCC unit operating with a single reactor (in upward or downward flow), only in an FCC unit operating with two reactors, one treating for example the liquid hydrocarbon feedstock derived from petroleum and or coal, the other the organic phase of the effluent from the hydroreforming step, optionally having undergone the hydrotreatment step and optionally separated and / or fractionated The injection of the organic phase can be done via dedicated injectors or via the injectors of the hydrocarbon feedstock liquid from oil and or coal. This latter option is possible without prior treatment of the bio-oil due to immiscibility with hydrocarbon feedstocks and the unstable nature of the latter with temperature.

The FCC process converts heavy hydrocarbon feeds into lighter hydrocarbon fractions, ranging from dry gases to a conversion residue. Among the effluents, it is possible to distinguish the following cuts which are conventionally defined according to their composition or their boiling point (standard cutting points given as an indication): dry and acidic gases (essentially: H2, H2S, C1) , C2), - liquefied petroleum gases containing the C3-C4 molecules, - gasolines containing heavier hydrocarbons having a boiling point below 220 ° C (standard cutting point), - diesel fuels standard boiling range 220-360 °, which are very aromatic and therefore called LCO (light cycle oil) - the conversion residue, boiling point above 360 ° C. The catalytic cracking reactor (FCC) effluent separation unit generally comprises a primary separation of FCC effluents, a gas compression and fractionation section, and distillations for fractionation of the different liquid cuts. This type of fractionation unit is well known to those skilled in the art.

DESCRIPTION OF THE FIGURE

FIG. 1 illustrates a particular embodiment of the method according to the invention.

The bio-oil resulting from the rapid pyrolysis of the biomass is introduced via line (1), mixed with hydrogen (3) and the organic phase (8) resulting from the hydroreforming step, in the first hydroreforming zone (2). The liquid effluent from the hydroreforming zone via line (4) is introduced into a separator (5). A gaseous phase mainly containing CO 2, IF 2 S and light C 1 -C 4 gases such as, for example, methane is separated via line (7) and an aqueous phase is also separated via line (6). An organic phase containing the partially deoxygenated bio-oil and hydrocarbons is withdrawn through line (8) and part of said organic phase is recycled to the hydroreforming zone. The non-recycled portion of said organic phase is then sent to a catalytic cracking zone (FCC) (10), optionally mixed with a hydrocarbon effluent (9). The effluent from the catalytic cracking step is introduced via line (11) into a separation zone (12) making it possible to separate a gaseous effluent containing dry and acid gases (13), an effluent of liquefied gas containing C3-C4 molecules (14), a liquid hydrocarbon effluent having a boiling point of less than 220 ° C (15), a liquid hydrocarbon effluent having a boiling range of 220-360 ° C (16), and a residual boiling point conversion greater than 360 ° C (17).

The examples below illustrate the invention without limiting its scope. Example 1 corresponds to a configuration of the prior art namely the coprocessing of a mixture comprising 90% by weight of a VGO feedstock and 10% of Bio oil not post-treated in a catalytic cracking step.

Examples 2 and 3 cover the innovation namely to subject the bio-oil respectively a hydroreforming step and a hydroreforming step followed by a hydrotreatment step before being co-processed with a VGO in a catalytic cracking step in the same proportions as Example 1.

For the four examples, the capacity of the FCC unit considered is 300t / h and the standard conversion is defined by the formula 100- (cutting yields 220-360 ° C & 360 ° C +)

Example 1: not in accordance with the invention

The results are summarized in Table 1.

Table 1

The introduction of non-post-treated bio-oil into a catalytic cracking unit will result in an increase in the unit's delta coke and result in a large increase in regenerator temperature and coke efficiency. The thermal stability limits of the catalyst being at 800 ° C a maximum temperature below this Imite is required. Thus in the treated case no more than 10% of non-hydrotreated bio oil can be coprocessed with the VGO feed. At this high temperature value of the regenerator, the closure of the heat balance imposes a higher riser output temperature (denoted ROT) and a stronger C / O. As a result, the selectivity in dry gas (unearned products) is greatly degraded as well as the standard conversion and yields of the desired products ie LPG, gasoline (PI-220 ° C) and middle distillate (220-360 ° C). In the end, the bio non-treated oil degrades the performance of the unit.

Example 2: in accordance with the invention

In Example 2 the bio-oil was post-treated in a hydroreforming thus improving its crackability properties.

The results are summarized in Table 2.

Table 2:

Thanks to the hydroreforming step, the system's delta coke is improved (0.88 against 1.1) which limits the temperature of the regenerator to 730 ° C against 785 ° C previously. The closure of the heat balance imposes a riser output temperature (ROT) of 530 ° C, which is more basic than in the case of an unposted bio oil. This results in a lower yield of dry gas, a limitation of the coke yield as well as an improvement in conversion and desired product yields. However, even with a hydroreforming step, the performance of the 100% VGO case is still not found.

Example 3: in accordance with the invention

In this last example, the bio oil undergoes two post-treatment namely a hydrorreforming followed by a hydrotreatment improving all its properties and among them its crackability.

The results are summarized in Table 3.

Table 3:

Thanks to the two post-treatments of the bio-oil, the delta coke is strongly limited and close to the case 100% VGO. Thus, the performances in terms of selectivity and yields of desired products are greatly improved and almost identical to those obtained in the case of 100% VGO.

Claims (11)

1. Method for converting a liquid feedstock comprising at least one bio-oil, said feedstock being introduced in at least the following stages: one or more hydroreforming step (s), possibly preceded by a pretreatment of the bio-oil in particular to improve the thermal stability, in the presence of hydrogen and one or more hydroreforming catalysts comprising at least one transition metal selected from the elements from 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 metal aluminates transition mixture, 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, operating at a temperature of between 100 and 450 ° C., at an absolute pressure e between 3 and 30 MPa, at a space hourly speed with respect to the bio oil greater than 0.2 h'1, and with a quantity of hydrogen introduced such that the volume ratio hydrogen on hydrocarbons is between 50 and 2000 Nm3 / m3, a step of catalytic cracking of at least a portion of the effluent from the hydroreforming step (s) in at least one reactor operating in upward or downward flow containing a catalytic cracking catalyst, operating with a catalyst to charge ratio of between 4 and 15 and with an outlet temperature of the reactor (s) of between 450 and 600 ° C., a separation of the effluent obtained at the end of the catalytic cracking stage. 2. Method according to claim 1, wherein said hydroreforming step is carried out at a temperature of between 250 and 400 ° G, at an absolute pressure of between 3.5 and 25 MPa and at a space velocity of between 0.5. h-1 and 5 h-1, and with a quantity of hydrogen introduced such that the volume ratio hydrogen on hydrocarbons is between 100 and 1000 Nm3 / m3. 3. Method according to one of claims 1 and 2, wherein said liquid feed comprising at least one bio-oil also contains other liquid feedstock from the biomass, said liquid feedstock being selected from vegetable oils, baking oils and the like. algae or algae, fish oils, fats of vegetable or animal origin, and alcohols derived from the fermentation of sugars from biomass, or mixtures of such fillers, whether pre-processed or not. 4. Method according to one of claims 1 and 2, wherein said liquid charge consists entirely of bio-oil. 5. Method according to one of claims 1 to 4, wherein said 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) and a support selected from silicas, transition aluminas, silica aluminas, porous carbon and aluminum aluminates. transition metals, alone or in mixture. The process according to claim 5, wherein said hydroreforming catalyst is a catalyst selected from catalysts comprising nickel (Ni), nickel and chromium (NiCr) or nickel and manganese (NiMn) on porous carbon and catalysts comprising nickel and molybdenum (NiMo) on alumina or nickel aluminate. 7. Method according to one of claims 1 to 6, wherein a step of separating at least one organic phase, at least one ausused phase and at least one gaseous phase can be implemented between said step hydroreforming and said catalytic cracking step. 8. Method according to one of: claims 1 to 7, wherein a pre-hydrogenation step is carried out upstream of said hydroreforming step, said pre-hydrogenation step being carried out at a temperature between 70 and 250 ° C., at an absolute pressure of between 3 and 30 MPa, at a space hourly velocity with respect to said bio-oil greater than 0.2 h -1, and with a quantity of hydrogen introduced such as the hydrogen volume ratio. on bio-oil is between 50 and 2000 Nm3 / m3. 9. Method according to one of claims 1 to 8, wherein at least a portion of the organic phase of the effluent from the hydroreforming step, is sent in a hydrotreating step in the presence of hydrogen in at least one reactor containing a hydrotreatment catalyst, operating at a temperature of between 250 and 400 ° C., at a pressure of between 2 MPa and 25 MPa, and at a space velocity of between 0.1 h -1 and 20 h. h-1 and with a total amount of hydrogen mixed with the feed such that the volume ratio hydrogen / hydrocarbon is between 100 and 3000 Nm3 / m3. 10. Method according to one of claims 1 to 9, wherein said cracking step operates with a catalyst to charge ratio between 6 and 12 and at an outlet temperature of the reactor or between 480 and 580 ° C. 11. Method according to one of claims 1 to 10, wherein at least one hydroGarbonée liquid feed derived from oil and / or coal is sent in said catalytic cracking step in mixture with at least a portion of the effluent from the hydroreforming step.