PROCESS FOR THE TRANSFORMATION OF LIGNOCELLULOSIC BIOMASS TO OXYGENIC MOLECULES AND HYDROCARBONS WIT

专利摘要:
The invention describes a process for producing bioproducts from lignocellulosic biomass, comprising a) a step of converting the lignocellulosic biomass into at least one cellulosic fraction comprising a cellulose content of at least 60% by weight relative to the material. drying said cellulosic fraction and at least one liquid effluent, b) a step of separating at least a portion of the solvent from the liquid effluent obtained at the end of step a) to produce an effluent comprising predominantly said solvent and an effluent comprising mainly a bio-oil, c) a step of conversion of the effluent comprising mainly a bio-oil from step b) into an effluent comprising mainly hydrocarbons, d) a step of separating said liquid effluent comprising mainly hydrocarbons from step c) to produce cuts that can be incorporated into fuel cuts and / or cuts comprising aromatics (e) A step of converting the liquid effluent resulting from step a) into a liquid effluent mainly comprising mono or poly-oxygenated compounds, by contact with a homogeneous / heterogeneous catalytic system and f) a step separation of the liquid effluent comprising predominantly mono or poly-oxygenated compounds in an effluent predominantly composed of alcohols and polyols.
公开号:FR3030561A1
申请号:FR1462832
申请日:2014-12-18
公开日:2016-06-24
发明作者:Amandine Cabiac；Damien Delcroix；Etienne Girard；Marc Jacquin
申请人:IFP Energies Nouvelles IFPEN；
IPC主号:

专利说明:

[0001] FIELD OF THE INVENTION The present invention relates to a process for converting lignocellulosic biomass into bioproducts. Under the term bioproduct, we mean the products of the energy, chemistry and materials industries derived from vegetable raw materials. The bioproducts can be in particular hydrocarbon bases that can be incorporated in the fuel pool or chemical intermediates used in the field of petrochemistry. PRIOR ART Lignocellulosic biomass represents one of the most abundant renewable resources on Earth, and certainly one of the least expensive. The substrates considered are very varied, since they concern both woody substrates (hardwood and softwood), agricultural by-products (straw) or lignocellulosic waste-generating industries (agro-food industries, paper mills).
[0002] In the current energy context, lignocellulosic biomass has emerged as a source of renewable and alternative raw material. In addition to its large-scale availability, the richness and diversity of the chemical groups present in biomass make it possible to envisage the partial replacement, or even substitution, of a large part of products used in industry and everyday life. from fossil resources. By its nature, lignocellulosic biomass is essentially a source of carbohydrates and aromatic compounds. It is composed of three constituents: lignin, a macromolecule of complex structure and high molecular weight, composed of aromatic groups mainly linked together by ether bonds, cellulose, a cellobiose polymer, itself a dimer of glucose, and hemicellulose, a polysaccharide composed of pentoses and hexoses.
[0003] However, the supramolecular organization and the diversity of the chemical and enzymatic reactivities of the fractions constituting the lignocellulosic biomass constitute a brake on the respective valorization of each of its fractions. The transformation of a renewable resource from biomass thus presents significant challenges on an industrial scale, which have hitherto hampered the development of lignocellulosic biomass recovery processes. The transformation of lignocellulosic biomass into second-generation biofuels and "bio-sourced" chemical intermediates has already been the subject of numerous studies at both the industrial and academic levels. The so-called thermochemical processes, including gasification or pyrolysis steps, make it possible to produce "bio-sourced" fuels by destructuring the biomass under severe and energy-consuming conditions.
[0004] Another widely explored route is the "biochemical" route, for example for the production of ethanol, according to a process which comprises steps of pretreatment of a lignocellulosic substrate, followed by enzymatic hydrolysis of the pretreated substrate and then a fermentation. alcoholic of the hydrolyzate obtained. Here again, the pretreatment steps necessary to activate the cellulosic fraction with respect to the enzymes prove to be costly in energy and have a significant impact on the cost price of the final product. The constituents of lignocellulosic biomass can also be transformed into bioproducts after pretreatment / fractionation steps. The cellulosic portion of the biomass can thus be upgraded by homogeneous, heterogeneous or combined catalyst systems to obtain alcohols and polyols. The patent applications WO2009 / 31469, US2010 / 126501, WO2009 / 147522 relate, for example, to the catalytic hydrolysis of cellulose to glucose on heteropolyanion type acid clusters. US2009 / 217922 describes the use of bifunctional metal / acid catalysts for the hydrolysis of cellulose to sugar alcohols. The patent application WO2013 / 170767 discloses a system combining a homogeneous catalyst and a heterogeneous catalyst for upgrading the cellulose and hemicellulose part to polyols with 2 and 3 carbons (mainly ethylene glycol and propylene glycol). The lignin fraction can be valued in simple aromatic compounds and / or in "bio-oil", themselves recoverable in chemical intermediates and in fuel. This is illustrated, for example, in US patent application 2014/047905 and the article published by Ferrini and Rinaldi in Angewandte Chemie International Edition (Volume 53, Issue 33, pages 8634-8639, 2014).
[0005] The discovery of a process freed from any pretreatment step, in particular chemical pretreatment and making it possible to valorize the different constituents of lignocellulosic biomass under mild and energy-saving conditions, would therefore make it possible to access "bio-sourced" products at more competitive cost prices.
[0006] OBJECT OF THE INVENTION The present invention describes a process for producing bioproducts from lignocellulosic biomass, comprising at least the following steps: a) A first step of converting lignocellulosic biomass into at least one cellulosic fraction comprising a cellulose content at least 60% by weight relative to the dry matter of said cellulosic fraction and at least one liquid effluent, said conversion step operating in the presence of a mass or supported heterogeneous catalyst, of molecular hydrogen and / or solvent, at a temperature between 150 and 300 ° C and at a pressure between 0.5 and 20 MPa, b) A first step of separation b) at least a portion of the solvent of the liquid effluent obtained at from step a) of conversion to produce an effluent comprising mainly said solvent and an effluent comprising mainly a bio-oil, c) A second step of conversion of the effluent comprising predominantly a bio-oil from step b) of separation into an effluent comprising predominantly hydrocarbons, said conversion step operates in the presence of hydrogen and a heterogeneous catalyst, at a temperature above 200 ° C, at a pressure of between 2 and 25 MPa and at a space velocity of between 0.1 and 20 h -1, d) a second stage of separation of said liquid effluent comprising mainly hydrocarbons from the second conversion step c), e) a third step e) of converting the cellulosic fraction resulting from the conversion step a) into a liquid effluent mainly comprising mono or poly-oxygenated compounds, in which said cellulosic fraction is brought into contact simultaneously with a combination of one or more homogeneous catalysts and one or more heterogeneous catalysts, in the same reaction chamber, in the presence of at least one solvent wherein said solvent is water alone or in admixture with at least one other solvent, under a reducing atmosphere, and at a temperature of between 50 and 300 ° C, and at a pressure of between 0.5 and 20 MPa, ) A third step of separation of the liquid effluent comprising predominantly mono or poly-oxygenated compounds obtained at the end of the conversion step e), into an effluent predominantly composed of alcohols and polyols, a fraction containing the heterogeneous catalysts, a fraction comprising unconverted lignin and a fraction comprising the homogeneous catalyst (s). In the present invention, the term "homogeneous catalyst" means a catalyst that is soluble in the operating conditions of the reaction. By heterogeneous catalyst is meant a catalyst that is not soluble in the reaction operating conditions. An advantage of the present invention is to allow both the production of hydrocarbons and poly-oxygenated compounds from biomass by a succession of steps, and preferably a succession of conversion steps using a heterogeneous catalyst common. Another advantage of the present invention is that it allows the production of hydrocarbon products obtained at the end of the second separation step d) which can be directly used as intermediates or reagents for the petrochemical industry and the chemical industry. Another advantage of the present invention is to allow the production of products obtained at the end of the third stage f) of separation which can be used as intermediates or reagents for the petrochemical industry and the chemical industry.
[0007] DETAILED DESCRIPTION OF THE INVENTION Charcie The lignocellulosic raw material may consist of wood or vegetable waste. Other non-limiting examples of lignocellulosic biomass material are farm residues (straw, grass, stems, kernels, shells, etc.), logging residues (thinning products, bark, sawdust, chips). , falls, ...), logging products, dedicated crops (short-rotation coppice), residues from the agri-food industry (residues from the cotton industry, bamboo, sisal, banana, maize , panicum virgatum, alfalfa, coconut, bagasse, sorghum, ...), household organic waste, waste from wood processing facilities, used timber for construction, paper, recycled or not. Biomass contains a large and variable amount of water; the constitutive elements of the latter are expressed as a percentage of dry matter. Cellulose (C61-11005), a semi-crystalline linear homopolymer of cellobiose, itself a dimer of glucose, accounts for most of the composition of lignocellulosic biomass.
[0008] The cellulose content of the filler used in the process according to the invention is greater than 25% by weight of the total dry matter, preferably greater than 30% by weight of the total dry matter. The other carbohydrate used in the composition of lignocellulosic biomass is hemicellulose. The dry mass of hemicellulose in the filler used in the process according to the invention is less than 50% by weight of the total solids, preferably less than 45% by weight of the total solids and, very preferably less than 40% by weight of the total dry matter. Unlike cellulose, this polymer consists mainly of pentose monomers (sugars with five carbon atoms) and hexoses (sugars with six carbon atoms). Hemicellulose is a heteropolymer with a lower degree of polymerization than cellulose.
[0009] Lignin is an amorphous macromolecule present in lignocellulosic compounds in varying proportions depending on the origin of the material. The dry mass of lignin in the lignocellulosic biomass is less than 50% by weight of the total dry matter, preferably less than 45% by weight of the total dry matter and, very preferably, less than 40% by weight of the total dry matter. Its function is mechanical strengthening, hydrophobization and plant support. This macromolecule rich in phenolic units can be described as resulting from the combination of three monomeric units of propylmethoxy-phenol type. Its molar mass varies from 5,000 g / mol to 10,000 g / mol for hardwoods and reaches 20,000 g / mol for softwoods. The lignocellulosic charge is often described by the quantity of these different constitutive elements. Cellulose Hemicellulose Lignin Hardwood 40-55% 24-40% 18-25% Softwood 45-50% 25-35% 25-35% Straws 30-43% 22-35% 15-23% Herbs 25-40% 35 -50% 10-30% The lignocellulosic biomass also has a fraction of products extractable with water or with an organic solvent such as acetone, 2-methylfuran or y-valerolactone, as well as ashes. The lignocellulosic biomass feedstock is used in the process according to the invention in its raw form, that is to say in its entirety of these three constituents cellulose, hemicellulose and lignin. The raw biomass is generally in the form of fibrous residues or powder. In general, it is crushed or shredded to allow its transport. In the case where the percentages indicated in the description of the invention are given in dry matter basis of the effluent or of the fraction considered, the percentage weight of dry matter, the mass ratio of the effluent or the fraction considered obtained after drying at 105 ° C for 24 hours on the initial mass of said effluent or said fraction considered.
[0010] In the case where the percentages indicated in the description of the invention are given in solvent-free material base of the effluent or of the fraction considered, the percentage weight of material without solvent, the mass ratio of the effluent or of the fraction considered obtained after drying for 24 hours at a temperature greater than 5 ° C. at the boiling point of the solvent or solvent mixture considered on the initial mass of the said effluent or of the fraction in question. a) The first conversion step In accordance with the invention, the process comprises a first step of converting the lignocellulosic biomass into at least one cellulosic fraction comprising a cellulose content of at least 60% by weight relative to the dry matter of said cellulosic fraction and at least one liquid effluent, said conversion step operating in the presence of a mass or supported heterogeneous catalyst, of molecular hydrogen and / or a solvent, at a temperature of between 150 and 300 ° C and at a pressure of between 0.5 and 20 MPa. The objective of the first conversion step a) is to transform the lignocellulosic biomass in the presence of a mass or supported heterogeneous catalyst, of molecular hydrogen and / or of a solvent into a cellulosic fraction and a liquid effluent, recoverable separately. in later stages. For example, the cellulosic fraction containing predominantly cellulose has an improved reactivity with respect to the feedstock. The liquid effluent contains degradation products of the lignin fraction which is converted in said first conversion step, for example, alcohols, ketones, aldehydes, ethers, polyoxygen compounds, monosaccharides, polysaccharides, compounds aromatics including alkylphenols, alkylmethoxyphenols, alkylbenzenediols, alkylmethoxybenzenes, alkylanilines, alkylaromatic and alkylcyclohexanones, aromatic compounds such as naphthenes, linear or cyclic alkanes, terpenes or terpenoids and lignin oligomers. The cellulosic fraction and the liquid effluent from the first conversion step are separated by any technique known to those skilled in the art.
[0011] According to the invention, the cellulosic fraction obtained at the end of the first conversion step comprises a cellulose content of at least 60% by weight relative to the dry matter of said cellulosic fraction, preferably at least 70% by weight. weight, and preferably at least 80% by weight. Said cellulosic fraction also advantageously contains less than 20% by weight of lignin relative to the dry matter of said cellulosic fraction, preferably less than 15% by weight, and preferably less than 10% by weight and less than 20% by weight of hemicellulose. relative to the dry matter of said cellulosic fraction, preferably less than 15% by weight, and preferably less than 10% by weight. The heterogeneous catalyst also remains in the cellulosic fraction. Preferably, the liquid effluent obtained at the end of the first conversion step comprises more than 50% by weight relative to the dry matter of said liquid effluent of lignin degradation products in the form, for example, of oligomers of lignins, alcohols, polyols, ethers, organic acids, aromatic compounds and phenolic compounds, preferably more than 70% by weight, and more preferably more than 85% by weight. Preferably, said liquid effluent also comprises less than 50% by weight relative to the dry matter of said liquid effluent of sugars in the form of hexoses and pentoses, preferably less than 30% by weight, and preferably less than 15% by weight. of sugars. Said liquid effluent also contains the solvent used in said conversion step a).
[0012] This liquid effluent freed of the solvent is called "bio-oil" thereafter. According to the invention, the first conversion step a) operates in the presence of a mass or supported heterogeneous catalyst. Preferably, said catalyst comprises at least one metal chosen from metals of the group 10 alone or in admixture with a metal chosen from metals of groups 6 to 14 of the periodic table, and optionally a support chosen from the oxides of the elements chosen from aluminum, titanium, silicon, zirconium, cerium, lanthanum and niobium, alone or as a mixture and mixed oxides chosen from zinc, copper and cobalt aluminates, said oxides being dopable or non-doping by at least one metal compound chosen from tungsten, tin, molybdenum and antimony, taken alone or as a mixture, the perovskites of formula ABO3 in which A is chosen from the elements Mg, Ca, Sr, Ba and La and B is selected from Fe, Mn, Ti and Zr elements, crystallized aluminosilicates or not, aluminophosphates and amorphous or crystallized carbon compounds. Said metal chosen from the metals of group 10 of the periodic table is preferably chosen from the following metals: Ni, Pd, Pt, alone or as a mixture with the metals of groups 6 to 14 of the periodic table chosen from the following metals: Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, and Hg, on the one hand, and among : Ge, Sn and Pb on the other hand. Preferably, said group 10 metal is selected from metals Ni, Pt, alone or in admixture with the metals of groups 6 to 14 of the periodic table selected from the following metals: Mo, W, Pt, Sn, Co.
[0013] According to a very preferred embodiment, said group 10 metal is nickel, alone or in admixture with metals of groups 6 to 14 of the periodic table selected from the following metals: Mo, W, Co. Preferably, the content Group 10 metal on said heterogeneous catalyst is between 0.1 and 30% by weight based on the total mass of said heterogeneous catalyst. In the case where said metal of group 10 is used in admixture with the metals of groups 6 to 14 of the periodic table, the content of groups 6 to 14 on said heterogeneous catalyst is between 5 and 15% by weight relative to the total mass of said heterogeneous catalyst. In the case where the heterogeneous catalyst used is a mass catalyst, the preferred heterogeneous catalyst is a Raney nickel catalyst.
[0014] In the case where the heterogeneous catalyst used is a supported catalyst, the metal (s) of the supported heterogeneous catalyst (s) are advantageously deposited on a support chosen from the oxides of the elements chosen from aluminum, titanium, silicon and zirconium. cerium, lanthanum and niobium, and mixed oxides chosen from zinc, copper and cobalt aluminates, said oxides possibly being doped with or not by at least one metal compound chosen from tungsten, tin and molybdenum and antimony, taken alone or in mixture, the perovskites of formula ABO3 in which A is selected from the elements Mg, Ca, Sr, Ba and La, and B is selected from Fe, Mn, Ti and Zr elements, aluminosilicates crystallized or not, aluminophosphates and amorphous or crystallized carbon compounds. Preferably, the amorphous or crystallized carbon compounds are chosen from active carbons, carbon blacks, carbon nanotubes, mesostructured carbons and carbon fibers. In the case where said support is selected from doped oxides of the elements selected from aluminum, titanium, silicon, zirconium, cerium, lanthanum, niobium, the metal element is advantageously added to said support. Preferably, the content of metal element chosen from tungsten, tin, antimony and molybdenum alone or as a mixture is advantageously between 0.1 and 30% by weight and preferably between 1 and 20% by weight relative to to the total mass of said catalyst. The support can be used shaped or in powder form.
[0015] Said support is preferably hydrothermally stable, ie stable under conditions combining water and temperature. Thus, the support may undergo a treatment step to improve its stability in the hydrothermal conditions of the reaction. For example, surface passivation, carbon film deposition, oxide deposition may be mentioned.
[0016] The deposition of the metal selected from the group 10 alone or in admixture with a metal selected from the metals of groups 6 to 14 of the periodic table on said carrier of the heterogeneous catalyst supported according to the invention generally involves a precursor of the metal or metals. For example, they may be metal organic complexes, metal salts such as metal chlorides, metal nitrates. The introduction of the metal or metals is carried out by any technique known to those skilled in the art such as ion exchange, dry impregnation, impregnation by excess, vapor deposition, etc.
[0017] The step of introducing the metal or metals may advantageously be followed by a heat treatment step. The heat treatment is advantageously carried out between 300 and 700 ° C. under an oxygen or air atmosphere. The heat treatment step may be followed by a temperature reduction treatment. The reducing heat treatment is advantageously carried out at a temperature of between 200 and 600 ° C. under a flow or atmosphere of hydrofoil. Preferably, said heterogeneous catalyst also undergoes an in situ reduction step, that is to say in the reactor where the reaction takes place, before the introduction of the reaction charge. Said reduction step may also advantageously be carried out ex-situ. The size of the metal particles of the mass heterogeneous catalyst used in the process according to the invention is preferably less than 100 nm. The supported heterogeneous catalyst used in the present invention may be in the form of extrudates, beads or powders, or dispersed in a solvent. Preferably, it is in powder form. The shaping can be carried out before or after the introduction of the metal. The mass or supported heterogeneous catalysts used in the present invention are characterized by techniques known to those skilled in the art. For example, to characterize the texture of the catalyst, the adsorption-desorption of nitrogen at 77K will be mentioned. According to the invention, the first conversion step a) operates at a temperature of between 50 and 300 ° C., preferably between 100 and 300 ° C. and preferably between 150 and 250 ° C. and at a pressure between 0.5 and 20 MPa, preferably between 1 and 10 MPa. Preferably, the first conversion step a) operates for a time varying between 1 minute and 24 hours, preferably between 1 and 16 hours, very preferably between 2 and 12 hours. Preferably, the filler / catalyst ratio, the filler being expressed in dry basis, is less than 15, preferably less than 10, and most preferably less than 5.
[0018] According to the invention, the first conversion step a) operates in the presence of molecular hydrogen and / or a solvent. The solvents are advantageously chosen from hydrogen donor solvents and non-hydrogen donor organic solvents. In the case where the solvent is chosen from hydrogen-donor solvents, the hydrogen donor solvents, known to those skilled in the art, are advantageously chosen from secondary alcohols preferably chosen from linear or cyclic secondary alcohols. comprising 3 to 6 carbon atoms and very preferably isopropanol, 2-butanol, 2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol, cyclohexanol, cyclohexanediols.
[0019] Said hydrogen donor solvent is advantageously used in step a) alone or in admixture with water. In the case where the solvent is chosen from organic solvents which are not hydrogen donors, said non-hydrogen donor organic solvent is preferably chosen from alcohols chosen from methanol, ethanol, isopropanol and isobutanol. butanol, ethers selected from tetrahydrofuran, 2-methyltetrahydrofuran and diethyl ether, and organic acids selected from formic acid and acetic acid and polyols, preferably ethylene glycol. Preferably, the solvents used in the process according to the invention are advantageously chosen from hydrogen donor solvents. In the case where said conversion step a) operates in the presence of a solvent alone, said solvent is a hydrogen donor solvent. In this case, said step a) operates under an inert atmosphere and preferably under nitrogen.
[0020] In the case where said conversion step a) operates in the presence of a solvent and of molecular hydrogen, said solvent may advantageously be either a hydrogen donor solvent or a non-hydrogen donor organic solvent.
[0021] The first conversion step a) carried out according to the method of the invention can be implemented according to different embodiments. The compositions of the cellulosic fraction and of the liquid effluent differ according to the choice of the operating conditions.
[0022] In a first embodiment, said conversion step a) operates in the presence of a mass or supported heterogeneous catalyst, and of a hydrogen donor solvent, alone or as a mixture with water. In this case, said conversion step a) preferably operates under an inert atmosphere, and preferably under a nitrogen atmosphere. In this case, the lignocellulosic biomass feedstock is preferably brought into contact in a closed reactor with a mass or supported heterogeneous catalyst, in powder or dispersed form, under an atmosphere, preferably with nitrogen, with a mixture of water and a hydrogen donor solvent selected, for example, from isopropanol or formic acid. The mass ratio donor solvent / water is advantageously greater than 0.5, preferably greater than 0.75, and very preferably greater than 1. The mass ratio filler / catalyst dry base is advantageously less than 15, preferably less than 10. , and very preferably less than 5.
[0023] In a second embodiment, said conversion step a) operates in the presence of a mass or supported heterogeneous catalyst and of molecular hydrogen. In this case, said conversion step a) can advantageously operate in the presence of a non-hydrogen donor organic solvent, alone or in admixture with water. In this case, the charge is preferably brought into contact with a mixture of water and a non-hydrogen donor organic solvent as defined above. The weight ratio organic solvent / water is advantageously greater than 0.3, preferably greater than 0.5, and very preferably greater than 0.7. The assembly is placed in a closed reactor for a period of between 2 and 12 hours with a heterogeneous catalyst mass or supported, powdered or dispersed in said solvent, under a hydrogen atmosphere.
[0024] After transforming the feed into said first conversion step a), the liquid effluent is sent to the first separation step and the cellulosic fraction is sent to a third conversion step. 13) The first separation step In accordance with the invention, the process comprises a first separation step b) of at least a part of the solvent of the liquid effluent obtained at the end of step a) of conversion for produce an effluent comprising predominantly said solvent and an effluent comprising predominantly a bio-oil. The objective of the first separation step b) is to separate the liquid effluent from the first conversion step a) into an effluent containing predominantly said solvent and a second effluent containing predominantly "bio-oil".
[0025] The separation step is advantageously carried out by means known to those skilled in the art such as, for example, liquid-liquid separation, distillation, etc. Said effluent comprising for the most part a bio-oil advantageously comprises more than 85% by weight of monoaromatic compounds, polyaromatic compounds, linear or cyclic alkanes and alkenes, preferably more than 90% by weight, and very preferably more than 95% by weight. , with respect to the total mass of said effluent. The percentage of oxygen contained in said effluent comprising predominantly a bio-oil is advantageously between 5 and 25% by weight relative to the total mass of said effluent. Said effluent containing predominantly said solvent advantageously comprises less than 50% by weight of water, preferably less than 40% by weight and even more preferably less than 30% by weight relative to the total weight of effluent and more than 50% by weight of saturated compounds or unsaturated compounds comprising primary, secondary alcohols, aldehydes, ketones, polyols, carboxylic acids, esters, linear or cyclic ethers, preferably more than 60% by weight and even more preferably more than 70% by weight, relative to to the total mass of said effluent.
[0026] C) The second conversion step In accordance with the invention, the process comprises a second effluent conversion stage comprising for the most part a bio-oil resulting from the separation step b) into a liquid effluent comprising mainly hydrocarbons, said conversion step operating in the presence of hydrogen and a catalyst, at a temperature above 200 ° C, at a pressure of between 2 and 25 MPa and at a space velocity of between 0.1 and 20 h -1, preferably at a temperature between 350 and 450 ° C, at a pressure between 2 and 12 MPa and at a space velocity of between 0.2 and 10h-1. Since the bio-oil still contains a high oxygen content, it is not a pure hydrocarbon and therefore requires further processing to convert it to a fuel-grade hydrocarbon product for road, air transport. or maritime or petrochemical quality before separation. The objective of the second conversion step c) is to transform the bio-oil effluent into a hydrocarbon effluent whose compounds can serve as fuel formulations, of the gasoline, kerosene or middle distillate type, or to applications for as chemical intermediates after the second step b) of separation. The second conversion step c) is preferably a step of hydrotreating and / or hydrocracking the bio-oil to obtain a hydrocarbon effluent.
[0027] Preferably, the second conversion step is a hydrocracking step, optionally preceded by a hydrotreating step. According to a preferred embodiment, said second conversion step c) is a mild hydrocracking. In this case, said step c) gives rise to a net conversion of products whose boiling point is below 375 ° C. Said second mild hydrocracking stage advantageously operates at a pressure of between 2 and 12 MPa, preferably between 2 and 10 MPa, preferably between 3 and 9 MPa and more preferably between 4 and 7 MPa, at a temperature of between between 350 and 450 ° C, at a space velocity of between 0.2 and 5 hr-1 and with a total amount of hydrogen mixed with the feedstock (including the chemical consumption and the amount recycled) such as the ratio by volume hydrogen / hydrocarbon is between 100 and 2000 Nm / m, preferably between 200 and 1500 Nm / m.
[0028] According to a very preferred embodiment, said second conversion step c) is a hydrotreatment step of the effluent comprising predominantly a bio-oil from the first step b) of separation followed by a mild hydrocracking 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 step is carried out in the presence of a conventional hydrorefining catalyst known to those skilled in the art. The one or more hydrotreatment and / or hydrocracking steps can 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. Said steps can be carried out industrially in one or more reactors, with one or more catalytic beds. The hydrocracking catalysts used in the second conversion step are all of the bifunctional type which combine an acid function and a hydro-dehydrogenating function. The acid function is provided by substrates which have surface areas generally of between 150 and 800 m 2 / g and a surface acidity, such as halogenated aluminas (in particular chlorinated or fluorinated aluminas), aluminas, zeolites and preferably zeolites Y FAU type and amorphous silica-aluminas, or combinations thereof. The hydro-dehydrogenating function is provided by one or more metals from Groups 8 to 10 of the Periodic Table of Elements, or by a combination of at least one Group 6 metal and at least one Group 8 to 10 metal. The catalyst may comprise metals of groups 8 to 10, for example nickel and / or cobalt, most often in combination with at least one Group 6 metal, molybdenum and / or tungsten, for example. It is possible to use, for example, a catalyst comprising between 0.5 and 10% by weight of nickel (expressed in terms of nickel oxide NiO) and between 1 and 30% by weight of molybdenum, preferably between 5 and 25% by weight. of molybdenum (expressed in terms of MoO3 molybdenum oxide) on an amorphous mineral substrate. The total content of the Group 6 and Groups 8 to 10 metal oxide catalyst is generally from 5 to 40% by weight, preferably from 7 to 30% by weight. In the case where the catalyst comprises at least one group 6 metal associated with at least one non-noble metal of groups 8 to 10, the catalyst is preferably a sulphide catalyst. According to another preferred embodiment in which the objective is the production of fuel base fractions that can be incorporated into the gasoline, gas oil and kerosene pools, said conversion step c) is advantageously carried out according to the sequence and the operating conditions described in FIG. the application FR2987842. According to another preferred embodiment in which the objective is the production of aromatic fractions that can be incorporated in the aromatic complex, said conversion step c) is advantageously carried out according to the sequence and the operating conditions described in application FR2991335. The liquid effluent comprising mainly hydrocarbons obtained at the end of the conversion step c) is a liquid hydrocarbon effluent at least partially and preferably completely deoxygenated.
[0029] Said hydrocarbon liquid effluent 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 boiling point of said hydrocarbon liquid effluent, measured by simulated distillation by gas chromatography, according to ASTM method D2887 for example, is less than about 500 ° C, preferably inferior to 450 ° C. The overall yield of liquid effluent comprising mainly hydrocarbons obtained at the end of step c) of conversion relative to the starting dry biomass is advantageously between 10 and 48% by weight and preferably between 10 and 40% by weight. The hydrogen consumption during this step is preferably less than 2% by weight relative to the effluent mass comprising mainly the bio-oil introduced. d) The second separation step According to the invention, said liquid effluent comprising mainly hydrocarbons from the second conversion step c) undergoes a separation step to obtain at least fuel base sections that can be incorporated into the gasoline, diesel fuel pools, kerosene and / or aromatic cuts that can be incorporated into the aromatic complex. A section comprising light compounds comprising 1 to 4 carbon atoms and a section comprising water is also advantageously separated during said second separation step. The separation step is advantageously carried out by means known to those skilled in the art such as, for example, liquid-liquid separation, distillation, etc.
[0030] C ') The first step of optional regeneration The method according to the invention may also advantageously comprise an optional step of regeneration of said effluent containing mainly said solvent from the first step b) of separation. Said step c ') produces a regenerated effluent. The objective of the first regeneration step of the effluent containing predominantly said solvent is to regenerate this effluent and then recycle it to serve as a solvent in the first step a) of conversion.
[0031] The regeneration step of the effluent containing predominantly said solvent operates in the presence of a heterogeneous catalyst. The operating conditions and the catalyst, known to those skilled in the art, make it possible to obtain an outlet effluent of the first regeneration stage composed mainly of said solvent, water and alcohols, that is to say containing more than 50% by weight of alcohols, preferably more than 60% by weight of alcohols, more preferably more than 70% by weight of alcohols. The concentration of the medium can be adjusted by dilution, that is to say by addition of solvent, the solvent preferably being water, or by evaporation, that is to say by removing solvent from the reaction medium to increase the concentration of reagents. Preferably, the medium is not diluted and the medium is used as it is after the first separation step. The regeneration step of the effluent containing predominantly said solvent is advantageously carried out at temperatures between 40 and 300 ° C, preferably between 60 and 250 ° C, and at a pressure between 0.1 and 20 MPa, preferably between 0.5 and 15 MPa. Said step c ') can be performed according to different embodiments. Thus, the reaction can be carried out batchwise or continuously, for example in a fixed bed or in a slurry reactor. It can operate in closed reactor or semi-open reactor. In a preferred manner, the reaction is carried out continuously, for example in a continuous stirred tank.
[0032] Stage c ') of regeneration of the effluent containing predominantly said solvent is advantageously carried out in the presence of pure hydrogen or in mixture. The regeneration step c ') is advantageously carried out in the presence of a catalyst, preferably a heterogeneous catalyst, chosen by those skilled in the art, for hydrogenating the effluent containing predominantly said solvent. Preferably, the catalyst is composed of a metal phase mass or dispersed on a support. The metal phase is preferably chosen from Pt, Ni, Pd, Ru, Rh, Co, Cu, Ir, Sn alone or as a mixture. In a preferred manner, the mass heterogeneous catalyst is, for example, Raney nickel. If the catalyst comprises a metal dispersed on a support, the support is preferably chosen from oxides alone or in a mixture chosen from aluminum, titanium, silicon, zirconium, cerium, niobium and carbon supports. The metal content is between 0.1 and 100% based on the weight of the catalyst and preferably between 0.5 and 100% by weight. The catalyst is prepared according to any technique known to those skilled in the art, such as, for example, for metal catalysts dispersed on an ion exchange support, impregnation, vapor deposition followed by a heat treatment step. The catalyst introduced into the reactor can undergo a reducing heat treatment step before the introduction of the reaction charge. The reducing heat treatment is carried out at a temperature of between 50 and 500 ° C. under a flow or atmosphere of hydrogen. If the reaction is carried out in a closed reactor, the catalyst is introduced into the reactor in an amount corresponding to a mass ratio of filler / catalyst mass of between 0.1 and 1000, preferably between 0.5 and 500. a continuous process is chosen, the hourly mass velocity (mass flow rate of dry base load per mass of catalyst) is between 0.01 and 50 h -1, preferably between 0.05 and 30 h -1. On leaving the hydrogenation reaction, the liquid fraction obtained contains water and saturated compounds. It is separated from the gaseous fraction containing hydrogen. Preferably, the gas fraction contains predominantly hydrogen. The H2 / solvent molar ratio is between 1 and 100.
[0033] The first regeneration step c ') thus makes it possible to produce a regenerated effluent comprising less than 50% by weight of water, preferably less than 40% by weight and even more preferably less than 30% by weight relative to the total mass of said effluent and more than 50% by weight of saturated compounds comprising primary and secondary alcohols, preferably more than 60% by weight and even more preferably more than 70% by weight relative to the total mass of said effluent. The regenerated effluent can advantageously be recycled in the first step a) of conversion of the lignocellulosic biomass. e) The third conversion step In accordance with the invention, the process comprises a third step e) of converting the cellulosic fraction resulting from conversion step a) into a liquid effluent comprising mainly mono or poly-oxygenated compounds, wherein said cellulosic fraction is simultaneously contacted with a combination of one or more homogeneous catalysts and one or more heterogeneous catalysts in the same reaction chamber in the presence of at least one solvent, said solvent being water alone or mixed with at least one other solvent, under a reducing atmosphere, and at a temperature of between 50 and 300 ° C, and at a pressure of between 0.5 and 23 MPa. The objective of the third step e) of conversion is to transform in an aqueous medium and in the presence of hydrogen alone or in mixture and of a catalytic system comprising one or more homogeneous catalysts and one or more heterogeneous catalysts, the cellulosic fraction resulting from of step a) of conversion into a liquid effluent comprising predominantly mono or poly-oxygenated compounds and in particular mono or poly-oxygenated compounds containing between 1 and 6 carbon atoms, said effluent also comprising said homogeneous catalyst (s) and said one or more heterogeneous catalysts. The third conversion step e) makes it possible to produce a liquid effluent comprising mainly mono or poly-oxygenated compounds. Said effluent advantageously comprises at least 40% by weight of polyols, preferably at least 45% by weight, and preferably at least 50% by weight of polyols relative to the total mass of said solvent-free effluent. Said effluent advantageously also comprises less than 25% by weight of monoalcohols preferably comprising from 1 to 6 carbon atoms, preferably less than 20% by weight, and preferably less than 15% by weight of sugars relative to the total mass of said effluent. without a solvent and less than 5% by weight of linear or cyclic ethers, preferably less than 3% by weight, and even more preferably less than 2% by weight, relative to the total mass of said solvent-free effluent. Said effluent advantageously also comprises less than 15% of insoluble products such as lignin and coke, preferably less than 10% by weight, and preferably less than 5% by weight relative to the total mass of said solvent-free effluent. Said liquid effluent comprising predominantly mono or poly-oxygenated compounds obtained at the end of said third conversion step e) also contains the heterogeneous catalyst and the homogeneous catalyst or catalysts.
[0034] According to the invention the third conversion step e) operates in the presence of at least one solvent, said solvent being water alone or in admixture with at least one other solvent.
[0035] Preferably, the third conversion step e) operates in the presence of water in admixture with at least one alcohol or at least one organic solvent, under sub- or supercritical conditions. The alcohols are advantageously chosen from methanol, ethanol and propanols.
[0036] The organic solvents may advantageously be chosen from tetrahydrofuran, ethyl acetate and rvererolactone. In the case where the third conversion stage e) operates in the presence of water in a mixture with at least one other solvent, the solvent mixture comprises a mass content of water greater than 5% by weight and preferably greater than 30% by weight. and very preferably greater than 50% by weight relative to the total mass of said mixture. Very preferably, the third conversion step e) operates only in the presence of water.
[0037] Preferably, the third conversion step e) operates in the presence of at least one solvent with the exception of the solvents chosen from ionic liquids. According to the invention, the third conversion step e) is carried out under a reducing atmosphere, preferably under a hydrogen atmosphere. Hydrogen can be used pure or as a mixture. Preferably, the third conversion step e) operates at a temperature of between 50 and 300 ° C. and preferably between 100 and 250 ° C., and at a pressure of between 0.5 and 20 MPa and, preferably, between 1 and 50 ° C. and 10 MPa.
[0038] Generally the third step e) conversion can be performed according to different embodiments. Thus, the third conversion step e) may advantageously be carried out batchwise or continuously, for example in a fixed bed. It can be carried out in a closed reaction chamber or in a semi-open reactor.
[0039] The cellulosic fraction resulting from the conversion step a) constituting the feedstock of said conversion step e) is introduced into said step e) in an amount corresponding to a weight ratio solvent / effluent dry base of between 1 and 1000. preferably between 1 and 500 and more preferably between 5 and 100.
[0040] If the third conversion stage e) is carried out in a closed reactor, said homogeneous catalysts are advantageously introduced into the reaction chamber in an amount corresponding to a mass ratio dry filler (cellulosic fraction from step a)) homogeneous catalysts of between 1.5 and 1000, preferably between 5 and 1000, and preferably between 10 and 500. The heterogeneous catalyst or catalysts are introduced into the reaction chamber in an amount corresponding to a mass ratio. dry-base feedstock (cellulosic fraction resulting from step a)) / heterogeneous catalyst (s) of between 1 and 1000, preferably between 1 and 500, preferably between 1 and 100, preferably between 1 and 50, and more preferably between 1 and 25. The heterogeneous catalyst or catalysts introduced into the reactor may undergo a reducing heat treatment step before the introduction of the reactio charge. nal. The reducing heat treatment is preferably carried out at a temperature of between 150 and 600 ° C. under a flow or atmosphere of hydrofoil. In the case where said third conversion step e) is carried out continuously, the hourly mass velocity (mass flow rate of dry base load per mass of catalyst) is between 0.01 and 5 h -1, preferably between 0, 02 and 2 h-1. The third conversion step e) performed according to the method of the invention can be implemented according to different embodiments. The composition of the resulting liquid effluent comprising predominantly mono or poly-oxygenated compounds differs according to the choice of operating conditions. According to the invention, the third conversion step e) operates in the presence of a combination of one or more homogeneous catalysts and one or more heterogeneous catalysts. Preferably, the heterogeneous catalyst or catalysts used in said step e) are identical to those used in the first conversion step a). Preferably, said heterogeneous catalyst or catalysts are chosen from heterogeneous supported or mass catalysts. Preferably, said heterogeneous catalyst or catalysts comprise at least one metal chosen from group 10 metals alone or in admixture with a metal chosen from metals of groups 6 to 14 of the periodic table, and optionally a support chosen from oxides of elements chosen from aluminum, titanium, silicon, zirconium, cerium, lanthanum and niobium alone or as a mixture, and mixed oxides chosen from zinc, copper and cobalt aluminates, said oxides being doped or not with at least one metal compound chosen from tungsten, tin, molybdenum and antimony, taken alone or as a mixture, the perovskites of formula ABO3 in which A is chosen from the elements Mg, Ca, Sr, Ba and La and B are selected from Fe, Mn, Ti and Zr elements, crystallized aluminosilicates or not, aluminophosphates and amorphous or crystallized carbon compounds. Said metal chosen from the metals of group 10 of the periodic table is preferably chosen from the following metals: Ni, Pd, Pt, alone or as a mixture with the metals of groups 6 to 14 of the periodic table chosen from the following metals: Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, and Hg, on the one hand, and among : Ge, Sn and Pb on the other hand. Preferably, said group 10 metal is selected from metals Ni, Pt, alone or in admixture with the metals of groups 6 to 14 of the periodic table selected from the following metals: Mo, W, Pt, Sn, Co.
[0041] According to a very preferred embodiment, said group 10 metal is nickel, alone or in admixture with metals of groups 6 to 14 of the periodic table selected from the following metals: Mo, W, Co. Preferably, the content metal on said one or more heterogeneous catalysts is advantageously between 0.1 and 30% by weight, and preferably between 5 and 15% by weight relative to the total mass of said heterogeneous catalyst.
[0042] In the case where the one or more heterogeneous catalysts used are chosen from bulk catalysts, the preferred heterogeneous catalyst is a Raney nickel type catalyst.
[0043] In the case where the heterogeneous catalyst used is a supported catalyst, the metal (s) of the supported heterogeneous catalyst (s) are advantageously deposited on a support chosen from the oxides of the elements chosen from aluminum, titanium, silicon and zirconium. cerium, lanthanum and niobium alone or as a mixture, and mixed oxides chosen from zinc, copper and cobalt aluminates, said oxides possibly being doped with or not by at least one metal compound chosen from among tungsten, tin, molybdenum and antimony, taken alone or in mixture, the perovskites of formula ABO3 in which A is selected from the elements Mg, Ca, Sr, Ba and La and B is selected from Fe, Mn, Ti and Zr, crystallized aluminosilicates or not, aluminophosphates and amorphous or crystallized carbon compounds. Preferably, the amorphous or crystallized carbon compounds are chosen from active carbons, carbon blacks, carbon nanotubes, mesostructured carbons and carbon fibers.
[0044] In the case where said support is selected from the oxides of elements selected from aluminum, titanium, silicon, zirconium, cerium, lanthanum, niobium, doped or not, a metal element preferably selected from tungsten , tin, antimony and molybdenum alone or in mixture is advantageously added to said support. Preferably, the content of metal element chosen from tungsten, tin, antimony and molybdenum alone or as a mixture is advantageously between 0.1 and 30% by weight and preferably between 1 and 20% by weight relative to to the total mass of said catalyst. The support can be used shaped or in powder form. Preferably, it is in powder form.
[0045] Said support is preferably hydrothermally stable, ie stable under conditions combining water and temperature. Thus, the support may undergo a treatment step to improve its stability in the hydrothermal conditions of the reaction. For example, surface passivation, carbon film deposition, oxide deposition may be mentioned.
[0046] Preferably, the mass or supported heterogeneous catalyst used in the third conversion step e) is identical to that used in the first conversion step a). Preferably, said catalyst used is the Raney nickel type bulk catalyst. Preferably, the homogeneous catalyst or catalysts used in said step e) are chosen from hydrated or non-hydrated metal salts, the inorganic compounds comprising an element chosen from among the metals of group 6 of the periodic table and the organic or inorganic acids of Bronsted, taken alone or mixed. In a first variant, the at least one homogeneous catalyst is chosen from hydrated metal salts or not. In this case, said metal salts have a general formula EXn.n'H20 in which E is an element chosen from metals of groups 3 to 16 or the group of lanthanides of the periodic table, n is an integer between 1 and And n 'is an integer from 0 to 20 and X is at least one anion selected from halides, nitrates, carboxylates, oxalates, halocarboxylates, acetylacetonates, alkoxides, phenolates, substituted or unsubstituted, sulphates, alkyl sulphates, phosphates, alkyl phosphates, halosulfonates, alkyl sulphonates, perhaloalkyl sulphonates, bis (perhaloalkylsulphonyl) amides, arenesulphonates, which may or may not be substituted by halogen or haloalkyl groups, said X anions being identical or different in the case where n is greater than 1. Preferably, said element E can be chosen from groups 3 to 16 or from the group lanthanide pe of the periodic table, preferably selected from the following elements: Al, Sc, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, La, Hf, Ta, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, Ac, Rf, Db, Bh, Hs, Mt, Ds, Rg, Uub, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu. Preferably, said element E is chosen from the elements Mn, Fe, Co, Ni, Cu, Zn, Al, Ga, In, Sn, La, Ce, Er and Yb. In a very preferred manner, said element E is chosen from the following elements: Fe, Zn, Al, Sn, La and Ce.
[0047] Preferably, in the composition of the metal salt, the element E chosen from the elements mentioned is associated with one or more anions X, which may be identical or different.
[0048] Preferably, the anion X is at least one anion selected from halides, oxalates, alkylsulfonates, perhaloalkylsulfonates, bis (perhaloalkylsulfonyl) amides. Preferably, the halide is fluoride, chloride, bromide and iodide.
[0049] Preferably, the alkylsulfonate is mesylate and tosylate. Preferably, the perhaloalkylsulfonate is triflate. Preferably, the bis (perhaloalkylsulfonyl) amide is bis (triflimide). Very preferably, in the case where n is equal to 3, the anion X is a chloride.
[0050] Said preferred homogeneous catalyst or catalysts comprise a hydrated metal salt or not of general formula EXn.n'H20, n and n 'having the aforementioned meanings, in which E is a member chosen from the elements Mn, Fe, Co, Ni, Cu , Zn, Al, Sn, La and Ce and X is at least one anion selected from halides, alkylsulfonates, perhaloalkylsulfonates, bis (perhaloalkylsulfonyl) amides, said anions X may be identical or different in the case where n is greater than to 1. Said or even more preferred homogeneous catalysts comprise a hydrated metal salt or not of general formula EXn.n'H20, n and n 'having the aforementioned meanings, wherein E is a member selected from metals Fe, Zn, Al, Sn, La and Ce and X is at least one anion selected from fluoride, chloride, bromide, iodide, mesylate, tosylate, triflate and bis (triflimide), said anions X may be identical or Diff erents in the case where n is greater than 1.
[0051] In the case where several homogeneous catalysts are used, said homogeneous catalysts are advantageously chosen from hydrated or non-hydrated metal salts of general formula EXn.n'H 2 O, n and n 'having the abovementioned meanings, in which E is a member chosen from metals Fe, Zn, Al, Sn, La and Ce and X is at least one anion selected from fluoride, chloride, bromide, iodide, mesylate, tosylate, triflate and bis (triflimide), said anions X may be identical or different in the case where n is greater than 1 and said homogeneous catalysts may be identical or different.
[0052] According to this variant, the cellulosic fraction resulting from the conversion step a) is brought into contact in a closed reactor for a period of between 10 minutes to 12 hours with the heterogeneous catalyst resulting from the first conversion step and at least one catalyst. homogeneous, in a pure hydrogen atmosphere or in a mixture. The total or partial hydrogen pressure is preferably between 0.5 and 20 MPa, preferably between 1 and 10 MPa. The mixture is brought to temperature between 50 and 300 ° C., preferably between 100 and 250 ° C. The solvent / cellulose fraction ratio is between 1 and 1000, preferably between 1 and 500 and preferably between 5 and 100.
[0053] The homogeneous charge / catalyst ratio is between 1.5 and 1000, preferably between 5 and 1000 weight and preferably between 10 and 500. The heterogeneous charge / catalyst ratio is between 1 and 1000, preferably between 1 and 1000. and 500 and preferably between 1 and 50 and more preferably between 1 and 25.
[0054] In a second variant, the at least one homogeneous catalyst is chosen from inorganic compounds comprising an element chosen from metals of group 6 of the periodic table, taken alone or as a mixture. Preferably, said compounds are chosen from the following inorganic compounds: chromium oxide, molybdenum oxide, molybdenum bronze, molybdic acid, molybdate, metamolybdic acid, metamolybdate, paramolybdic acid, paramolybdate, peroxomolybdic acid, peroxymolybdate or any heteropolyacid containing molybdenum , tungsten oxide, tungsten bronze, tungstic acid, tungstate, metatungstic acid, metatungstate, paratungstic acid, paratungstate, peroxotungstic acid, peroxytungstate or any heteropolyacid containing tungsten. Preferably, said inorganic compounds of group 6 of the periodic table are chosen from the following inorganic compounds: tungsten oxide, tungsten bronze, tungstic acid, tungstate, metatungstic acid, metatungstate, paratungstic acid, paratungstate, peroxotungstic acid, peroxytungstate or any heteropolyacid containing tungsten. Very preferably, said inorganic compounds of group 6 of the periodic table are chosen from the following inorganic compounds: tungsten bronze, tungstic acid, metatungstic acid, paratungstic acid or any heteropolyacid containing tungsten. According to this second variant, the cellulosic fraction resulting from the conversion step a) is brought into contact in a closed reactor for a period of between 10 minutes to 12 hours with the heterogeneous catalyst resulting from the first conversion step and a homogeneous catalyst. . The assembly is brought to temperature between 50 and 300 ° C., preferably between 100 and 250 ° C. The hydrogen pressure is between 0.5 and 20 MPa, preferably between 1 and 10 MPa. The solvent / cellulose fraction ratio is between 1 and 1000, preferably between 1 and 500 and preferably between 5 and 100. The homogeneous charge / catalyst ratio is between 1.5 and 1000, preferably between 5 and 100. 1000 weight and preferably between 10 and 500. The heterogeneous charge / catalyst ratio is between 1 and 1000, preferably between 1 and 500 and preferably between 1 and 50 and even more preferably between 1 and 25. alternatively, the at least one homogeneous catalyst is selected from organic or inorganic Bronsted acids. Preferably, said inorganic Bronsted acid (s) are chosen from the following inorganic acids: HF, HCl, HBr, HI, H 2 O 3, H 2 O 4, H 3 PO 2, H 3 PO 4, HNO 2, HNO 3, H 3 BO 3, H0 10 4, HBF 4, HSbF 5, HPF 6, H 2 PO 3 P, 01503H, FSO3H, HN (502F) 2 and HI03. Preferably, the inorganic Bronsted acids are chosen from the following inorganic acids: HCl, H 2 SO 4, H 3 PO 4.
[0055] A very preferred inorganic Bronsted acid is hydrochloric acid (HCl). Preferably, the organic Bronsted acids are chosen from organic acids of general formulas R-000H, RSO2H, RSO3H, (R502) NH, (R0) 2PO2H, ROH where R is a hydrogen or a carbon chain composed of alkyl groups or aryls, substituted or not by heteroatoms. Preferably, the organic acids of Bronsted are chosen from the following organic acids: formic acid, acetic acid, trifluoroacetic acid, lactic acid, levulinic acid, methanesulfinic acid, acid methanesulfonic acid, trifluoromethanesulfonic acid, bis (trifluoromethanesulfonyl) amine, benzoic acid, para-toluenesulfonic acid, 4-biphenylsulfonic acid, diphenylphosphate, and 1,11-binaphthyl-2,2'-dihydrogenphosphate. A most preferred organic Bronsted acid is methanesulfonic acid.
[0056] According to this variant, the cellulosic fraction resulting from the conversion step a) is brought into contact in a closed reactor for a period of between 10 minutes and 12 hours. The mixture is brought to temperature between 50 and 300 ° C., preferably between 100 and 250 ° C. The hydrogen pressure is between 0.5 and 20 MPa, preferably between 1 and 10 MPa. The solvent / cellulose fraction ratio is between 1 and 1000, preferably between 1 and 500 and preferably between 5 and 100. The homogeneous charge / catalyst ratio is between 1.5 and 1000, preferably between 5 and 100. 1000 weight and preferably between 10 and 500. The heterogeneous charge / catalyst ratio is between 1 and 1000, preferably between 1 and 500 and preferably between 1 and 50 and more preferably between 1 and 25.
[0057] The third conversion step e) may be optionally preceded by a hydrolysis step. During this step, the cellulosic fraction resulting from conversion step a) is mainly converted into a monomeric sugar mixture; that is, for example, in hexoses and pentoses. This mixture can also be advantageously hydrogenated to sugar alcohols, that is to say in hexitols and pentitols, for the purposes of the process. At the outlet of the third conversion step e), the liquid effluent obtained comprising predominantly mono or poly-oxygenated compounds is sent to the third separation step f). f) The third separation step According to the invention, the process comprises a third step of separating the liquid effluent comprising mainly mono or poly-oxygenated compounds obtained at the end of the conversion step e), in an effluent predominantly composed of alcohols and polyols, a fraction containing the heterogeneous catalyst or catalysts, a solid fraction comprising the unconverted lignin and a fraction comprising the homogeneous catalyst or catalysts.
[0058] The objective of the third step of separation of the liquid effluent mainly comprising mono or poly-oxygenated compounds is to isolate a fraction composed of the heterogeneous catalyst (s), a fraction comprising the homogeneous catalyst (s) and to obtain effluents mostly composed of alcohols or polyols of high purity so that they are directly usable for applications of the intermediate chemical type. The liquid effluent comprising predominantly poly-oxygenated compounds obtained at the end of the conversion step e) is composed of high purity polyols so that they can be used directly for intermediate chemical type applications. Said liquid effluent is preferably composed of more than 95% by weight of polyols, preferably more than 97% by weight and even more preferably more than 99% by weight relative to the total mass of said effluent. The separation step f) is advantageously carried out by means known to those skilled in the art such as, for example, liquid-liquid separation, distillation, etc. e ') The second regeneration step (optional) The process according to the invention may also advantageously comprise a second optional step e') of regeneration of said fraction comprising the heterogeneous catalyst or catalysts resulting from the third separation step f). Said step e ') produces a regenerated fraction comprising the heterogeneous catalyst (s). The objective of the second regeneration step (e ') of the fraction comprising the heterogeneous catalyst or catalysts in the regenerated fraction is to carry out, in a consecutive or simultaneous manner, the decoking of the catalyst (s) and their reduction. In the case where the catalysts of steps a) and e) are identical, the regenerated fraction comprising the regenerated heterogeneous catalyst or catalysts is thus advantageously recycled in the first conversion step a). The method used for the regeneration of the heterogeneous catalyst or catalysts is implemented by a conventional method known to those skilled in the art. This method may, for example, include heat treatment, sonochemical treatment, treatment with acidic or basic solutions, etc. DESCRIPTION OF THE FIGURES FIG. 1 illustrates a preferred embodiment of the invention. The lignocellulosic biomass (1) is introduced in a first conversion step a) to produce a cellulosic fraction (9) and a liquid effluent (2) containing the lignin degradation products and the solvent used in step a) conversion. The liquid effluent (2) is then sent to a first separation step b) to separate the solvent from the liquid effluent obtained at the end of the conversion step a) and to produce an effluent comprising mainly said solvent (3). ') and an effluent mainly comprising a bio-oil (3). The effluent comprising mainly the solvent (3 ') is sent in a first regeneration step (e') supplied via line (7) with hydrogen, to produce a regenerated effluent (8) comprising the solvent which is then recycled. in said first conversion step a). The effluent comprising mainly a bio-oil (3) is then sent to a second conversion step c) fed via line (4) with hydrogen to produce an effluent comprising predominantly hydrocarbons (5). The effluent comprising mainly hydrocarbons (5) is then sent to a second separation step d) to obtain a cut (6) that can be incorporated into the gasoline, gas oil, kerosene or an aromatic cut-off that can be incorporated in the aromatic complex. The cellulosic fraction (9) resulting from the conversion step a) is sent to a third conversion step e) fed via the pipe (10) with hydrogen to produce a liquid effluent mainly comprising mono or poly compounds. -oxygenated (11) which is then sent in a third separation step f) to produce an effluent predominantly composed of alcohols and polyols (12), a fraction containing the heterogeneous catalyst (s) (12 "), a fraction comprising lignin unconverted (12 ') and a fraction comprising the homogeneous catalyst (s) (12 "). The fraction containing the heterogeneous catalyst (s) (12 ") is sent to a second regeneration step (e ') to produce a regenerated fraction (13) comprising the heterogeneous catalyst (s) which is recycled in the first conversion step (a).
[0059] The examples illustrate the invention without limiting its scope. Example 1 (in accordance with the invention) The starting biomass is shredded poplar and put in the form of chips.
[0060] The composition of the dry lignocellulosic biomass is given in Table 1. 100 kg of poplar (dry matter) are treated according to the sequence of steps according to the process according to the invention. % weight Hemicellulose 21.5 Lignin 28.1 Cellulose 50.4 Table 1 Mass composition of initial poplar biomass (dry matter basis) a) First conversion step The starting lignocellulosic biomass undergoes the first step a) 180 ° conversion C. and at a pressure of 5 MPa, under an inert atmosphere of nitrogen, in a mass mixture of water and 2-propanol (20:80) for 6 hours, in the presence of a mass heterogeneous catalyst of the nickel-nickel type. Raney comprising a Ni content of 15.4% by weight relative to the total mass of said catalyst. The filler / catalyst ratio is 4. This allows to isolate a cellulosic fraction whose cellulose content in% by weight relative to the dry matter of said cellulosic fraction is reported in Table 2 and at least one liquid effluent whose composition is detailed in Table 2. A cellulosic fraction rich in cellulose is obtained. Nature Cellulose fraction (kg) Liquid effluent (kg) Cellulose 49.6 0 Lignin 11.2 0 Hemicellulose 11.5 0 Bio-oil 0 27.7 Water 0 192 2-propanol 0 693 Acetone 0 16 Table 2: Mass composition of fractions and effluent at the outlet of the first conversion step. b) First separation step The liquid effluent then undergoes the first separation step making it possible to obtain an effluent comprising mainly said solvent and an effluent comprising mainly a bio-oil, the compositions of which are described in Table 3.
[0061] Effluent nature mainly comprising said solvent (kg) (stream 2 ') effluent mainly comprising a bio-oil (kg) (stream 2) Water 185 0 2-propanol 679 0 Acetone 71 0 Bio-oil 0 27.1 Table 3 Composition by mass effluents from the separation step b). c ') First Regeneration Stage The effluent comprising predominantly said solvent undergoes the first regeneration step at 120 ° C. under 4.8 MPa of hydrogen in the presence of a mass heterogeneous catalyst of the Raney nickel type identical to that used in FIG. step a) of conversion, in a reactor with continuous stirring, the catalyst is introduced into the reactor in an amount corresponding to a mass ratio load / catalyst of 50. It leaves the flow (8) comprising the regenerated solvent whose composition is given in Table 4. Traces of primary alcohols are also noted.
[0062] Nature effluent regenerated solvent (kg) Water 180 2-propanol 730 Table 4 Mass composition of the stream 8) .20 C) Second conversion stage The effluent comprising mainly a bio-oil undergoes the second conversion step c) to give an effluent comprising mainly hydrocarbons.
[0063] This step is a hydrotreatment step which gives a stream 3) mainly comprising hydrocarbons. The catalyst is a hydrotreatment catalyst comprising, by weight, 4.3% NiO and 21% MoO.sub.3 supported on gamma-alumina. Before testing, the catalyst is sulphurized at 350 ° C. using an additive load of 2% by weight of dimethyl disulphide. Flow 2) is subjected to operating conditions of 360 ° C., 6 MPa of hydrogen, with a vvh of 1 hr. d) Second separation step During the second separation step, the stream 3) comprising mainly hydrocarbons from the second conversion step c) is converted into 14.9 tonnes of a 99.8% wt. hydrocarbons and 0.2% by weight of oxygen which can be incorporated into the fuel cuts and / or sections comprising aromatic compounds. e) Third Conversion Step The liquid effluent from conversion step a) undergoes the third conversion step. The charge is converted to give a liquid effluent mainly comprising mono or poly-oxygenated compounds in a batch reactor at 245 ° C. under 6 MPa of hydrogen introduced at ambient temperature, for two hours, in the presence of a homogeneous catalyst, tungstic acid, and Raney nickel-type mass heterogeneous catalyst identical to that used in the first conversion step. The cellulosic fraction resulting from the conversion step a) constituting the feedstock of said conversion step e) is introduced into said step e) in an amount corresponding to a mass ratio solvent / dry base effluent of 40. The catalyst homogeneous is advantageously introduced into the reaction chamber in an amount corresponding to a mass ratio dry filler (cellulosic fraction from step a)) / homogeneous catalysts of 55. The heterogeneous catalyst is introduced into the reaction chamber in an amount corresponding to a mass ratio dry filler (cellulosic fraction from step a)) / heterogeneous catalyst (s) of 2.4. f) Third separation step The components of the liquid effluent comprising mainly mono or poly-oxygenated compounds from the conversion step e) are separated by the third separation step to give a liquid effluent predominantly composed of alcohols and polyols, a fraction containing the heterogeneous catalyst, a fraction comprising the unconverted lignin and a fraction comprising the homogeneous catalyst. The composition of the liquid effluent is given in Table 5. Traces of lactones and cyclic ethers are also noted. The different compounds are then separated to be useful as chemical intermediates.
[0064] Nature liquid effluent predominantly composed of alcohols and polyols (kg) fraction comprising unconverted lignin (kg) Alcohols 5.8 0 Diols 35.0 0 Upper polyols 9.8 0 Lignin 0 11.2 Table 5 Mass composition of the liquid effluent predominantly composed of alcohols and polyols The fraction containing the heterogeneous catalyst is subjected to the second step of regeneration of the heterogeneous catalyst to give the fraction containing the regenerated catalyst. The fraction containing the homogeneous catalysts is recycled in the third conversion stage or is removed by an adequate recovery method.

权利要求:
Claims (4)
[0001]
REVENDICATIONS1. Process for producing bioproducts from lignocellulosic biomass, comprising at least the following steps: a) A first step of converting the lignocellulosic biomass into at least one cellulosic fraction comprising a cellulose content of at least 60% by weight with respect to the dry matter of the said cellulosic fraction and at least one liquid effluent, the said conversion step operating in the presence of a mass or supported heterogeneous catalyst, of molecular hydrogen and / or of a solvent, at a temperature of between 150 and 300; ° C and at a pressure of between 0.5 and 20 MPa, + b) A first step of separation b) of at least a part of the solvent of the liquid effluent obtained at the end of step a) of conversion to produce an effluent comprising predominantly said solvent and an effluent comprising mainly a bio-oil, c) A second effluent conversion stage comprising mainly a bio-oil is said step of b) separating into an effluent comprising predominantly hydrocarbons, said conversion step operates in the presence of hydrogen and a heterogeneous catalyst, at a temperature above 200 ° C, at a pressure of between 2 and 25 MPa and at a space velocity of between 0.1 and 20h-1, d) A second stage of separation of said liquid effluent comprising mainly hydrocarbons from the second conversion step c), e) A third step e) of converting the cellulosic fraction resulting from conversion step a) into a liquid effluent mainly comprising mono or poly-oxygenated compounds, in which said cellulosic fraction is brought into contact, simultaneously, with a combination of one or more homogeneous catalysts and one or more heterogeneous catalysts, in the same reaction chamber, in the presence of at least one solvent, said solvent being water alone or in melan with at least one other solvent, under a reducing atmosphere, and at a temperature between 50 and 300 ° C, and at a pressure of between 0.5 and 20 MPa, f) A third step of separating the liquid effluent comprising predominantly mono or poly-oxygenated compounds obtained after the conversion step e), into an effluent predominantly composed of alcohols and polyols, a fraction containing the heterogeneous catalyst (s), a fraction comprising the unconverted lignin and a fraction comprising the homogeneous catalyst (s).
[0002]
2. Process according to claim 1, in which said mass or supported heterogeneous catalyst used in step a) comprises at least one metal chosen from metals of group 10 alone or in admixture with a metal chosen from metals of groups 6 to 14. of the periodic table and optionally a support is selected from the oxides of elements selected from aluminum, titanium, silicon, 41e zirconium, cerium, lanthanum and niobium, and mixed oxides selected from zinc aluminates , copper and cobalt, said oxides may be doped or not by at least one metal compound selected from tungsten, tin, molybdenum and antimony, taken alone or in mixture, the perovskites of formula ABO3 in which A is selected from the elements Mg, Ca, Sr, Ba and La and B is selected from Fe, Mn, Ti and Zr elements, crystallized aluminosilicates or not, aluminophosphates and carbon compounds am Orphids or crystallized. 20
[0003]
The process of Claim 2 wherein said Group 10 metal is nickel, alone or in admixture with the metals of Groups 6 to 14 of the Periodic Table selected from the following metals: Mo W, Co. Process according to one of the following: Claims 1 to 3 wherein the metal content of groups 6 to 14 on said heterogeneous catalyst is between 5 and 15% by weight based on the total weight of said heterogeneous catalyst, in the case where metals of groups 6 to 14 are used in said catalyst. Process according to one of Claims 1 to 3, in which the heterogeneous catalyst used in said step a) is a Raney-Nickel-type mass catalyst.6. Process according to one of Claims 1 to 5, in which the solvent used in the first conversion step a) is chosen from hydrogen donor solvents and non-hydrogen donor organic solvents. 7. Process according to claim 6, in which the hydrogen donor solvents are chosen from linear or cyclic secondary alcohols comprising 3 to 6 carbon atoms chosen from isopropanol, 2-butanol, 2-pentanol, 3- pentanol, 2-hexanol, 3-hexanol, cyclohexanol, cyclohexanediols. The method of claim 6 wherein the non-hydrogen donor organic solvents are selected from alcohols selected from methanol, ethanol, isopropanol, isobutanol and butanol, ethers selected from tetrahydrofuran, 2 methyltetrahydrofuran and diethyl ether, and organic acids selected from formic acid and acetic acid and polyols. The method according to one of claims 1 to 8 wherein said process also comprises a first regeneration step of said effluent containing predominantly said solvent from the first step b) of separation, said regeneration step producing a regenerated solvent effluent which is then Recycled in the first conversion step a). 10. The process as claimed in claim 9, wherein said first regeneration step is carried out at temperatures between 40 and 300 ° C., and at a pressure of between 0.1 and 20 MPa, in the presence of a mass heterogeneous catalyst of the following type. Raney nickel. 11. Method according to one of claims 1 to 10 wherein the heterogeneous catalyst or catalysts used in said third conversion step e) are selected from supported or bulk heterogeneous catalysts comprising at least one metal selected from Group 10 metals. alone or in admixture with a metal chosen from the metals of groups 6 to 14 of the periodic table, and optionally a support chosen from the oxides of the elements chosen from aluminum, titanium, silicon, zirconium, cerium, lanthanum and niobium alone or in admixture, and the mixed oxides chosen from zinc, copper and cobalt aluminates, said oxides possibly doped with at least one metal compound chosen from tungsten, tin and molybdenum and antimony, taken alone or in a mixture, the perovskites of formula AB03 in which A is chosen from the elements Mg, Ca, Sr, Ba and La and B is chosen from among the elements Fe, Mn, Ti and Zr, crystallized aluminosilicates or not, aluminophosphates and amorphous or crystallized carbon compounds. 12. The process according to claim 11 wherein the heterogeneous catalyst used in said third conversion step e) is a Raney nickel-type bulk catalyst. 13. Method according to one of claims 1 to 12 wherein said one or more homogeneous catalysts used in said third conversion step e) are selected from hydrated or non-hydrated metal salts having a general formula EXn.n'H20 in which E is an element selected from metals of Groups 3 to 16 or the group of lanthanides of the Periodic Table, n is an integer from 1 to 6 and n 'is an integer from 0 to 20 and X is at least one anion chosen from halides, nitrates, carboxylates, oxalates, halocarboxylates, acetylacetonates, alcoholates, phenolates, substituted or unsubstituted, sulphates, alkyl sulphates, phosphates, alkyl phosphates, halosulfonates, alkyl sulphonates, perhaloalkylsulfonates, bis (perhafogénoalkylsulfonypamidures, arenesulphonates, substituted or unsubstituted by halogen or haloalkyl groups, X anions may be the same or different in the case where n is greater than 1. 14. Method according to one of claims 1 to 12 wherein the or said homogeneous catalysts used in said third step e) conversion are selected from the inorganic compounds comprising an element selected from metals of Group 6 of the Periodic Table, alone or in admixture. Process according to one of Claims 1 to 12, in which the at least one homogeneous catalyst used in the said third conversion step e) is chosen from organic acids chosen from formic acid, acetic acid and trifluoroacetic acid. lactic acid, levulinic acid, methanesulfinic acid, methanesulfonic acid, trifluoromethanesulfonic acid, bis (trifluoromethanesulfonyl) amine, benzoic acid, paratofuenesulfonic acid, acid
[0004]
4-biphenylsulfonic, diphenylphosphate, and 1,1'-binaphthyl-2,2'-diyl hydrogenphosphate and inorganic Bronsted acids selected from the following inorganic acids: HF, HCl, HBr, HI, H2SO3, H2SO4, H3PO2, H3PO4, HNO2, 141 103, H3B03, HCI04, HBF4, HSbF5, HPF6, H2F03P, CISO3H, FSO3H, HN (SO2F) 2 and HI03.

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同族专利:

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公开号 | 公开日

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FR3030561B1|2017-01-27|

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WO2019158616A1|2018-02-13|2019-08-22|Cmblu Projekt Ag|Novel methods for processing lignocellulosic material|

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WO2020002361A1|2018-06-25|2020-01-02|Katholieke Universiteit Leuven|Fractionation and depolymerisation of lignocellulosic material|

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US11008284B2|2016-04-07|2021-05-18|Cmblu Projekt Ag|Sulfonated aromatic compounds|

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2016-06-24| PLSC| Publication of the preliminary search report|Effective date: 20160624 |

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2021-12-27| PLFP| Fee payment|Year of fee payment: 8 |

优先权:

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申请号 | 申请日 | 专利标题

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FR1462832A|FR3030561B1|2014-12-18|2014-12-18|PROCESS FOR THE TRANSFORMATION OF LIGNOCELLULOSIC BIOMASS TO OXYGENIC MOLECULES AND HYDROCARBONS WITHOUT PRETREATMENT STEPS|FR1462832A| FR3030561B1|2014-12-18|2014-12-18|PROCESS FOR THE TRANSFORMATION OF LIGNOCELLULOSIC BIOMASS TO OXYGENIC MOLECULES AND HYDROCARBONS WITHOUT PRETREATMENT STEPS|