FR2987281A1 - NEW TRIFUNCTIONAL BIMETALLIC CATALYSTS, PROCESS FOR THE PREPARATION THEREOF AND USE THEREOF - Google Patents

Abstract

The present invention relates to a trifunctional bimetallic catalyst consisting of a heteropoly acid (HPA), a Group IA or IIA Z element, a Group VIIB or VIIIB metal M 'and a group IB' M 'metal or This catalyst can be used in the transformation of lignocellulosic material into organic molecules constituting a biofuel.

Description

The invention relates to novel trifunctional bimetallic catalysts, process for their preparation and their use. 10 Various problems are linked to the constant rise in the consumption of fossil energy sources, particularly by developing countries, to produce energy (thermal power plants, transport) but also to transform them into energy sources. chemical products. The price of these non-renewable resources, which are more and more in demand, is constantly growing, as dependence on these sources of fossil energy can generate geopolitical problems. Another problem, of an environmental nature, is related to the production of CO2 creating a greenhouse effect and thus contributing to global warming. It is therefore urgent to find other sources of energy. Among renewable and recoverable sources of energy, lignocellulosic biomass, biomass from wood, is the subject of much research with the aim of producing liquid biofuels. Lignocellulosic biomass has the advantage of being abundant and easily accessible. A second advantage lies in the carbon footprint: between the production of wood, a major consumer of CO2 through photosynthesis, and the use of biofuels releasing CO2, the balance is neutral. Lignocellulosic biomass consists of 35 to 50% cellulose, 20 to 35% hemicellulose and 10 to 25% lignin. Cellulose is a glucose polysaccharide while hemicellulose is a polysaccharide consisting of a mixture of C5 and C6 sugars. Lignin, of very variable composition, is a polymer of monolignols. In order to convert lignocellulosic biomass into liquid fuels, it is therefore necessary to depolymerize its constituents, to deoxygenate them and to hydrogenate them. Processes for transforming lignocellulosic material are catalytic hydrolysis, liquefaction, pyrolysis, gasification. All the processes known to date comprise several steps and are not carried out in the same reactor. In addition, heating temperatures are high, often above 700 ° C. The catalysts used in these processes may be metals, organometallic compounds, zeolites, oxides, acids, especially HPA heteropolyacids and their derivatives (Zhou CH, Lin CX, Tong DS, Beltramin J., Chem Soc Rev 2011, 40, 5588-5617, W02011 / 092711, Dhepe P., Sahu R.). Of the HPAs, some are used without metal (Tian J., Wang J., Zhao S., Jiang C., Zhang X., Wang X., Cellulose, 2010, 17, 587-594); others are transition metal supports (Shimizu KI, Furukawa H., Kobayashi N., Itaya Y., Satsuma A., Green Chem., 2009, 11, 1627-1632, Liu M., Deng W., Zhang Q., Wang Y., Chem Comm., 2011, 1039). In both cases, metal-free HPA and monometallic HPA, the lignocellulosic material is converted into a mixture of simple sugars (sorbitol, glucose): these catalysts therefore do not make it possible to obtain a mixture of deoxygenated molecules that can constitute a liquid biofuel. It is therefore extremely rewarding to obtain catalysts that can act on the lignocellulosic material by fulfilling all the functions necessary for the preparation of a liquid biofuel. An object of the invention is to implement a process for preparing novel trifunctional bimetallic catalysts. Another object of the invention is to use these trifunctional bimetallic catalysts to ensure at the same time or in a consecutive manner, the depolymerization of lignocellulosic material, the hydrogenation and the deoxygenation of the molecules obtained by depolymerization. Another object of the invention is the use in industrial environments, using inexpensive reagents and heating temperatures of less than 500 ° C., of a process for converting the lignocellulosic material to obtain biofuels.

The invention relates to a trifunctional bimetallic catalyst consisting of: - a heteropoly acid (HPA), in the form of a monomer - of a group IA or IIA Z element, - a group VIIB M 'metal or - and of an M "metal of group IB or IIB" HPA "or" heteropoly acid "means a polyoxometalate containing labile hydrogen atoms, oxygen atoms, a metal such as tungsten, vanadium, chromium, molybdenum, an element such as silicon, phosphorus, arsenic "element Z of group IA or IIA" denotes an element chosen from alkalis or chosen from alkaline earth metals "metal M 'of group VIIB or VIIIB" denotes a metal of transition comprising ruthenium, rhenium, manganese, iron, cobalt or nickel, and all elements of their families "Metal M" of group IB or IIB "denotes a metal selected from copper, silver, gold, or zinc and cadmium. The catalyst is called a "bimetallic catalyst" because it contains two metals, supported by HPA.

According to an advantageous embodiment, the trifunctional bimetallic catalyst according to the invention forms solid nanoparticles, whose average size distributions are from 0.8 nm to 3 nm. The particles formed are nanoparticles of spherical shape. According to another advantageous embodiment, in the trifunctional bimetallic catalyst, the HPA is of the Keggin type or of the Wells-Dawson type, Andersson type, Lindqvist type, Strandberg type, Allman-Waugh type, Weakley-Yamase type, or Dexter type, in particular said type HPA type. Keggin. There are several types of HPA according to the geometric arrangement of the atoms or groups of atoms constituting them. Among these different types, the most used in catalysis are "Keggin type HPA" of general formula H3XM12040 and "Dawson type HPA" of general formula H6X2M18062. They are useful both in homogeneous or heterogeneous catalysis, both in oxidation catalysis and in acid catalysis. According to another embodiment, in the trifunctional bimetallic catalyst, the HPA is of the Keggin type and has the formula H3X1 \ 41204o wherein ^ X represents - a group IVA element selected from Si, Ge, Sn, Pb, - or an element of the group VA chosen from P, As, Sb, Bi, X being in particular the phosphorus element P, M represents an element of the group VB or VIB chosen from Cr, Mo, W, V, representing in particular Mo or W, being in particular W, said HPA having especially formula H3PW12040.

According to a particular embodiment, the trifunctional bimetallic catalyst of the invention is such that the element Z is in the form of a Z + cation chosen from Li +, Na +, K +, Rb +, Cs +, or Z2 + cation. chosen from Be2 Ca2 + mg2 + sr2 + Ba2 +, said cation being in particular Cs +. Cesium thermally stabilizes the Keggin-type HPA for use at temperatures above 450 ° C as a catalyst for reactions that require such temperatures to occur. Cesium also makes HPA support less soluble in water and increases its acidity.

According to another particular embodiment, in the trifunctional bimetallic catalyst according to the invention, the HPA is of Keggin type, Z belongs to group IA and is in the form of Z + cation, said HPA and Z + forming a derivative of formula ZnH3_11) Where n is the number of Z + cation such that n = 1 to 3.

It is therefore possible to use catalysts of formula Z1H2X1 \ 412040, Z2HX1 \ 41204o, Z25F105XM12040 or Z3XM12040. The number of cesium ions makes it possible to modulate the acidity of the HPA. According to another particular embodiment, in the trifunctional bimetallic catalyst of the invention, the metal M 'is supported by the derivative of formula ZnH3_n) (1 \ 412040, the metal M' belonging to group VIIB and being chosen from Mn or Re, or the metal M 'belonging to group VIIIB and being chosen from Fe, Ru, Os, Co, Rh, Ir, Ni, Pd or Pt, said metal M' being in particular Ru, Ni or Re. 25 "Supported metal Means that said metal is included in the structure of the catalyst by insertion into the structure of the HPA According to another particular embodiment, in the trifunctional bimetallic catalyst of the invention, the metal M "is supported by the derivative of formula ZnH3_nXM12040 The metal M "belonging to the group D3 and being chosen from Cu, Ag or Au, or the metal M" belonging to the group IIB and being chosen from Zn or Cd, said metal M "being in particular Cu The presence of the metal M ", especially copper, supported on HPA, allows to crush ux control the size of the nanoparticles. However, the smaller the nanoparticles, the greater the ratio of metals active towards catalysis (surface metals) to the amount of total metals (surface metals + core metals) is important. This reduces the amount of catalyst and therefore the cost of catalyst, which is an advantage for its use especially in industrial environments. According to another particular embodiment, in the trifunctional bimetallic catalyst of the invention, the mass proportion M '/ M "is from 0.1 to 3, in particular from 0.5 to 3, and in particular is equal to In accordance with a particular embodiment, the trifunctional bimetallic catalyst of the invention has the formula: ## STR2 ## wherein "@" means "supported", M '= Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd or Pt, in particular Ru, Ni or Re, M "= Cu, Ag, Au, Zn, Cd, in particular Cu, Z = Li +, Na +, K + , Rb +, Cs +, eB 2+, ca2 +, mg2 +, sr2 +, Ba2 +, especially Cs +, X = Si, Ge, Sn, Pb, P, As, Sb, Bi, especially P, M = Cr, Mo, W, V, in particular Mo or W, in particular W, x and y being from 0.01 to 1, n = 1 to 3, said metal M 'having a mass percentage of from 0.1 to 3%, said metal M " having a weight percentage of from 0.1 to 3%. More particularly, the invention relates to a trifunctional bimetallic catalyst having the formula M''M "y @ CsnH3 PW-12 40, in which" @ "means" supported ", M '= Mn, Re, Fe, Ru, Os, Co , Rh, Ir, Ni, Pd or Pt, especially Ru, Ni or Re, M "= Cu, Ag, Au, Zn, Cd, especially Cu, x and y being from 0.01 to 1, n = 1 to 3, said metal M 'having a weight percentage of from 0.1 to 3%, said metal M "having a weight percentage of from 0.1 to 3% .The catalysts according to the invention more particularly consist of HPA containing phosphorus. Advantageously, the trifunctional bimetallic catalyst according to the invention has the formula Ru'Cuy @ CsnH3 PW-12 40, in which "@" means "supported", x and y being from 0.01 to 1 , n = 1 to 3, the weight percentage of ruthenium being from 0.1 to 3%, the weight percentage of copper being from 0.1 to 3%. The ruthenium and copper combinations are particularly preferred. surely advantageous. These two metals are supported on the surface and inside the structure of said HPA. The percentages by weight of each of these two metals are variable, within the limits indicated above.

Advantageously, the trifunctional bimetallic catalyst according to the invention has the formula Ni'Cuy @ Cs'H3 PW-12-40, in which "@" means "supported", x and y being from 0.01 to 1 , n = 1 to 3, the weight percentage of nickel being from 0.1 to 2%, the weight percentage of copper being from 0.1 to 2%. The combinations of nickel and copper are particularly advantageous. These two metals are supported on the surface and inside the structure of said HPA.

The percentages by weight of each of these two metals are variable, within the limits indicated above. Advantageously, the trifunctional bimetallic catalyst according to the invention has the formula RexCuy @ CSni13_n) (1 \ 412040, in which "@" means "supported", x and y are from 0.01 to 1, n = 1 at 3, the weight percentage of rhenium is from 0.1 to 2%, the weight percentage of copper is from 0.1 to 2%.

The rhenium and copper combinations are particularly advantageous. These two metals are supported on the surface and inside the structure of said HPA. The percentages by weight of each of these two metals are variable, within the limits indicated above.

The combinations of rhenium and zinc or rhenium and cadmium are also advantageous. Particularly advantageously, the trifunctional bimetallic catalyst according to the invention has the formula Cu 3 @ Csi 2 H 6 P 6 W 7 O 2 O 2 O containing 1% by weight of Ru and 1% by weight of Cu. Particularly advantageously, the trifunctional bimetallic catalyst according to the invention has the formula Ni3Cu3 @ Csi2H6P6W72024o, containing 1% by weight of Ni and 1% by weight of Cu. In a particularly advantageous manner, the trifunctional bimetallic catalyst according to the invention has the formula Re Cu3 @ Csi2H6P6W72024o containing 1% by weight of Re and 1% by mass of copper. The invention also relates to the use of a mixture of HPA, a salt of element Z of group IA or IIA, a salt of metal M 'of group VIIB or VIIIB and a salt of metal M of the group IB or IIB, for the preparation of a trifunctional bimetallic catalyst as defined above The invention also relates to a process for the preparation of the trifunctional bimetallic catalyst designated above, comprising: a step of calcination at atmospheric pressure under air dry of a partially dry solid containing the following components: an HPA, a Z element of group IA or IIA in the form of a Z + or Z2 + cation originating from an aqueous solution of a salt of this element, a metal M 'of the group VIIB or VIIIB in the form of a cation at the oxidation state + II or + III, a metal M "of the group IB or IIB in the form of a cation at the oxidation state + I or + II, - and the anions associated with the above cations, the anions being chosen from the carboxylate ion (RC 00), R being a linear or branched alkyl group containing from 1 to 6 carbon atoms, the carboxylate ion being in particular the acetate ion (AcO), the nitrate ion (NO3-), the chloride ion (Cl ), the oxide ion (02), the cyanide ion (CN), the sulfate ion (SO421) to remove the physisorbed water from the solid, to reduce the metals M 'and M ", to decompose the aforementioned anions and to obtaining a dry solid containing the aforesaid components, then a stage of treatment under atmospheric pressure with hydrogen of the aforesaid dry solid to obtain a dry solid in which M 'and M "are reduced to the zero oxidation state. The calcination is carried out under dry air, consisting of a gaseous mixture of 78% N 2 and 21% O 2. The treatment under hydrogen makes it possible to reduce the metals M 'and M ", initially in the form of cations with oxidation levels. + I, + II, + III or + VII, depending on the nature of the metal The invention also relates to a process for preparing the trifunctional bimetallic catalyst designated above, comprising: before the calcination step, a step of evaporation of the water of the aqueous solution containing the solid containing the following components: - an HPA, - a Z element of group IA or IIA in the form of a Z + or Z2 + cation originating from an aqueous solution of a salt of this element, - a Group VIIB metal M 'or VIIIB in the form of oxidation cation + II, + III or + VII, - Group IB or IIB metal M' in the form of oxidation cation + I or + II - and the anions associated with the above cations, the anions being chosen from the carboxylate ion (RC00-) , R being a linear or branched alkyl group containing from 1 to 6 carbon atoms, the carboxylate ion being in particular the acetate ion (AcO), the nitrate ion (NO3-), the chloride ion (Cl), l oxide ion (02), cyanide ion (CN), sulfate ion (SO42-), to obtain a dry solid containing the aforesaid components. The invention also relates to a process for the preparation of the trifunctional bimetallic catalyst designated above, comprising a mixing step - of a Keggin or Wells-Dawson-type HPA, Andersson, Lindqvist, Strandberg, Allman-Waugh, Weakley-Yamase , Dexter, in particular of the Keggin type, an aqueous solution of a salt of element Z of group IA or IIA, a metal salt M 'of group VIIB or VIIIB, and a salt of group IB or IIB metal M ", the water being then removed from said mixture, in particular by evaporation, to obtain a partially dry solid containing the following components: - an HPA, - a Z element of group IA or IIA in the form of cation Z + or Z2 + from an aqueous solution of a salt of this element, - a metal M 'of the group VIIB or VIIIB in the form of cation with the oxidation state + II, + III or + VII, - a metal M "Group IB or IIB in the form of cation at the oxidation state + I or + II, - and the anions associated with the above-mentioned the anions being chosen from the carboxylate ion (RC00), R being a linear or branched alkyl group containing from 1 to 6 carbon atoms, the carboxylate ion being in particular the acetate ion (AcO), the nitrate ion; (NO3), chloride ion (Cl), oxide ion (02), cyanide ion (CN), sulfate ion (SO42). The invention relates to a process for the preparation of the trifunctional bimetallic catalyst designated above, comprising: a mixing step of a Keggin or Wells-Dawson type HPA, Andersson, Lindqvist, Strandberg, Allman-Waugh, Weakley-Yamase , Dexter, in particular of the Keggin type, an aqueous solution of a salt of element Z of group IA or IIA, a salt of metal M 'of group VIIB or VIIIB, and a salt of Group IB or IIB metal M ", the water then being removed from said mixture, in particular by evaporation, to obtain a partially dry solid containing the following components: an HPA, a group IA or IIA Z element in the form of a cation Z + or Z2 + from an aqueous solution of a salt of this element, - a group VIIB or VIIIB metal M 'in the form of a cation with oxidation state + II, + III or + VII, - a metal M " of group IB or IIB in the form of oxidation cation + II, - and the anions associated with the above-mentioned cations, the ions being chosen from the carboxylate ion (RC00), R being a linear or branched alkyl group containing from 1 to 6 carbon atoms, the carboxylate ion being in particular the acetate ion (AcO), the nitrate ion (NO3- ), the chloride ion (Cl), the oxide ion (02), the cyanide ion (CN), the sulfate ion (SO421), a calcination step at atmospheric pressure in dry air of the said partially dry solid containing the components following: - an HPA, - a Z element of group IA or IIA in the form of a Z + or Z2 + cation originating from an aqueous solution of a salt of this element, - a group VIIB or VIIM metal M 'in the form of a cation at the oxidation state + II, + III or + VII, - an M "metal of the group IB or IIB in the form of a cation at the oxidation state + I or + II, - and the anions associated with the above cations, the anions being chosen from the carboxylate ion (RC00), R being a linear or branched alkyl group containing from 1 to 6 carbon atoms, the carboxylate ion being in particular the acetate ion e (AcO), nitrate ion (NO3-), chloride ion (Cl), oxide ion (02), cyanide ion (CN), sulfate ion (SO421) to remove solid from water physisorbed and to decompose the aforesaid anions (nitrate, chloride, acetate, carboxylate, ...) to obtain a dry solid, then a treatment step in hydrogen to obtain a dry solid in which M 'and M "are reduced to zero oxidation state.

All the stages of catalyst preparation are carried out in the same reactor (FIG. 1). The invention relates to a process for the preparation of the trifunctional bimetallic catalyst according to the invention, wherein the step of calcination of the partially dry solid containing the following components: an HPA, a Z element of the group IA or IIA in the form of cation Z + or Z2 + from an aqueous solution of a salt of this element, - a group VIIB or VIIM metal M 'in the form of a cation with oxidation state + II, + III or + VII, - a metal M " group IB or IIB in the form of oxidation cation + I or + II, - and the anions associated with the above cations, the anions being chosen from the carboxylate ion (RC00), R being a linear or branched alkyl group containing 1 to 6 carbon atoms, the carboxylate ion being in particular the acetate ion (AcO), the nitrate ion (NO3-), the chloride ion (Cl), the oxide ion (O2), the cyanide ion (CN), the sulphate ion (S0421 is carried out under dry air for a period of between 0.5 h to 5 h, in particular approximately equal to 3 hours, at a temperature of from 250 ° C to 400 ° C, in particular approximately equal to 300 ° C, to remove from the solid the physisorbed water and the aforementioned associated anions and to obtain a dry solid, then a hydrogen treatment step of said dry solid, to obtain a dry solid in which M 'and M "are reduced to the zero oxidation state.

According to an advantageous embodiment of the invention, the process for preparing a trifunctional bimetallic catalyst comprises a hydrogen treatment step carried out for a duration of from 0.5 h to 5 h, in particular a duration of approximately 3 hours. at a temperature of from 250 ° C. to 400 ° C., in particular approximately equal to 300 ° C., under a pressure of from 0.5 to 2 bar, in particular approximately equal to 1 bar, to obtain a dry solid in which M 'and M The majority of the processes use temperatures at least equal to 700 ° C. The catalyst according to the invention makes it possible not to heat at a temperature higher than 500 ° C. which constitutes a real advantage. in an industrial environment.

According to an advantageous embodiment of the invention, the process for preparing a trifunctional bimetallic catalyst comprises a mixing step carried out at room temperature with mechanical stirring, at a stirring speed of between 200 rpm and 600 rpm. / min, in particular about 300 rpm, for about 12 hours, the water being then removed, in particular by evaporation, to obtain a partially dry solid containing the following components: - an HPA, - a Z element of group IA or IIA in the form of a Z + or Z2 + cation originating from an aqueous solution of a salt of this element, - a Group VIIB or VIIIB metal M 'in the form of a cation with an oxidation state of + II, + III or + VII a group IB or IIB metal M "in the form of oxidation cation + I or + II, and the anions associated with the above cations, the anions being chosen from the carboxylate ion (RC00), R being a linear or branched alkyl group containing 1 to 6 carbon atoms, the carboxylate ion being in particular the acetate ion (AcO), the nitrate ion (NO3-), the chloride ion (Cl), the oxide ion (O2), the cyanide ion (CN), sulfate ion (SO42). According to an advantageous embodiment of the process for preparing a trifunctional bimetallic catalyst of the invention, the salt of the element Z contains this element in the form of a cation associated with an anion chosen from the carboxylate ion (RC00), R being a linear or branched alkyl group containing from 1 to 6 carbon atoms, the carboxylate ion being in particular the acetate ion (AcO), the nitrate ion (NO3), the chloride ion (Cl), the oxide ion (O2) ), the cyanide ion (CN), the sulfate ion (SO42), said salt being chosen from Cs2CO3, CsCl, Rb2CO3, RbCl, SrCO3, SrC12, BaSO4, BaCl2, BaCO3, and especially being cesium carbonate Cs2CO3; . The salts used are commercial and inexpensive. According to an advantageous embodiment of the process for preparing a trifunctional bimetallic catalyst of the invention, the Group VIIB or VIIIB metal salt M ', containing the metal at oxidation state + II or + III, is associated with an anion selected from the carboxylate ion (RC00), R being a linear or branched alkyl group containing from 1 to 6 carbon atoms, the carboxylate ion being in particular the acetate ion (AcO), the nitrate ion (NO3), the chloride ion (Cl), the oxide ion (O 2), said salt optionally being hydrated or combined with one or more ligands chosen from chloride, sulphate (5042), cyanide (CN) , carboxylate (RC00), R being a linear or branched alkyl group containing from 1 to 6 carbon atoms, the carboxylate ion being in particular the acetate ion (AcO), a phosphine chosen in particular from triphenylphosphine (PPh3) or trimethylphosphine (PMe3), allyl, phenyl, paracymene (cym), carbonyl (CO), cyclooctadiene (COD), cyclic ooctatetraene (TOC), acetylacetonate (acac), said group VIIB or VIIIB metal salt M 'being selected from Ni (OAc) 2, NiCl 2, Ni (acac) 2, RuCl 3, CymRuCl 2, RuCl 2 (PPh 3) 3, Ru 2 Cl 2 O 12, NH4ReO4, Fe (NO3) 3, Fe (OAc) 2, OsC12012, OsC13, Co2C808, Co504, RhC13, Rh (NO3) 3, IrC13, Ir4C12012, Pd (OAc) 2, PdCl3, Pt (NO3) 2, Pt ( OAc) 2, 25 - and the metal salt M "of the group TB or IIB containing the metal at the oxidation state + I or + II, being chosen from Cu (NO3) 2, 3H 2 O, CuCl 2, Zn (NO 3) 2 , ZnCl 2, AgNO 3, Ag 2 O, AuCl, AuCN, Cd (NO 3) 2, CdCl 2, and in particular Cu (NO 3) 2, 3H 2 O, the proportion M '/ M "being from 0.1 to 3, in particular from 0 to 5 to 3, and in particular being equal to 1. According to one advantageous embodiment, the invention relates to a process for preparing a trifunctional bimetallic catalyst of formula Ru'Cuy @ CsnH3_ PW 0 - 12 40, in which "@" means "supported", x and y being from 0.01 to 1, n = 1 to 3, the weight percent of ruthenium being from 0.1 to 3%, mass percentage of copper being from 0.1 to 3%. According to an advantageous embodiment, the invention relates to a process for the preparation of a trifunctional bimetallic catalyst of formula Ni'Cuy @ CsnH3 PW1240, in which "@" means "supported", x and y being from 0.01 to 1, n = 1 to 3, the weight percentage of nickel being from 0.1 to 2%, the weight percentage of copper being from 0.1 to 2%. According to an advantageous embodiment, the invention relates to a process for the preparation of a trifunctional bimetallic catalyst of formula RexCuy @ CsnH3 PW1240, in which x and y are from 0.01 to 1, n = 1 to 3, the mass percentage of rhenium is from 0.1 to 2%, the weight percentage of copper is from 0.1 to 2%. According to a particularly advantageous embodiment, the invention relates to a process for the preparation of a trifunctional bimetallic catalyst of formula Ru2Cu3 @ Csi2H6P6W720240, comprising a step of mixing - an HPA of formula H3PW12040, - an aqueous solution of Cs2CO3, - RuC12 (PPh3) 3, and Cu (NO3) 2,3H20, the water provided by the aqueous solution of Cs2CO3 then being removed from said mixture, in particular by evaporation, to obtain a partially dry solid containing a mixture of HPA, Cs + ions, Ru (II) and Cu (II), physisorbed water, carbonate and nitrate ions and PPh3 molecules, a step of calcination at atmospheric pressure in dry air of said solid partially dry, to remove physisorbed water, carbonate and nitrate ions, and PPh3 molecules, and to obtain a dry solid, then a hydrogen treatment step of said dry solid, to obtain a dry solid in which Ru and Cu are reduced to the degree of oxidation zero. According to a particularly advantageous embodiment, the invention relates to a process for preparing a trifunctional bimetallic catalyst of formula Ni3Cu3 @ Csi2H6P6W720240 comprising a step of mixing - an HPA of formula H3PW12040, - an aqueous solution of Cs2CO3 - Ni (OAc) 2, 10 - and Cu (NO3) 2,3H20, the water provided by the aqueous solution of Cs2CO3 then being removed from said mixture, in particular by evaporation, to obtain a partially dry solid containing a mixture of HPA, Cs + ions, Ni (II) and Cu (II), physisorbed water, carbonate, acetate and nitrate ions, a step of calcination at atmospheric pressure under air of said partially dry solid to remove the physisorbed water, the carbonate, acetate and nitrate ions, and to obtain a dry solid, then a hydrogen treatment step of said dry solid, to obtain a dry solid in which Ni and Cu are reduced to the degree zero oxidation. According to a particularly advantageous embodiment, the invention relates to a process for the preparation of a trifunctional bimetallic catalyst of formula ReCu3 @ Csi2H6P6W720240, comprising a step of mixing an HPA of formula H3PW12040, an aqueous solution. of Cs2CO3, - NH4Re04, - and Cu (NO3) 2,3H20, the water provided by the aqueous solution of Cs2CO3 then being removed from said mixture, in particular by evaporation, to obtain a partially dry solid containing a mixture of HPA , Cs + ions, Re (+ VII) and Cu (II), physisorbed water, carbonate ions, nitrate, ammonium, oxides, a step of calcination at atmospheric pressure in air of said partially dry solid, to remove the physisorbed water and the ions carbonate, nitrate, ammonium, oxides, and to obtain a dry solid, then a hydrogen treatment step of said dry solid, to obtain a dry solid in which Re and Cu are reduced to the degree zero oxidation. The invention also relates to the use of a previously defined trifunctional bimetallic catalyst for converting lignocellulosic material into low oxygen biofuel at a temperature of less than or equal to 500 ° C., in particular from 350 ° C. to 500 ° C. C, in particular between 400 ° C and 470 ° C, the mass of milled wood being from 1g to 20g for 0.001g to 2g of catalyst, in particular approximately equal to 10g of wood for about 1g of catalyst. "Lignocellulosic material" refers to biomass from wood, especially milled. The lignocellulosic material consists of 35 to 50% cellulose, 20 to 35% hemicellulose and 10 to 25% lignin. Cellulose is a glucose polysaccharide while hemicellulose is a polysaccharide consisting of a mixture of C5 and C6 sugars. Lignin, of very variable composition, is a polymer of monolignols. The lignocellulosic material is therefore very rich in carbon.

The invention relates more particularly to the use of a previously defined trifunctional bimetallic catalyst, to obtain a biofuel in the form of an organic phase containing a mixture of saturated or unsaturated hydrocarbons, aromatic or nonaromatic, and aromatic oxygen molecules. said mixture containing a percentage of oxygen in particular of less than or equal to 5%, in particular of from 3 to 4.5%, in particular equal to approximately 3.5%, the octane number of said mixture formed being comprised of 90 to 120. "Biofuel" refers to a fuel produced from non-fossil organic materials, especially from biomass. The "octane number" measures the resistance of a fuel used in a spark-ignition engine to the auto-ignition (ignition without intervention of the candle). The mixture obtained, analyzed by mass spectroscopy and by gas chromatography, is poor in oxygen element because the metal M ", in particular copper, allows deoxygenation of molecular weight molecules obtained low molecular weight.

In addition, the unsaturated molecules are partially saturated by hydrogenation. This reduces the polluting nature of these mixtures. According to an advantageous embodiment of the invention, a trifunctional bimetallic catalyst of formula RuxCuy @ CsnH3 PW-12 40 is used, in which "@" means "supported", x and y being from 0.01 to 1, n = 1. at 3, the mass percentage of ruthenium being from 0.1 to 3%, the weight percentage of copper being from 0.1 to 3%, said catalyst being in particular Ru2Cu3 @ Csi2H6P6W72024o The HPA ensures the depolymerization of the lignocellulosic material. The metal associations are, in particular, combinations of ruthenium and copper. Ruthenium will more particularly ensure the hydrogenation of the unsaturated functional groups C = C and C = O but not the cleavage of the C-O bonds. Copper will promote cleavage of C-O bonds, but not hydrogenation. According to another advantageous embodiment of the invention, a trifunctional bimetallic catalyst of formula NixCuy @ CsnH3 PW-12-40 is used, in which "@" means "supported", x and y being from 0.01 to 1, n = 1 to 3, the weight percentage of nickel being from 0.1 to 2%, the weight percentage of copper being from 0.1 to 2%, said catalyst being in particular Ni3Cu3 @ Csi2H6P6W72024o. The metal associations are, in particular, combinations of nickel and copper. Nickel will more particularly ensure the hydrogenation of the unsaturated functional groups C = C and C = O but not the cleavage of the C-O bonds. Copper will promote the cleavage of the C-O bonds, but not the hydrogenation.

According to another advantageous embodiment of the invention, a trifunctional bimetallic catalyst of formula RexCuy @ CsnH3 PW-12 40 is used, in which "@" means "supported", x and y are from 0.01 to 1, n = 1 to 3, the weight percentage of rhenium is from 0.1 to 2%, the weight percentage of copper is from 0.1 to 2%, said catalyst being in particular Re Cu3 @ Csi2H6P6W72024o.

The metal associations are, in particular, combinations of rhenium and copper. Rhenium will more particularly ensure the hydrogenation of the unsaturated functional groups C = C and C = O but not the cleavage of the C-O bonds. Copper will promote the cleavage of the C-O bonds, but not the hydrogenation. The invention relates to a process for converting lignocellulosic material into low oxygen biofuel comprising, in the same reactor, the following steps: a step of mixing the cellulosic material consisting of milled wood and previously defined catalyst, to obtain a mixture consisting of milled wood and catalyst, - a step of heating said mixture in hydrogen to obtain a heated heterogeneous mixture containing a liquid consisting of water and organic molecules, and a solid consisting of milled wood and catalyst, - a step of distilling said liquid to obtain a liquid consisting of an aqueous phase and an organic phase, said organic phase containing a mixture of saturated or unsaturated hydrocarbons, aromatic or non-aromatic and aromatic oxygen molecules, and wherein the percentage oxygen mass is in particular less than or equal to 5%, in particular from 3% to 4.5%, in particular about 3.5%. The mixture obtained in the organic liquid phase, analyzed by mass spectroscopy and by gas chromatography, contains the following molecules: linear or branched, branched or unbranched alkanes containing from 5 to 10 carbon atoms, comprising in particular from 5 to 8 carbon atoms, - Aromatic compounds containing from 6 to 15 carbon atoms, optionally substituted with one or more alkyl groups, especially with methyl, ethyl or / and propyl groups, or substituted with a hydroxyl group, Possible trace of alkenes. The proton NMR spectrum of a mixture constituting the organic phase is reproduced in FIG. 2. The mass spectrum of the organic phase of a mixture constituting the organic phase is reproduced in FIG. 3. The invention relates to a transformation method. lignocellulosic material in which hydrogen heating of the mixture of milled wood and catalyst results in (1) depolymerization of the molecules contained in the lignocellulosic material to obtain a mixture of molecules with a molar mass of less than 200 g.mo1-1, (2) the deoxygenation of the molecules obtained after depolymerization of the lignocellulosic material, (3) and the hydrogenation of the molecules produced after deoxygenation, the three functions being provided at once or in a consecutive manner.

After heating, a gaseous phase, a solid phase and a liquid phase are obtained. The gaseous phase contains hydrogen, carbon monoxide and alkanes having 1 to 4 carbon atoms. The residual solid is made of coal. The liquid consists of two phases: an aqueous phase and an organic phase, the latter containing the molecules constituting the biofuel. In order to demonstrate the advantageous action of the trifunctional bimetallic catalyst, tests have been carried out on several occasions from 10 g of milled wood: (1) without catalyst, (2) with a catalyst of formula 3% Ru / 1% Cu · HCs2PW12040 All other parameters are identical: temperature, hydrogen pressure, duration of heating, treatment, distillation. Without catalyst, the organic phase is virtually non-existent (0.5 g) while the solid residue made of coal is important since it represents up to 50% by weight of the mixture obtained.

On the other hand, with the catalyst of formula 3% Ru / 1% Cu · HCs2PW12040, the mass of organic phase is 3.1 g, while the residual solid is very scarce (0.9 g). In both cases, the gaseous phase generated by the transformation corresponds to about 2 g, ie about 20% by weight of the mixture. With substantially different catalysts, results are obtained making it possible to formulate the same conclusion: the trifunctional bimetallic catalyst has the following three functions: the depolymerization, provided by the HPA, the deoxygenation, provided by the metal M ", in particular by copper, hydrogenation, provided by the metal M ', in particular by rhenium, nickel or ruthenium.according to a particular embodiment of the process referred to above, the mixing step is carried out under the following conditions heating to 60 ° C under vacuum of the mixture of milled wood and catalyst to obtain a heated mixture of ground wood and catalyst, treatment in hydrogen of said heated mixture under a pressure of about 10 to 100 bar, in particular from about 20 to 60 bar, to obtain a mixture heated under hydrogen pressure, - mechanical stirring of the above mixture obtained at preceding step at a speed of 300 rpm to 1000 rpm, in particular approximately equal to 500 rpm, to obtain a mixture heated under hydrogen pressure and stirred, heating for a period of time ranging from 1 h to 5 h, in particular about 3 hours, at a temperature of less than or equal to 500 ° C, in particular about 350 ° C to 500 ° C, especially about 400 ° C to 470 ° C, to obtain a heterogeneous mixture containing a liquid and a solid. According to an advantageous aspect of the process designated above, the catalyst is recovered in the solid phase, calcined under O 2 to remove the residual carbon, and then reduced under H2 at 300 ° C for 3h under 1 bar pressure. The catalyst is recovered for recycling and re-engaged. According to a particular embodiment of the lignocellulosic material transformation method, the catalyst has the formula RuxCuy @ Csn1-13 PW-12 40, in which "@" means "supported", x and y being from 0.01 to 1, n = 1 to 3, the weight percentage of ruthenium being from 0.1 to 3%, the weight percentage of copper being from 0.1 to 3%, said catalyst being in particular Cu3 @ Csi2H6P6W72024o According to a particular mode of the process for converting the lignocellulosic material, the catalyst has the formula NixCuy @ Csn1-13 PW-12 40, in which "@" means "supported", x and y being from 0.01 to 1, n = 1 to 3, the weight percentage of nickel being from 0.1 to 2%, the weight percentage of copper being from 0.1 to 2%, said catalyst being in particular Ni3Cu3 @ Csi2H6P6W720240. According to a particular embodiment of the lignocellulosic material transformation method, the catalyst has the formula Re'M "y @ Cs'H3, x1 \ 41204o, in which" @ "means" supported ", x and y being 0 , 01 to 1, n = 1 to 3, the weight percentage of rhenium being from 0.1 to 2%, the weight percentage of copper being from 0.1 to 2%, said catalyst being in particular ReCu3 @ Csi2H6P6W72024o L ' The invention relates to a process for the transformation of lignocellulosic material and a process for the preparation of the catalyst described above.The invention relates to a process consisting of, or comprising: (1) a step of preparing a trifunctional bimetallic catalyst, comprising the following steps a step of mixing - an HPA, - a Z element of group IA or IIA in the form of Z + or Z2 + cation, coming from an aqueous solution of a salt of this element, - a metal M 'of group VIIB or VIIIB in the form of cation at the degree of o xydation + II, + III or + VII, and a metal M "of the group D3 or IIB in the form of a cation at the oxidation state + I or + II, the water then being removed from said mixture, in particular by evaporation to obtain a partially dry solid containing the following components: - an HPA, - a Z element of group IA or IIA in the form of a Z + or Z2 + cation originating from an aqueous solution of a salt of this element, - a metal M Group VIIB or VIIIB in the form of oxidation cation + II, + III or + VII, - Group IB or IIB metal M in the form of oxidation cation + I or + II, - and the anions associated with the above cations, the anions being chosen from the carboxylate ion (RC00), R being a linear or branched alkyl group containing from 1 to 6 carbon atoms, the carboxylate ion being in particular the acetate ion (AcO ), the nitrate ion (NO3), the chloride ion (Cl), the oxide ion (02), the cyanide ion (CN), the sulfate ion (SO421), a calcination step at atmospheric pressure etching in dry air of said partially dry solid to remove said physisorbed water and said anions from said solid, to obtain a dry solid, then a hydrogen treatment step of said dry solid to obtain a dry solid in which M 'and M "are reduced to zero oxidation state, to obtain a trifunctional bimetallic catalyst, (2) a step of transformation of the lignocellulosic material into biofuel comprising, in the same reactor, the following steps: a step of mixing the material cellulosic composition consisting of milled wood and catalyst, to obtain a mixture of milled wood and catalyst, a step of heating said mixture in hydrogen to obtain a heated heterogeneous mixture containing a liquid consisting of water and organic molecules, and a solid consisting of milled wood and catalyst, a distillation step of the aforesaid liquid to obtain a liquid consisting of a ph aqueous phase and an organic phase, said organic phase containing a mixture of saturated or unsaturated hydrocarbons, aromatic or non-aromatic and aromatic oxygen molecules, and wherein the percentage by mass of oxygen is in particular less than or equal to 5 %, in particular from 3% to 4.5%, in particular approximately equal to 3.5%.

FIGURE I represents the reactor and the mixture contained therein, heated to 350 ° C. At first, the mixture is calcined. Then, it is put under dry air (02 + N2), then under H2 (reduction). These different steps are carried out in the same reactor.

FIGURE II shows the 1 H-NMR spectrum of an organic phase obtained in Examples 10, 11, 12 and 13. The spectrum is recorded in DMSO-d6. On the abscissa, the chemical shift δ expressed in ppm and ordinate is the signal intensity. The spectrum shows a maximum of H in the alkane region (0.5 to 3 ppm) while few aromatics are present in the mixture (low signal intensity in the region 6 to 8 PPm). FIG. III represents the mass spectrum of the organic phase obtained in Examples 10, 11, 12 and 13. The retention times are indicated on the abscissa, in minutes.

EXAMPLES Meaning of Abbreviations Used: TEM: Transmission Electron Microscopy, BET: Stephen Brunauer- Hugh Emmett Paul-Edward Teller DRIFT: Diffuse Infrared Reflectance Fourier Transform, NPs: Nanoparticles GC-MS: Gas Chromatography Coupled to 1E1 Mass Spectroscopy NMR: proton nuclear magnetic resonance DMSO: dimethylsulfoxide Characteristics / types of analytical devices used: NMR: Bruker AC-300 spectrometer (1E1300 MHz, 13C 75 MHz), MET: Transmission Electron Microscopy (TEM) using a Philips CM120 120 kV BET: Micromeritics ASAP 2020 GC / MS: Agilent GC 6850 MS 5975C Elemental Analysis: CHNS / O Analyzer Thermo Electron Flash EA 1112 Welience Series - Molecular Chemistry Division Faculty of Mirande Sciences (Dijon, France). mass spectroscopy micrOTOF-Q II Electron Spray Ionization Mass Spectrometer.

Starting materials Ni (OAc) 2, NiCl 2, Ni (acac) 2, RuCl 3, CymRuCl 2, RuCl 2 (PPh 3) 3, Ru 2 Cl 2 O 12, NH 4 ReO 4, Fe (NO 3) 3, Fe (OAc) 2, OsCi 2 O 12, OsCl 3, Co 2 C 8 O 8, CoSO4, RhCl3, Rh (NO3) 3, IrC13, Ir4Cl2O12, Pd (OAc) 2, PdCl3, Pt (NO3) 2, Pt (OAc) 2, Cu (NO3) 2.3H2O, CuCl2, Zn (NO3) 2, ZnCl2, AgNO3, Ag2O, AuCl, AuCN, Cd (NO3) 2, CdCl2, are provided by Aldrich. Example 1: Solid support formation consisting of an HPA and a cesium salt 2 g of H3PW12040 are introduced into a 50 ml flask. 4.6 ml of an aqueous solution of Cs2CO3 (1M) are then added dropwise at room temperature. The solution is stirred overnight at room temperature. A white solid is obtained after evaporation of the solvent. The product formed is calcined at 300 ° C in dry air for 3h, then under hydrogen flow at 300 ° C for 3h.

The product obtained is characterized by TEM, BET (specific surface), DRIFT and by elemental analysis. Preparation of Bi-Metal Catalysts Supported on HPA: Example 2 Preparation of HPA-supported Nickel / Copper Bimetallic Particles, General Formula Ni / Cu® HPA in Which the Ratio is P / oNi / PACu 5 g of H3PW12040 are introduced into a flask 190 mg Cu (NO3) 23H20 (1% Cu) and 212 mg Ni (OAc) 2. 6 ml of an aqueous solution of cesium carbonate (Cs2CO3) of concentration 1 mol / l are then added to the mixture, dropwise and at room temperature. The medium is stirred overnight at room temperature. After evaporation of the water, the solid is calcined under dry air for 3 hours at 300 ° C. and then treated under hydrogen at 300 ° C. for 3 hours. The final product is characterized by elemental analysis of Cu and Ni (% Cu = 1.2% and% Ni = 1.1%) and by TEM. The TEM results show the formation of the 2.1 ± 0.5 nm average size NPs having a well-defined spherical structure with a homogeneous dispersion. EXAMPLE 3 Preparation of HPA-supported nickel / copper bimetallic particles, general formula Ni / Cu HPA which ratio is 1% Ni / 0.2% Cu 5g of H3PW12040 are mixed with 42.5mg of Cu (NO3) 23H20 (1% Cu) and 212mg of Ni (OAc) 2 in a flask. 6 ml of an aqueous solution of cesium carbonate (Cs2CO3) of concentration 1 mol / L are added to the mixture, dropwise and at room temperature. The medium is stirred overnight at room temperature. After evaporation of the water, the solid is calcined under dry air for 3 hours at 300 ° C. and then treated under hydrogen at 300 ° C. for 3 hours.

The final product is characterized by elemental analysis of Cu and Ni (% Cu = 0.26,% Ni = 1.08%) and by TEM. TEM results show the formation of medium-size bimetallic NPs equal to 1.6 ± 0.6 nm with a non-homogeneous dispersion. Example 4 Preparation of HPA-supported nickel / copper bimetallic particles, general formula Ni / Cu® HPA in which the ratio is 0.2% Ni / 1% copper. 5 g of H3PW12040 are mixed with 190 mg of Cu (NO3) 23H20 (1% of Cu) and 38 mg of Ni (OAc) 2 in a flask. 6 ml of an aqueous solution of cesium carbonate (Cs2CO3) of concentration 1 mol / L are added dropwise to the mixture at room temperature. The medium is stirred overnight at room temperature. After evaporation of the water, the solid is calcined under dry air for 3 hours at 300 ° C. and then treated under hydrogen at 300 ° C. for 3 hours. The final product is characterized by elemental analysis of Cu and Ni (Cu: 1.11% and Ni: 0.27%) and by TEM. TEMs show the formation of medium size bimetallic NPs of 2.4 ± 0.8 nm with a homogeneous dispersion. EXAMPLE 5 Preparation of ruthenium / copper bimetallic particles supported on HPA, general formula Ru / Cu® HPA in which the ratio is 1% Ru / 1% Cu 5g H3PW12040 are mixed with 190mg Cu (NO3) 23H20 (1% Cu) and 474.6mg RuC12 (PPh3) 3 in a flask. 6 ml of an aqueous solution of cesium carbonate (Cs2CO3) of concentration 1 mol / L are added dropwise to the mixture at room temperature.

The medium is stirred overnight at room temperature. After evaporation of the water, the solid is calcined under dry air for 3 hours at 300 ° C. and then treated under hydrogen at 300 ° C. for 3 hours. The final product is characterized by elemental analysis of Cu and Ru (Cu: 1.03% and Ru = 0.80%) and by TEM. TEM images show the formation of well-defined bimetallic NPs, of average size equal to 1.40 ± 0.24nm and with a homogeneous dispersion. Example 6: Preparation of ruthenium / copper bimetallic particles supported on HPA, general formula Ru / Cu @ HPA in which the ratio is 1% Ru / 0.2% Cu. 5 g of H3PW12040 are mixed with 42.5 mg of Cu (NO3) 23H20 (1% Cu) and 474.6 mg of RuC12 (PPh3) 3 in a flask. 6 ml of an aqueous solution of cesium carbonate (Cs2CO3) of concentration 1 mol / L are added dropwise to the mixture at room temperature. The medium is stirred overnight at room temperature. After evaporation of the water, the solid is calcined under dry air for 3 hours at 300 ° C. and then treated under hydrogen at 300 ° C. for 3 hours. The final product is characterized by elemental analysis of Cu and Ru (Cu: 0.22% and Ru 20: 0.81%) and by TEM. TEM images show the formation of NPs of average size equal to 1.7 ± 0.48 nm and with a heterogeneous dispersion on the support. Example 7 Preparation of ruthenium / copper bimetallic particles supported on HPA, general formula Ru / Cu @ HPA in which the ratio is 0.2% Ru / 1 / oCu. 5g of H3PW12040 are mixed with 190mg of Cu (NO3) 23H20 (1% Cu) and 95mg of RuC12 (PPh3) 3 in a flask. 6 ml of an aqueous solution of cesium carbonate (Cs2CO3) of concentration 1 mol / L are added dropwise to the mixture at room temperature. The medium is stirred overnight at room temperature. After evaporation of the water, the solid is calcined under dry air for 3 hours at 300 ° C. and then treated under hydrogen at 300 ° C. for 3 hours.

The final product is characterized by elemental analysis of Cu and Ni (Cu: 1.03% and Ru: 0.18%) and by TEM. TEM images show the formation of well-defined bimetallic NPs of average size equal to 1.60 ± 0.34 nm with a homogeneous dispersion.

Example 8 Preparation of ruthenium / copper bimetallic particles supported on HPA, general formula Ru / Cu @ HPA in which the ratio is 2% Ru / 1 / oCu.

In a 50mL flask, 5g of the HPA (H3PW12040) are introduced. 190 mg of Cu (NO3) 23H20 and 202 mg of RuC13 are then added. 6 ml of an aqueous solution of cesium carbonate (Cs2CO3) of concentration 1 mol / L are added dropwise to the mixture at room temperature. The medium is stirred overnight at room temperature. After evaporation of the water, the solid is calcined under dry air for 3 hours at 300 ° C. and then treated under hydrogen at 300 ° C. for 3 hours. The final product is characterized by elemental analysis of Ru and Cu by analysis of BET specific surface area and TEM. The BET analysis gives us a specific surface of the order of 9m2 / g. TEM images show the presence of very small particles (average size = 1.25 ± 0.34 nm) bimetallic distributed homogeneously on the support. Example 9 Preparation of ruthenium / copper bimetallic particles supported on HPA, general formula Ru / Cu @ HPA in which the ratio is 3% Ru / 1 / oCu.

In a 50mL flask, 5g of H3PW12040 are introduced. 190 mg of Cu (NO3) 23H20 and 303 mg of RuC13 are then added. 6 ml of an aqueous solution of cesium carbonate (Cs2CO3) of concentration 1 mol / L are added dropwise to the mixture at room temperature. The medium is stirred overnight at room temperature. After evaporation of the water, the solid is calcined under dry air for 3 hours at 300 ° C. and then treated under hydrogen at 300 ° C. for 3 hours. The final product is characterized by elemental analysis of Ru and Cu. The specific surface area, measured by BET, is of the order of 7 m 2 / g.

TEM images show the presence of bimetallic particles (mean size = 2.16 ± 0.54 nm) homogeneously distributed on the support.

Catalytic tests on lignocellulosic material consisting of crushed wood Example 10: mixture of wood and catalyst of formula 2% Ru / 1% Cu @ HCs2PW1204o, hydrogen pressure: 40 bars. 10 g of milled wood are mixed with 1 g of bimetallic catalyst of formula 2% Ru + 1% Cu · HCs2PW12040 prepared according to Example 8, ie 10% by weight of catalyst relative to wood. The mixture is heated to 60 ° C under vacuum (10-2 mbar). Hydrogen is then introduced into the reactor, the mixture then being under a pressure of 40 bar of hydrogen. The mixture is then mechanically stirred at a speed of 500 rpm and heated to 470 ° C with a heating rate of 2 ° C / min. The temperature is maintained at 470 ° C. for 3 hours. In-situ pressure at 470 ° C reaches 90bars. The liquids are then distilled under vacuum while hot (470 ° C.), the distillate being cooled in a trap at -195 ° C. (liquid nitrogen). The liquid part has two phases separated by decantation, then analyzed by GC-MS, 1H NMR in DMSO. The experiment is reproduced twice. The results below summarize the different amounts of liquid phase (aqueous and organic), solid phase and gas phase. Test 1: mass of aqueous phase = 3.6 g, mass of the organic phase = 3.0 g, total mass of the liquid phase = 6.6 g, mass of the residual solid = 1.0 g, gaseous phase mass = 2.4 g. aqueous phase mass = 4.0g, mass of the organic phase = 2.8g, total mass of the liquid phase = 6.8g, mass of the residual solid = 1.0g, gaseous phase mass = 2.2g.

Test 2: Example 11: mixture of wood and catalyst of formula 1% Ru / 1% Cu @ HCs2PW1204o, 40 bar hydrogen pressure 9.95 g of milled wood are mixed with 1 g of Ru / Cu @ HPA catalyst ( 1% Ru + 1% Cu @ HCs2PW12040) prepared according to Example 6, ie 10% by weight of catalyst relative to wood. The mixture is heated to 60 ° C under vacuum (10-2 mbar). Hydrogen is then introduced into the reactor, the mixture then being under a pressure of 40 bar of hydrogen. The mixture is then mechanically stirred at a speed of 500 rpm and heated to 470 ° C with a heating rate of 2 ° C / min. The temperature is maintained at 470 ° C. for 3 hours. In-situ pressure at 470 ° C reaches 84 bar. The liquids are then distilled under vacuum while hot (470 ° C.), the distillate being cooled in a trap at -195 ° C. (liquid nitrogen). The liquid part has two phases separated by decantation, then analyzed by GC-MS, EIRMN in DMSO. The following masses are obtained: mass of aqueous phase = 3.9 g, mass of the organic phase = 2.1 g, total mass of the liquid phase = 6 g, mass of the residual solid = 1.4 g, gas phase mass = 2.6 g.

Example 12: Mixture of Wood and Catalyst of Formula 3% R 1% Cu · HC 2 PW 1 0 040 40, 40 bar hydrogen pressure 10 g of milled wood are mixed with 1 g of the catalyst of formula 3% Ru + 1% Cu · HCs 2 PW 1 20 40 prepared according to US Pat. Example 9, 10% by weight of catalyst relative to wood. The mixture is heated to 60 ° C under vacuum (10-2 mbar). Hydrogen is then introduced into the reactor, the mixture then being under a pressure of 40 bar of hydrogen. The mixture is then mechanically stirred at a speed of 500 rpm and heated to 470 ° C with a heating rate of 2 ° C / min. The temperature is maintained at 470 ° C. for 3 hours. In situ pressure at 470 ° C reaches 88 bar. The liquids are then distilled under vacuum while hot (470 ° C.), the distillate being cooled in a trap at -195 ° C. (liquid nitrogen). The liquid part has two phases separated by decantation, then analyzed by GC-MS, EIRMN in DMSO. The following masses are obtained: mass of aqueous phase = 3.9 g, mass of the organic phase = 3.1 g, total mass of the liquid phase = 7 g, mass of the residual solid = 0.9 g, gaseous phase mass = 2.1 g.

Example 13: Wood and catalyst mixture of formula 2% Ru / 1% Cu · HCs2PW12040, hydrogen pressure 60 bar 10.1g of ground wood are mixed with 1.05 g of the catalyst of formula 2% Ru / 1% Cu @ HCs2PW12040 prepared according to Example 8, ie about 10% by weight of catalyst relative to wood. The mixture is heated to 60 ° C under vacuum (10-2 mbar). Hydrogen is then introduced into the reactor, the mixture then being under a pressure of 60 bar of hydrogen. The mixture is then mechanically stirred at a speed of 500 rpm and heated to 470 ° C with a heating rate of 2 ° C / min. The temperature is maintained at 470 ° C. for 3 hours. In-situ pressure at 470 ° C reaches 110 bar. The liquids are then distilled under vacuum while hot (470 ° C.), the distillate being cooled in a trap at -195 ° C. (liquid nitrogen). The liquid part has two phases separated by decantation, then analyzed by GC-MS, 1H NMR in DMSO.

The following masses are obtained: mass of aqueous phase = 3.9 g, mass of the organic phase = 2.9 g, total mass of the liquid phase = 6.8 g, mass of the residual solid = 0.6 g, gas phase mass = 2.6 g.

Example 14: Mixture of Wood and Catalyst of Formula 1% Ni / 1% Cu @ HCs 2 PW120409 Hydrogen Pressure 20 Bars In an autoclave, 10.1 g of milled wood are mixed with 1.05 g of the catalyst of formula 1% Ni / 1% Cu @ HCs2PW12040) prepared according to Example 2, ie approximately 10% by weight of catalyst relative to wood. The mixture is then heated to 60 ° C under vacuum (10-2 mbar). Hydrogen is then introduced into the reactor, the mixture then being under a pressure of 20 bar of hydrogen. The mixture is then mechanically stirred at a speed of 500 rpm and heated to 400 ° C with a heating rate of 2 ° C / min. The temperature is maintained at 400 ° C. for 1 h. The pressure in situ at 400 ° C reaches 50 bar. The liquids are then distilled under vacuum while hot (400 ° C.), the distillate being recovered in a trap cooled to -195 ° C. (liquid nitrogen). The liquid is analyzed by GC-MS. The following masses are obtained: mass of liquid phase = 3.4 g, mass of residual solid = 4.1, mass of gaseous phase = 2.5 g. Example 15: comparative test, milled wood without catalyst, heated under hydrogen 9.95 g of milled wood are heated to 60 ° C under vacuum (10-2 mbar). Hydrogen is then introduced into the reactor, the milled wood then being under a pressure of 40 bar of hydrogen. The milled wood is then mechanically stirred at a speed of 500 rpm and heated to 470 ° C with a heating rate of 2 ° C / min. The temperature is maintained at 470 ° C. for 3 hours. In-situ pressure at 470 ° C reaches 78 bar. The liquids are then distilled under vacuum while hot (470 ° C.), the distillate being recovered in a trap cooled to -195 ° C. (liquid nitrogen). The liquid part has a single phase analyzed by GC-MS, 1H NMR in DMSO.

The masses are obtained: mass of aqueous phase = 3 g, mass of organic phase - 0.5 g, total mass of liquid phase = 3.5 g, mass of residual solid = 4.5 g, mass of gaseous phase = 2. Og. EXAMPLE 16 Comparative Test, Wood Grinded with HPA Without Supported Metals, Pressure of 60bars in Hydrogen In an autoclave, 10.1 g of milled wood are mixed with 1 g of HPA. The mixture is heated at 20 ° C under vacuum (10-2 mbar). Hydrogen is then introduced into the reactor, the milled wood then being under a pressure of 20 bars of hydrogen. The mixture is then mechanically stirred at a speed of 500 rpm and heated to 400 ° C with a heating rate of 2 ° C / min. The temperature is maintained at 400 ° C. for 1 h. The pressure in situ at 400 ° C reaches 45 bar. The liquids are then distilled under vacuum while hot (400 ° C.), the distillate being recovered in a trap cooled to -195 ° C. (liquid nitrogen). The recovered liquid phase is analyzed by GC-MS. The following masses are obtained: mass of liquid phase = 3.8 g, mass of residual solid = 3.6 g, mass of gaseous phase = 1.6 g. Example 17: Table "The Different Molecules Observed by GC-MS Analysis in the Organic Phases corresponding to Examples 10, 11, 12 and 13" go ---....--, - 4 -...... -, - 6 7 8 3 5 OH 1101 1.1 lel 9 10 11 12 13 14 15 16 OH OH OH O OH 01 01 01 0 the 1.11) lei se 17 18 19 20 21 22 23 24 OH 10 * el 01. 25 26 27 20

Claims (14)

REVENDICATIONS1. Trifunctional bimetallic catalyst consisting of - a heteropoly acid (HPA), in the form of a monomer - of a Z element of group IA or IIA, - a metal M 'of group VIIB or VIIIB, - and a metal M "of group IB or IIB. 2. trifunctional bimetallic catalyst according to claim 1, forming solid nanoparticles, whose mean size distribution is between 0.8 nm and 3 nm. 3. Trifunctional bimetallic catalyst according to one of claims 1 or 2, wherein the HPA is of Keggin type or Wells-Dawson type, Andersson, Lindqvist, Strandberg, Allman-Waugh, Weakley-Yamase, or Dexter, said HPA being especially of the Keggin type, and in particular, in which: the HPA is of Keggin type and has the formula H3X1V11204o in which ^ X represents - an element of the group IVA chosen from Si, Ge, Sn, Pb, - or an element of the group VA chosen from P, As, Sb, Bi, X being in particular the phosphorus element P, M represents an element of the group VB or VIB chosen from Cr, Mo, W, V, in particular representing Mo or W, being in particular W Said HPA having especially the formula H3PW1204o, and in particular, in which the element Z is in the form of cation Z +, chosen from Li +, Na +, K +, Rb +, Cs +, or of cation Z2 + chosen from Be2 +, Ca2 + , Mg2 +, Sr a2 +, said cation being in particular cs +. 4. Trifunctional bimetallic catalyst according to one of claims 1 to 3: in which the HPA is of Keggin type, Z belongs to group IA and is in the form of Z + cation, said HPA and Z + forming a derivative of formula ZnH3_nXIV11204o in wherein n represents the number of Z + cation such that n = 1 to 3.7 - or, in which the metal M 'is supported by the derivative of formula ZnH3_, X1 \ 41204o, the metal M' belonging to group VIIB and being chosen from Mn or Re, or the metal M 'belonging to the group VIIIB and being chosen from Fe, Ru, Os, Co, Rh, Ir, Ni, Pd or Pt, said metal M' being especially Ru, Ni or Re, or in which the metal M "is supported by the derivative of formula 41-13_nXM1204o, the metal M" belonging to group IB and being selected from Cu, Ag or Au, or the metal M "belonging to group IIB and being chosen among Zn or Cd, said metal M "being in particular Cu. 25 A trifunctional bimetallic catalyst according to one of claims 1 to 4, having the formula M'xiVry @ ZnH3-nXI \ 412040, in which "@" means "supported", M '= Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd or Pt, in particular Ru, Ni or Re, M "= Cu, Ag, Au, Zn, Cd, in particular Cu, Z = Li +, Na +, K +, Rb +, Cs +, Be2 + , Ca 2+, Mg 2+, Sr 2+, a 2+, especially Cs +, X = Si, Ge, Sn, Pb, P, As, Sb, Bi, especially P, M = Cr, Mo, W, V, in particular Mo or W , in particular W, x and y being from 0.01 to 1, n = 1 to 3, said metal M 'having a weight percentage of from 0.1 to 3%, said metal M "having a weight percentage of from 0 to , 1 to 3%, and especially having the formula M'xM "yg CsnE13_nPW120-4o, in which" @ "means" supported ", M '= Mn, Re, Fe, Ru, Os, Co, Rh, Ir , Ni, Pd or Pt, especially Ru, Ni or Re, M "= Cu, Ag, Au, Zn, Cd, in particular Cu, x and y being from 0.01 to 1, n = 1 to 3, said metal M 'having a mass percentage of 0.1 to 3%, said metal M "having a weight percentage of 0.1 to 3%. * and in particular, having the formula Ru'Cuy @ CsnH3_nPW120-4o, in which "@" means "supported", x and y being from 0.01 to 1, n = 1 to 3, the mass percentage of ruthenium being comprised of 0.1 to 3%, the weight percentage of copper being from 0.1 to 3%, and especially, having the formula NixCuy @ CsnH3 PW o -n- - 12-40, in which "g" means "supported X and y being from 0.01 to 1, n = 1 to 3, the weight percentage of nickel being from 0.1 to 2%, the weight percentage of copper being from 0.1 to 2%, and especially, having the formula RexCuy @ Csr, H3, PW1204o, in which "@" means "supported", x and y are from 0.01 to 1, n = 1 to 3, the weight percentage of rhenium is from 0 1 to 2%, the weight percentage of copper is from 0.1 to 2%, and especially having the formula Cu 3 @ Cs 12 H 6 P 6 O 7 O 2 O 5 containing 1% by weight of Ru and 1% by weight of Cu. * and in particular, having the formula Ni3Cu3 @ Cs12H6P6W72024o, 20 containing 1% by weight of Ni and 1% by weight of Cu, * and in particular, having the formula ReCu3 @ Cs12H6P6W720240 containing 1% by weight of Re and 1 1% by weight of copper. 6. Process for the preparation of a trifunctional bimetallic catalyst according to one of claims 1 to 5, comprising a step of calcination at atmospheric pressure in dry air of a partially dry solid containing the following components: an HPA, a element Z of group IA or IIA in the form of a Z + or Z2 + cation originating from an aqueous solution of a salt of this element, - a Group VIIB or VIIIB metal M 'in the form of a cation with oxidation state + II, or + III, - a metal M "of the group IB or IIB in the form of cation with the degree of oxidation + I or + II, - and the anions associated with the above cations, the anions being chosen from the carboxylate ion (RC00) , R being a linear or branched alkyl group containing from 1 to 6 carbon atoms, the carboxylate ion being in particular the acetate ion (AcO), the nitrate ion (NO3-), the chloride ion (Cl), l oxide ion (02), cyanide ion (CN), sulfate ion (SO42), to remove physisorbed water from the solid, to reduce meta and M "and M", to decompose the aforesaid anions and to obtain a dry solid containing the aforesaid components, then a step of treating under atmospheric pressure hydrogen of the aforesaid dry solid to obtain a dry solid in which M 'and M " are reduced to the zero oxidation state, and in particular comprising a mixing step of a Keggin-type or Wells-Dawson-type HPA, Andersson, Lindqvist, Strandberg, Allman-Waugh, Weakley-Yamase, Dexter, in particular of the Keggin type, - an aqueous solution to a salt of element Z of group IA or IIA, - a metal salt M 'group VIIB or VIIIB, - and a salt of metal M " group IB or IIB, the water being then removed from said mixture, in particular by evaporation, to obtain a partially dry solid containing the following components: - an HPA, - a Z element of group IA or IIA in the form of Z + or Z2 + cation from an aqueous solution of a salt of this element, a group VIIB or VIIIB metal M ' or form of cation at the oxidation state + II, or + III, - a metal M "of the group IB or IIB in the form of oxidation cation - and the anions associated with the above cations, the anions being chosen from 1 carboxylate ion (RC00-), R being a linear or branched alkyl group containing from 1 to 6 carbon atoms, the carboxylate ion being in particular the acetate ion (AcO-), the nitrate ion (NO3-), l chloride ion (CF), the oxide ion (02.), the cyanide ion (CN-), the sulfate ion (SO421 *) and in particular in which the mixing step is carried out at room temperature, especially with mechanical stirring. at a stirring speed of from 200 rpm to 600 rpm, in particular about 300 rpm, for about 12 hours, the water then being removed, in particular by evaporation, to obtain a partially dry solid containing the following components: - an HPA, - a Z element of group IA or IIA in the form of a Z + or Z2 + cation originating from an aqueous solution of a salt of this element, - a metal M 'of the group VIIB or VIIIB in the form of cation with the oxidation state + II, or + III, - a metal M "of the group IB or IIB in the form of cation with the degree of oxidation + I or + II, - and the anions associated with the above cations, the anions being chosen from the carboxylate ion (RC00-), R being a linear or branched alkyl group containing from 1 to 6 carbon atoms, the carboxylate ion being especially the acetate ion (AcO-), the nitrate ion (NO3 "), the chloride ion (C1-), the oxide ion (02), the cyanide ion (CN-), the sulfate ion ( S0421 ^ a step of calcination at atmospheric pressure in dry air of said partially dry solid containing the following components: - an HPA, - a Z element of the group IA or IIA in the form of Z + or Z2 + cation coming from an aqueous solution of a salt of this element, - a Group VIIB or VIIIB metal M 'in the form of oxidation cation + II, or + III, - a Group IB or IIB metal M' in the form of oxidation state cation tion + I or + II, - and the anions associated with the above cations, the anions being chosen from the carboxylate ion (RC00-), R being a linear or branched alkyl group containing from 1 to 6 carbon atoms, the ion carboxylate being in particular the acetate ion (AcO-), the nitrate ion (NO3-), the chloride ion (CF), the oxide ion (02), the cyanide ion (C1 \ -1), the sulfate ion (SO42), to remove the physisorbed water from the solid and to decompose the above anions (nitrate, chloride, acetate, carboxylate, etc.) to obtain a dry solid, then a hydrogen treatment step to obtain a dry solid in which M 'and M "are reduced to the zero oxidation state, and in particular, in which the step of calcination of the partially dry solid containing the following components: - an HPA, - a Z element of the group IA or IIA in the form of a Z + or Z2 + cation originating from an aqueous solution of a salt of this element, a metal M 'of the group VIIB or VIIIB in the form of a cation with an oxy degree dation + II, or + III, - a metal M "of the group IB or IIB in the form of cation at the oxidation state + I or + II, - and the anions associated with the above cations, the anions being chosen from the ion carboxylate (RC00-), R being a linear or branched alkyl group containing from 1 to 6 carbon atoms, the carboxylate ion being in particular the acetate ion (AcO-), the nitrate ion (NO3-), the ion chloride (Cl-), the oxide ion (02-), the cyanide ion (CI \ F), the sulphate ion (SO421 is carried out in dry air for a period of time ranging from 0.5 h to 5 h, in particular about 3 hours, at a temperature of 250 ° C to 400 ° C, especially about 300 ° C, to remove the physisorbed water and the above associated anions from the solid and to obtain a dry solid, then a hydrogen treatment step of said dry solid, to obtain a dry solid in which M 'and M "are reduced to the zero oxidation state, and in particular, wherein the hydrogen treatment step is carried out for a duration of from 0.5 h to 5 h, in particular a duration of about 3 hours, at a temperature of 250 ° C. to 400 ° C., in particular about 300 ° C., under a pressure of 0, 5 to 2 bar, in particular approximately equal to 1 bar, to obtain a dry solid in which M 'and M "are reduced to the zero oxidation state, and in particular in which the salt of the element Z contains this element in the form of cation associated with an anion chosen from the carboxylate ion (RC00-), R being a linear or branched alkyl group containing from 1 to 6 carbon atoms, the carboxylate ion being in particular the acetate ion (AcO), the nitrate ion (NO3-), chloride ion (Cl), oxide ion (02), cyanide ion (CN), sulfate ion (SO42), said salt being selected from Cs2CO3, CsCl, Rb2CO3, RbCl, SrCO3, SrCl2, BaSO4, BaCl2, BaCO3, and especially being cesium carbonate Cs2CO3, and in particular, in which - the group VIIB or VIIIB metal salt M ', containing the at the oxidation state 20 + II or + III, is associated with an anion chosen from the carboxylate ion (RC00-), R being a linear or branched alkyl group containing from 1 to 6 carbon atoms, the carboxylate ion being in particular the acetate ion (AcO-), the nitrate ion (NO3-), the chloride ion (CF), the oxide ion (O2), the said salt being optionally hydrated or associated with one or more ligands (s) ) chosen from chloride ion, sulfate (SO42), cyanide (CN), carboxylate (RC00), R being a linear or branched alkyl group containing from 1 to 6 carbon atoms, the carboxylate ion being in particular the acetate ion (AcO-), a phosphine chosen in particular from triphenylphosphine (PPh3) or trimethylphosphine (PMe3), an allyl group, phenyl, paracymene (Cym), carbonyl group (CO), cyclooctadiene (COD), cyclooctatetene (COT), acetylacetonate (acac), said group VIIB or VIIIB metal salt M 'being selected from Ni (OAc) 2, NiC12, Ni (acac) 2, RuC13, CymRuCl2, RuC12 (PPh) 3) Ru2C12012, NH4ReO4, Fe (NO3) 3, Fe (OAc) 2, OsC12012, OsC13, Co2C808, CoSO4, RhCl3, Rh (NO3) 3, IrC13, It4Cl2O12, Pd (OAc) 2, PdCl3, O3) 2, Pt (OAc) 2, - and the metal salt M "of group IB or IIB containing the metal at oxidation state + I or + II, being chosen from Cu (NO 3) 2, 3H 2 O, CuCl 2, Zn ( NO 3) 2, ZnCl 2, AgNO 3, Ag 2 O, AuCl, AuCN, Cd (NO 3) 2, CdCl 2, and especially Cu (NO 3) 2, 3H 2 O, the proportion M '/ M "being from 0.1 to 3, in particular from 0.5 to 3, and especially being equal to 1. A process for preparing a trifunctional bimetallic catalyst according to claim 6 having the formula Ruj, Cuy @ Cs.H3-nPW120-4o, wherein "@" means "supported", x and y being 0, 01 to 1, n = 1 to 3, the weight percentage of ruthenium being from 0.1 to 3%, the weight percentage of copper being from 0.1 to 3%, and in particular comprising a mixing step; an HPA of formula H3PW1204o, an aqueous solution of Cs2CO3, RuC12 (PPh3) 3, and Cu (NO3) 2,3H20, the water supplied by the aqueous solution of Cs2CO3 being then removed from said mixing, in particular by evaporation, to obtain a partially dry solid containing a mixture of HPA, cs + ions, Ru (II) and Cu (II), physisorbed water, carbonate and nitrate ions and PPh3 molecules a step of calcination at atmospheric pressure in dry air of said partially dry solid, to eliminate the physisorbed water, the carbonate and nitrate ions, and the PPh3 molecules, and to obtain a dry solid, then a hydrogen treatment step of said dry solid, to obtain a dry solid in which Ru and Cu are reduced to the zero oxidation state. 8. Process for the preparation of a trifunctional bimetallic catalyst according to claim 6, having the formula NixCuy @ Cs ,, H3 P o _n-W 12-40, in which "@" means "supported", x and y being included from 0.01 to 1, n = 1 to 3, the weight percentage of nickel being from 0.1 to 2%, the weight percentage of copper being from 0.1 to 2%, and in particular comprising step of mixing - an HPA of formula H3PW1204o, - an aqueous solution of Cs2CO3, - Ni (OAc) 2, - and Cu (NO3) 2,3H20, the water provided by the aqueous solution of Cs2CO3 then being removed from said mixture, in particular by evaporation, to obtain a partially dry solid containing a mixture of HPA, cs + ions, Ni (II) and Cu (II), physisorbed water, carbonate ions, acetate and nitrate, mu a calcination stage at atmospheric pressure under air of said partially dry solid, to eliminate physisorbed water, carbonate, acetate and nitrate ions, and for obtaining a dry solid, then a hydrogen treatment step of said dry solid, to obtain a dry solid in which Ni and Cu are reduced to the zero oxidation state. 9. Process for preparing a trifunctional bimetallic catalyst according to claim 6, RexCuy @ Csii113 PW _n. 12-40, in which x and y are from 0.01 to 1, n = 1 to 3, the weight percentage of rhenium is from 0.1 to 2%, the weight percentage of copper is from 0.1 at 2%, and in particular, comprising a mixing step of an HPA of formula H 3 PW 120 O 4, an aqueous solution of Cs 2 CO 3, NH 4 ReO 4, and Cu (NO 3) 2, 3H 2 O, water supplied by the aqueous solution of Cs2CO3 then being removed from said mixture, in particular by evaporation, to obtain a partially dry solid containing a mixture of HPA, cs + ions, Re (VII) and Cu (II), water physisorbed, carbonate ions, nitrate, ammonium, oxides, a calcination step of said partially dry solid, to remove the physisorbed water, carboxylate ions, nitrate, sulfate, and to obtain a dry solid, then a step of hydrogen treatment of said dry solid, to obtain a dry solid in which Re and Cu are reduced to the zero oxidation state. 10. Use of a trifunctional bimetallic catalyst according to one of claims 1 to 5, for the transformation of the lignocellulosic material into low oxygen biofuel, at a temperature of less than or equal to 500 ° C, in particular from 350 ° C to 500 ° C. C., in particular between 400 ° C. and 470 ° C., the mass of milled wood being comprised from 1 g to 20 g per 0.001 g to 2 g of catalyst, in particular approximately equal to 10 g of wood per 1 g of catalyst, and in particular Wherein the biofuel is obtained in the form of an organic phase containing a mixture of saturated or unsaturated hydrocarbons, aromatic or nonaromatic, and aromatic oxygen molecules, said mixture containing a percentage of oxygen in particular less than or equal to 5 %, in particular from 3 to 4.5%, especially equal to about 3.5%, the octane number of said mixture formed being from 90 to 120. 11. Use of a trifunctional bimetallic catalyst according to claim 10, of formula RuxCuy @ CsnH3_, PW1204o, in which "@" means "supported", 10 x and y being from 0.01 to 1, n = 1 to 3. , the mass percentage of ruthenium being from 0.1 to 3%, the weight percentage of copper being from 0.1 to 3%, said catalyst being in particular Cu3 @ Cs12H6P6W72024o, OR, of a trifunctional bimetallic catalyst of Ni'Cuy formula @ CsnE13 PW - 12 -40, wherein 20 "@" means "supported", x and y being from 0.01 to 1, n = 1 to 3, the weight percentage of nickel being from 0.1 to 2%, the percentage the weight of copper being from 0.1 to 2%, said catalyst being especially Ni3Cu3 @ Cs12H6P6W72024o. OR, a trifunctional bimetallic catalyst of the formula ## STR1 ## wherein "@" means "supported", x and y are from 0.01 to 1, n = 1 to 3, the percentage the mass percentage of rhenium is from 0.1 to 2%, the weight percentage of copper is from 0.1 to 2%, said catalyst being in particular ReCu3 @ Cs12H6P6W72024o. 12. Process for converting lignocellulosic material into low oxygen biofuel comprising, in the same reactor, the following steps: a step of mixing the cellulosic material consisting of milled wood and catalyst according to one of claims 1 to 5, to obtain a mixture of ground wood and catalyst, - a step of heating said mixture in hydrogen to obtain a heated heterogeneous mixture containing a liquid consisting of water and organic molecules, and a solid consisting of milled wood and catalyst, a distillation step of the aforesaid liquid to obtain a liquid consisting of an aqueous phase and an organic phase, said organic phase containing a mixture of saturated or unsaturated, aromatic or non-aromatic hydrocarbons and aromatic oxygen molecules, and in which the percentage by mass of oxygen is in particular less than or equal to 5%, in particular inclusive of e 3% to 4.5%, in particular approximately equal to 3.5%. 13. The process according to claim 12, wherein the catalyst has the formula RuxCuy @ CsnH3 PW n _n- - 12-40, wherein "@" means "supported", x and y being from 0.01 to 1, n = 1 to 3, the mass percentage of ruthenium being from 0.1 to 3%, the weight percentage of copper being from 0.1 to 3%, said catalyst being in particular Cu3 @ Cs12H6P6W72024o OR, in which the catalyst has for formula NixCuy @ CSnH3n- - 12-PW 0 40, in which "@" means "supported", x and y being from 0.01 to 1, n = 1 to 3, the mass percentage of nickel being from 0, 1 to 2%, the mass percentage of copper being from 0.1 to 2%, said catalyst being in particular Ni3Cu3 @ Cs12H6P6W72024o, OR, in which the catalyst has the formula RexCuy @ Csi, H3 PW _n- 12-40 wherein "@" means "supported", x and y being from 0.01 to 1, n = 1 to 3, the mass percentage of rhenium being 0.1 to 2%, the percent being the mass of copper being from 0.1 to 2%, said catalyst being in particular ReCu3 @ Cs12H6P6W72024o. 20 14. A process comprising (1) a step of preparing a trifunctional bimetallic catalyst according to one of claims 1 to 5 and comprising the following steps: 1. a step of mixing - an HPA, - a element Z of group IA or IIA in the form of a Z + or Z2 + cation, originating from an aqueous solution of a salt of this element, - a Group VIIB or VIIIB metal M 'in the form of a cation at the degree of oxidation + II, or + III, - and a metal M "of the group IB or IIB in the form of cation at the oxidation state + I or + II, the water then being removed from said mixture, in particular by evaporation, for to obtain a partially dry solid containing the following components: an HPA, a Z element of group IA or IIA in the form of a Z + or Z2 + cation originating from an aqueous solution of a salt of this element, a metal M 'of the group VIIB or VIIIB in the form of oxidation cation + II, or + III, - an M "metal of group IB or IIB in the form of cation at degree o xydation + I or + II, - and the anions associated with the above cations, the anions being chosen from the carboxylate ion (RC00-), R being a linear or branched alkyl group containing from 1 to 6 carbon atoms, the ion carboxylate being in particular the acetate ion (AcO-), the nitrate ion (NO3-), the chloride ion (Cl), the oxide ion (O2-), the cyanide ion (CN-), the ion sulfate (S0421) a step of calcination at atmospheric pressure in dry air of the aforesaid partially dry solid to remove from said solid the physisorbed water and the aforesaid anions, to obtain a dry solid, then a hydrogen treatment step of the aforesaid dry solid To obtain a dry solid in which M 'and M "are reduced to the zero oxidation state, to obtain a trifunctional bimetallic catalyst, (2) a step of transformation of the lignocellulosic material into biofuel comprising, in the same reactor, the following steps: 25 ^ a mixing step of the const cellulosic material 3. The crushed wood and catalyst system according to one of claims 1 to 5, for obtaining a mixture of ground wood and catalyst, a step of heating said hydrogen mixture in order to obtain a heated heterogeneous mixture containing a liquid consisting of water and organic molecules, and a solid consisting of milled wood and catalyst, a distillation step of the aforesaid liquid to obtain a liquid consisting of an aqueous phase and an organic phase, - said organic phase containing a mixture saturated or unsaturated hydrocarbons, aromatic or nonaromatic hydrocarbons and aromatic oxygen molecules, and wherein the percentage by mass of oxygen is in particular less than or equal to 5%, in particular from 3% to 4.5%, especially about 3.5% .5