WO2013178920A1 - Method for converting polyols in an aqueous phase in the presence of a catalyst containing titanium oxide and tungsten - Google Patents

Method for converting polyols in an aqueous phase in the presence of a catalyst containing titanium oxide and tungsten Download PDF

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Publication number
WO2013178920A1
WO2013178920A1 PCT/FR2013/051166 FR2013051166W WO2013178920A1 WO 2013178920 A1 WO2013178920 A1 WO 2013178920A1 FR 2013051166 W FR2013051166 W FR 2013051166W WO 2013178920 A1 WO2013178920 A1 WO 2013178920A1
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Prior art keywords
catalyst
tungsten
polyol
sorbitol
weight
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PCT/FR2013/051166
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French (fr)
Inventor
Lea VILCOCQ
Amandine Cabiac
Catherine Especel
Daniel Duprez
Sylvie Lacombe
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IFP Energies Nouvelles
Centre National De La Recherche Scientifique
Université de Poitiers
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Publication of WO2013178920A1 publication Critical patent/WO2013178920A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6527—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
    • B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/47—Catalytic treatment characterised by the catalyst used containing platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • B01J35/613—
    • B01J35/615—
    • B01J35/633—
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates to a process for converting polyols, for example obtained from the treatment of biomass, into hydrocarbons and mono-oxygenated compounds.
  • the products obtained can be used as biofuels that can be incorporated into the fuel pool or as chemical intermediates used in the petrochemical field.
  • Huber et al. (Angewandte Chemie-lnternational Edition 43, 1549-1551, 2004) report the production of a mixture of hydrogen, C0 2 and hydrocarbons by conversion of sorbitol in aqueous phase using a catalyst comprising 4% by weight of Pt on a silica alumina.
  • the hydrocarbons produced have a chemical composition C n H 2n + 2 with n less than or equal to six.
  • the patent application WO2004 / 039918 describes a process for producing C1 -C6 alkanes from water-soluble oxygenated hydrocarbons in the presence of a catalyst containing a group 8 element.
  • Li et al. (ChemSusChem 2010, 3, 1 154-1 157) studied the conversion of sorbitol in aqueous medium in the presence of a catalyst comprising 4% by weight of Pt on a silica alumina.
  • bimetallic catalysts supported on carbonaceous materials is also known.
  • a catalyst containing 5% by weight Pt, 5% by weight Re on a carbon support makes it possible to obtain a mixture of CO 2 (corresponding to approximately 30% of the introduced carbon), of alkanes and of oxygenated compounds (approximately 70% carbon introduced).
  • the carbon ratio between the hydrocarbon products and the oxygenated compounds varies with the operating conditions (Kunkes et al., Science 2008, 332, 417).
  • One of the aims of the invention is therefore to provide a process for converting an aqueous feedstock containing at least one polyol which makes it possible to selectively transform the polyols into hydrocarbons and mono-oxygen compounds containing a number of carbon atoms greater than or equal to at 5.
  • the present invention therefore relates to a process for converting into an aqueous medium a feedstock comprising at least one polyol of formula C n H 2 n + 20n with 3 ⁇ n ⁇ 6 in hydrocarbons and in mono-oxygen compounds containing a number of atoms. of carbon greater than or equal to 5, wherein the charge is contacted at a temperature between 180 and 350 ° C and at a pressure between 0.5 and 20 MPa with a catalyst, said catalyst comprising at least one metal selected from groups 7 to 11 of the periodic table of elements and a support, said support comprising a titanium oxide on which is deposited tungsten with a tungsten element content of between 1 and 50% by weight relative to the total weight of catalyst.
  • the process according to the invention makes it possible to carry out a total conversion of the polyol and to obtain a specific selectivity of at least 30% C in hydrocarbons and mono-oxygenated compounds having a number of carbon atoms greater than or equal to 5
  • the specific selectivity is defined as the ratio of the carbon contained in the hydrocarbon or the mono-oxygenated compound to the sum of the total carbon contained in the gas phase and in the liquid phase.
  • the conversion reaction is carried out at a temperature of between 200 and 270 ° C. and at a pressure of between 2 and 8 MPa.
  • the conversion reaction is carried out under a reducing atmosphere or under an inert atmosphere.
  • the conversion reaction is carried out under a dihydrogen atmosphere and in which the dihydrogen / polyol molar ratio is between 1 and 400 mol / mol.
  • each metal chosen from groups 7 to 11 of the periodic table of the elements is preferably between 0.01 and 10% by weight relative to the total weight of catalyst.
  • the content of tungsten element is preferably between 2 and 30% by weight relative to the total weight of catalyst.
  • the catalyst has undergone a heat treatment step under a reducing atmosphere at a temperature of between 100 and 600 ° C. before being used in the conversion reaction.
  • the catalyst used in the process may be in any form known to those skilled in the art, such as for example in the form of beads, extrudates or pellets.
  • the process according to the invention is particularly suitable for the conversion of polyols selected from glycerol, erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, dulcitol, fucitol, iditol, inositol, pounding, maltitol, lactitol, polyglycitol.
  • the polyol is sorbitol, xylitol or mannitol.
  • the polyol is derived from the treatment of biomass.
  • the polyol can be obtained by transformation of sugar plants, starch plants or by transformation of lignocellulosic biomass such as wood or vegetable waste.
  • the invention relates to a process for converting into a aqueous medium a feedstock comprising at least one polyol of formula C n H 2 n + 20n with 3 ⁇ n ⁇ 6 in hydrocarbons and in monooxygen compounds containing a higher number of carbon atoms. or equal to 5, wherein the charge is brought into contact at a temperature of between 180 and 350 ° C. and at a pressure of between 0.5 and 20 MPa with a catalyst, said catalyst comprising at least one metal chosen from the groups 7 to 11 of the periodic table of the elements and a support, said support comprising a titanium oxide on which is deposited tungsten with a tungsten element content of between 1 and 50% by weight relative to the total weight of catalyst.
  • a filler containing a 6-carbon polyol such as sorbitol or mannitol
  • a filler containing a 6-carbon polyol such as sorbitol or mannitol
  • dihydrogen, poly-oxygenated compounds such as isosorbide
  • hydrocarbons and monooxygen compounds containing a number of carbon atoms of less than or equal to six with predominantly hydrocarbons and mono-oxygen containing compounds containing a number of atoms
  • the solution obtained at the end of conversion contains, for example, methane, ethane, propane, butane, pentane, hexane, cyclopentane and methylcyclopentane as non-limiting examples of hydrocarbons; hexanol, pentanol, butanol, propanol, ethanol and methanol as non-limiting examples of mono-alcohol compounds; hexanone, pentanone, butanone, propanone, acetone as
  • Polyoxygenated compounds such as diols and diones containing a carbon chain of 1 to 6 carbon atoms can also be obtained.
  • the maximum carbon chain length of the products obtained depends on that of the starting polyol; for example six carbon atoms for sorbitol and mannitol, five for xylitol etc.
  • the selectivity observed is probably due to the fact that the catalyst favors the C-0 rupture reactions compared with those of C-C rupture.
  • the process according to the invention makes it possible to obtain high conversions of the polyol and important selectivities, in particular high yields of products comprising hydrocarbons and mono-oxygen compounds containing a number of carbon atoms greater than or equal to 5, while limiting the formation of short-chain compounds such as carbon dioxide.
  • the reaction atmosphere may be a neutral atmosphere or a reducing atmosphere.
  • the catalytic conversion reaction is preferably carried out continuously in the condensed phase.
  • the filler contains at least one polyol.
  • polyol refers to a compound having the chemical formula C n H 2 n + 20n with 3 ⁇ n ⁇ 6.
  • the filler may contain one or more polyols chosen from glycerol, erythritol, threitol, arabitol, xylitol, ribitol, manitol, sorbitol, dulcitol, fucitol, iditol, inositol, Pounded, maltitol, lactitol, polyglycitol.
  • the filler contains sorbitol.
  • the filler may also contain impurities related, for example, to the process for obtaining polyols, in particular from biomass.
  • the feed may contain monomeric sugars such as glucose or xylose, inorganic or organic compounds.
  • the impurity content is preferably less than 10% by weight of the filler.
  • the feedstock to be treated contains water, the content of which is between 1% and 99% by weight relative to the weight of the filler, preferably between 30% and 99%, more preferably between 40% and 98% by weight. water relative to the weight of the load.
  • the concentration of polyol (s) in the filler is generally between 1% and 99%, preferably between 1% and 70% by weight, very preferably between 2% and 60% by weight relative to the weight of the filler.
  • the polyol (s) contained in the feed is (are) preferably of biobased origin.
  • the polyols can thus be produced, for example, by transformation of sugar plants such as sugar beet or sugar cane, by transformation of starchy plants such as wheat, corn, potato, cassava or by transformation of lignocellulosic biomass.
  • the lignocellulosic raw material may consist of wood or vegetable waste.
  • lignocellulosic biomass material are farm residues (straw, grass, stems, cores, shells, etc.), logging residues (first-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, coconut, bagasse ...), household organic waste, waste from wood processing facilities, used timber from construction, paper, recycled or not.
  • Obtaining polyols from sugar plants or starch plants involves steps of hydrolysis and hydrogenation.
  • obtaining polyols from raw lignocellulosic biomass is more complex and requires several simultaneous or successive steps, namely:
  • the lignocellulosic biomass feed can be used in its raw form, that is to say in its entirety with its 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.
  • the biomass is preferably pretreated to increase the reactivity and accessibility of the cellulose within the biomass prior to processing.
  • These pretreatments are of a mechanical, thermochemical, thermomechanical-chemical and / or biochemical nature and cause the decystallinization of the cellulose, the solubilization of hemicellulose and / or lignin or the partial hydrolysis of the hemicellulose according to the treatment. .
  • the lignocellulosic biomass feed may also be pretreated to be in the form of water-soluble oligomers.
  • These pretreatments are of a mechanical, thermochemical, thermomechanical-chemical and / or biochemical nature. They cause decystallinization and solubilization of cellulose in the form of water-soluble oligomers.
  • the hydrogenation step makes it possible to transform part of the monosaccharides of the biomass into polyol (s). For example, it allows to partially transform hexoses such as glucose into a hydrogenated product such as sorbitol or mannitol, according to the following equation:
  • the hydrogenation step is carried out at temperatures between 40 ° and 300 ° C., preferably between 60 ° C. and 250 ° C., and at a hydrogen pressure of between 0.5 MPa and 20 MPa, preferably between 1 MPa and 15 MPa.
  • the catalyst used for converting polyols to hydrocarbons and mono-oxygenated products containing a number of carbon atoms greater than or equal to 5 comprises at least one metal selected from groups 7 to 11 of the table. periodic elements.
  • the metal or metals are advantageously deposited on a support.
  • the support comprises a titanium oxide on which tungsten is deposited with a tungsten element content of between 1 and 50% by weight relative to the total weight of catalyst.
  • Titanium oxide is prepared according to any technique known to those skilled in the art, for example by hydrolysis of titanium chloride, by hydrolysis / condensation of titanium alkoxide solutions and the like. (Handbook of Porous Solids, Schuth, Wiley-VCH Edition, Volume 3).
  • the titanium oxide of the invention may be in rutile crystallographic form, anatase, brookite pure or in admixture.
  • the deposition of tungsten on the titanium oxide support can be carried out according to all the techniques known to those skilled in the art, for example by dry impregnation, excess impregnation, ion exchange, vapor phase deposition of a precursor containing tungsten on said support or a precursor of titanium oxide such as titanium hydroxide Ti (OH) 4 .
  • a possible synthetic route is co-precipitation of tungsten and titanium oxides.
  • the tungsten precursors may be, for example, tungsten oxides, tungsten chlorides, tungsten sulphides, tungsten carbides, tungsten fluorides, tungsten oxychlorides, tungsten-based organic derivatives, iso or heteroamines.
  • polyanions containing tungsten Preferably, the tungsten precursors are selected from tungstic acid, peroxotungstic acid, ammonium metatungstate, or isopolyanions or heteropolyanions based on tungsten.
  • the precursors are ammonium metatungstate or tungstic acid.
  • the use of tungstic acid in solution in hydrogen peroxide allows the formation of monomeric tungsten species in solution, and the preparation of tungsten support by ion exchange.
  • the tungsten support can be subjected to a heat treatment.
  • the treatment is preferably a calcination at a temperature between 300 and 800 ° C under air flow.
  • the tungsten is partially or completely oxidized to form the species WO x with x between 0.5 and 5.
  • a method for preparing the tungsten titanium oxide support is to dry-impregnate an ammonium metatungstate solution (NH 4 C 2 O) on a titanium oxide support followed by underflow calcination. air.
  • an ammonium metatungstate solution NH 4 C 2 O
  • the tungsten content of the catalyst is generally between 1 and 50% by weight relative to the weight of the catalyst, preferably between 2% and 30% by weight, more preferably between 2 and 25% by weight.
  • the catalysts used in the invention also contain at least one metal selected from Groups 7 to 11 of the Periodic Table (according to the new notation of the Periodic Table of Elements: Handbook of Chemistry and Physics, 76th Edition, 1995-1996 ).
  • the metal or metals may be chosen from: Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Re, Au or Ag.
  • the metal or metals are chosen from: Ru, Rh, Pd, Pt, Ni, Cu, Ir, Re. Even more preferably, the metal chosen is platinum.
  • the deposition of said metal chosen from groups 7 to 11 of the periodic table generally involves a precursor of the metal.
  • a precursor of the metal may be metal organic complexes, metal salts such as metal chlorides, metal nitrates.
  • each introduced metal element is advantageously between 0.01 and 10% by weight, and preferably between 0.05 and 5% by weight relative to the weight of the catalyst.
  • the introduction of the metal can be carried out by any technique known to those skilled in the art such as ion exchange, dry impregnation, excess impregnation, vapor phase deposition, etc.
  • the introduction of the metal can be carried out before or after the shaping of the support on which the tungsten is deposited. However, it should be noted that it is also possible to first deposit the metal on the support based on titanium oxide before the deposition of tungsten. After the step of introducing the metal element and tungsten, it is possible to carry out a step of heat treatment of the catalyst.
  • the heat treatment is advantageously carried out between 250 ° and 800 ° C.
  • 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 100 ° C. and 600 ° C. under a flow or dihydrogen atmosphere.
  • the reduction step can be carried out in situ, that is to say in the reactor where the reaction takes place, before the introduction of the reaction charge.
  • the reduction can also be performed ex situ.
  • the catalysts used in the present invention may be in the form of powder, extrudates, beads or pellets.
  • the titanium oxide may be in the form of powder or shaped, for example, balls, extrudates, pellets or any other form commonly used.
  • the shaping can be carried out before or after the deposition of the tungsten oxide and before or after the introduction of the metal.
  • the catalyst preferably has a specific surface area of between 15 and 450 m 2 / g and a pore volume of between 0.05 and 2.0 ml / g.
  • the process for converting polyol (s) according to the invention comprises the reaction in a medium containing water in the presence of a catalyst described above.
  • the polyol conversion process according to the invention is advantageously carried out under a reducing atmosphere or under an inert atmosphere such as dinitrogen or argon.
  • the reaction is carried out under a dihydrogen atmosphere.
  • the dihydrogen can be used pure or in mixture.
  • the dihydrogen / polyol molar ratio may be between 1 and 400, preferably between 5 and 300 mol / mol.
  • the process is carried out at a temperature of between ⁇ ⁇ ' ⁇ and 350 ° C, preferably between 200 ° and 270 ° C, and at a total pressure of between 0.5 MPa and 20 MPa, preferably between 2 MPa and 8 ° C. MPa.
  • the reaction is carried out continuously, for example in a fixed bed.
  • the hourly mass velocity mass flow rate of polyol / mass of catalyst
  • the hourly mass velocity is between 0.01 and 10 h -1 , preferably between 0.05 and 3 h -1 .
  • EXAMPLE 1 Preparation of Catalyst C1 (in Accordance with the Invention): 1.2% wt. Pt / TiOp-WC 50 g of TiO 2 -WO x are prepared by anionic exchange of titanium oxide of rutile crystallographic phase with 150 ml. of tungstic acid in solution (0.25 mol / L) in 30% volume hydrogen peroxide. The resulting solution is filtered and the collected solid is dried at 110 ° C. for 18 hours. The resulting solid is then calcined under a flow of dry air at a temperature of 600 ° C. for 3 hours.
  • the solid S1 obtained contains, by weight, 1.17% of tungsten.
  • the specific surface area of the solid S 1 is 106 m 2 / g and the pore volume 0.4 m 2 / g.
  • Catalyst C1 is prepared by dry impregnation of solid S1 with an aqueous solution of hexachloroplatinic acid H 2 PtCl 6 .6H 2 0.
  • the aqueous solution is prepared at 25 ° C. by dilution of 1.6 g of H 2 PtCl 6 .6H 2 0 in demineralised water at a volume which corresponds to the pore volume of the solid S1. This solution is then impregnated with 50 g of the previously prepared solid S1.
  • the solid obtained is dried at 120 ° C. for 12 h and then calcined under a flow of dry air at a temperature of 550 ° C. for 2 hours.
  • Catalyst C1 thus obtained contains 1.2% by weight of platinum and 1.16% by weight of tungsten.
  • the solid S2 thus contains by weight 9.7% of tungsten.
  • the specific surface area of the solid S 2 is 73 m 2 / g and the pore volume 0.2 m 2 / g.
  • Catalyst C2 is prepared by dry impregnation of solid S 2 with an aqueous solution of hexachloroplatinic acid H 2 PtCl 6 .6H 2 O.
  • An aqueous solution is prepared at 25 ° by dilution of 1.6 g of H 2 PtCl 6 . 6H 2 O in deionized water to a volume which corresponds to the pore volume of the solid S2.
  • This solution is then impregnated with 50 g of the previously prepared solid S2.
  • the solid obtained is dried at 120 ° C. for 12 hours and then calcined under a dry air flow at a temperature of 550 ° C. for 2 hours.
  • the catalyst C2 obtained contains 1.2% by weight of platinum and 9.6% by weight of tungsten.
  • Example 3 Preparation of a Catalyst C3 (Not in Accordance with the Invention): 1.2% by Weight Pt / SiO 2
  • 50 g of catalyst C3 are prepared by dry impregnation with a silica alumina (30% SiO 2 /70% Al 2 O 3 , Siralox 30, from Sasol) with an aqueous solution of hexachloroplatinic acid H 2 PtCl 6 . 6H 2 0.
  • An aqueous solution is prepared at 25 ° C by dilution of 1.6 g of H 2 PtCl 6 .6H 2 O in demineralized water to a volume which corresponds to the pore volume of the silica alumina Siralox 30 This solution is then impregnated with 50 g of the previously prepared solid.
  • the solid obtained is dried at 120 ° C. for 12 hours and then calcined under a flow of dry air at a temperature of 550 ° C. for two hours.
  • the catalyst C3 obtained contains 1.2% by weight of platinum.
  • aqueous solution is prepared at 25 ° by dilution of 1.6 g of H 2 PtCl 6 .6H 2 O in deionized water to a volume which corresponds to the pore volume of the S4 solid. This solution is then impregnated on 50 g of the previously prepared solid.
  • the solid obtained is dried at 120 ° C. for 12 hours and then calcined under a dry air flow at a temperature of 550 ° C. for 2 hours.
  • the catalyst C4 obtained contains 1.2% by weight of platinum and 4.4% by weight of tungsten.
  • EXAMPLE 5 Transformation of a Solution Containing Sorbitol Using the Catalysts Prepared in Examples 1 to 4 This example relates to the conversion of a feed containing 10% by weight of sorbitol in water by the catalysts C1, C2, C3 and C4 for the production of hydrocarbon and monofunctional products containing at least 5 carbon atoms.
  • the course of a standard catalytic test is as follows. 4 g of crushed catalyst and sieved to the particle size 150-355 ⁇ are loaded into the reactor. The catalyst is then dried and reduced under dihydrogen in situ for 2 hours at 450 ° C. After cooling to 50 ° C., degassed water is sent to the reactor. The reactor pressure rises gradually to the set value of 3.8 MPa. The reactor is then heated to the test temperature of 240 ° C. The mass flow rate / catalyst mass ratio is set at 2 h -1 The flow rate of hydrogen is set to have an H 2 / sorbitol molar ratio of 75.
  • reaction products contained in the gas phase for example CO, CO 2 , dihydrogen, hydrocarbons containing one to six carbon atoms, as well as certain light oxygenated compounds, are analyzed by gas chromatography.
  • reaction products contained in the liquid phase are analyzed by gas chromatography, by high performance liquid chromatography (HPLC).
  • HPLC high performance liquid chromatography
  • polyols, monoalcohols in particular sorbitol, xylitol, glycerol, isosorbide, anhydrosorbitol, hexanol, pentanol, butanol, propanol, isopropanol, ethanol and methanol; , hexanediol, pentanediol, butanediol, propylene glycol, ethylene glycol, hexanetriol, butanetriol, pentanetriol,
  • ketones for example hexanone, hexanedione, pentanone, pentanedione, butanone, propanone and acetone,
  • carboxylic acids and their esters, lactones for example formic acid, acetic acid, lactic acid, levulinic acid, alkyl levulinates, lactic acid, pentanoic acid, hexanoic acid, 3-hydroxybutyrolactone, ⁇ -butyrolactone,
  • cyclic ethers for example tetrahydrofuran (THF), methyltetrahydrofuran (MTHF), dimethyltetrahydrofuran, 5- (hydroxymethyl) furfural, acetylfuran, tetrahydropyran, hydrocarbon compounds such as, for example, hexane, pentane, methylcyclopentane, cyclopentane or butane.
  • THF tetrahydrofuran
  • MTHF methyltetrahydrofuran
  • dimethyltetrahydrofuran dimethyltetrahydrofuran
  • 5- (hydroxymethyl) furfural acetylfuran
  • acetylfuran tetrahydropyran
  • hydrocarbon compounds such as, for example, hexane, pentane, methylcyclopentane, cyclopentane or butane.
  • the sum of the carbon contained in the water-soluble reaction products is determined by the TOC analysis (Total Organic Carbon).
  • Sorbitol conversion (t) (Qm sorbitol charge - Qm sorbitol (t)) / Qm sorbitol charge
  • HC hydrocarbons
  • mono-oxygenated compounds monoalcohols, monocetones
  • cyclic ethers C0 2 .
  • the amount of the C5-C6 hydrocarbons is 1 1, 1% carbon and 15.1% C0 2 carbon for the catalyst C1.
  • the amount of C5-C6 hydrocarbons is 9.2% of the carbon and the CO 2 14.0% of the carbon.
  • the use of the catalyst C1 according to the invention makes it possible to increase by 40% the carbon yield of C5-C6 hydrocarbons in comparison with the reference catalyst C3 (Pt on SiO 2 -Al 2 O 3 ).
  • the carbon yield in CO 2 form undesired product, is decreased compared to the catalysts of the prior art.
  • heterogeneous catalysts containing at least one metal element selected from groups 7 to 11 of the periodic table deposited on a support consisting of titanium oxide on which tungsten is deposited makes it possible to transform selectively polyols to hydrocarbon products and mono-oxygenated products containing a number of carbon atoms greater than or equal to 5.

Abstract

The invention relates to a method for converting, in an aqueous medium, a load comprising at least one polyol of formula CnH2n+20n where 3 ≤ n ≤ 6, into hydrocarbons and mono-oxygenated compounds containing a number of carbon atoms higher than or equal to 5, wherein the load is brought into contact with a catalyst, at a temperature of between 180 and 350°C and at a pressure of between 0.5 and 20 MPa, said catalyst comprising at least one metal selected from groups 7 to 11 of the periodic table of elements deposited on a substrate, said substrate comprising a titanium oxide on which tungsten is deposited, the content of the tungsten element being between 1 and 50 wt.% in relation to the total weight of the catalyst.

Description

PROCEDE DE TRANSFORMATION DE POLYOLS EN PHASE AQUEUSE EN PRESENCE D'UN PROCESS FOR THE TRANSFORMATION OF AQUEOUS POLYOLS IN THE PRESENCE OF A
CATALYSEUR A BASE D'OXYDE DE TITANE TUNGSTE CATALYST BASED ON TUNGANE OXIDE
Domaine de l'invention Field of the invention
La présente invention concerne un procédé de transformation de polyols, par exemple obtenus à partir de traitement de la biomasse, en hydrocarbures et en composés mono-oxygénés. Les produits obtenus sont notamment utilisables comme biocarburants incorporables au pool carburant ou bien comme intermédiaires chimiques utilisés dans le domaine de la pétrochimie.  The present invention relates to a process for converting polyols, for example obtained from the treatment of biomass, into hydrocarbons and mono-oxygenated compounds. The products obtained can be used as biofuels that can be incorporated into the fuel pool or as chemical intermediates used in the petrochemical field.
Art Antérieur Previous Art
Depuis quelques années, l'augmentation des coûts des combustibles fossiles et les préoccupations environnementales ont stimulé l'intérêt mondial pour le développement d'alternatives aux produits dérivés du pétrole.  In recent years, rising fossil fuel costs and environmental concerns have stimulated global interest in developing alternatives to petroleum products.
Il existe notamment un vif intérêt pour l'incorporation de produits d'origine renouvelable au sein des filières carburant et chimie, en complément ou en substitution des produits d'origine fossile. En effet, la production de produits chimiques et de carburants à partir de la biomasse permet notamment de réduire la dépendance énergétique vis-à-vis du pétrole.  In particular, there is a keen interest in the incorporation of renewable products into the fuel and chemical sectors, in addition to or in substitution for products of fossil origin. In fact, the production of chemicals and fuels from biomass makes it possible to reduce energy dependence on oil.
La transformation de polyols, issus de la transformation de biomasse notamment, en produits hydrocarbures et mono-oxygénés contenant un nombre d'atomes de carbone supérieur ou égal à 5, est une voie particulièrement intéressante car ces produits peuvent par exemple être incorporés dans le pool essence après transformation.  The transformation of polyols, resulting from the transformation of biomass in particular, into hydrocarbon and mono-oxygenated products containing a number of carbon atoms greater than or equal to 5, is a particularly advantageous route because these products can for example be incorporated into the pool. essence after transformation.
La littérature est abondante dans le domaine de la conversion catalytique des polyols. Ainsi les catalyseurs métalliques massiques (Ni Raney, Cu Raney) ou supportés du type M/Si02 (M=Ru, Rh, Pt, Ir, Co, Cu) permettent la transformation d'une solution aqueuse de polyols (glycérol, érythritol, xylitol ou sorbitol) en molécules poly-oxygénées et en hydrocarbures contenant majoritairement moins de trois atomes de carbone comme le glycérol, l'éthylène glycol, et les alcanes C1 -C3 (Montassier et al. Bulletin de la Société Chimique de France 148-155, 1989). The literature is abundant in the field of catalytic conversion of polyols. Thus the mass metal catalysts (Ni Raney, Cu Raney) or supported of the M / SiO 2 type (M = Ru, Rh, Pt, Ir, Co, Cu) allow the transformation of an aqueous solution of polyols (glycerol, erythritol, xylitol or sorbitol) into poly-oxygenated molecules and hydrocarbons containing predominantly less than three carbon atoms, such as glycerol, ethylene glycol, and C1-C3 alkanes (Montassier et al., Bulletin de la Société Chimique de France 148-155 , 1989).
Huber et al. (Angewandte Chemie-lnternational Edition 43, 1549-1551 , 2004) observent la production d'un mélange de dihydrogène, de C02 et d'hydrocarbures par conversion du sorbitol en phase aqueuse en employant un catalyseur comprenant 4% poids de Pt sur une silice alumine. Les hydrocarbures produits ont une composition chimique CnH2n+2 avec n inférieur ou égal à six. Huber et al. (Angewandte Chemie-lnternational Edition 43, 1549-1551, 2004) report the production of a mixture of hydrogen, C0 2 and hydrocarbons by conversion of sorbitol in aqueous phase using a catalyst comprising 4% by weight of Pt on a silica alumina. The hydrocarbons produced have a chemical composition C n H 2n + 2 with n less than or equal to six.
La demande de brevet WO2004/039918 décrit un procédé de production d'alcanes C1 -C6 à partir d'hydrocarbures oxygénés solubles dans l'eau en présence d'un catalyseur contenant un élément du groupe 8. Li et al. {ChemSusChem 2010, 3, 1 154-1 157) ont étudié la conversion du sorbitol en milieu aqueux en présence d'un catalyseur comprenant 4% poids de Pt sur une silice alumine. Ainsi à 245^, à une vitesse volumique horaire de 3h~\ avec une charge aqueuse contenant 5% poids en sorbitol, ils observent au bout de 36 heures de test une sélectivité spécifique en alcanes C5- C6 de 34% et un rendement carbone en alcanes de 10% (d'où un rendement carbone en composés C5-C6 de l'ordre de 3,4%). Ces mêmes auteurs ont également étudié les performances d'un catalyseur ayant 4% poids de Pt sur un support WOx/Zr02 dans les mêmes conditions; ils observent une sélectivité spécifique (la sélectivité spécifique en alcane Ci étant définie comme le rapport du carbone contenu dans l'alcane Ci sur la somme du carbone contenu dans les alcanes détectés dans la phase gaz) en alcanes C5-C6 équivalente à celle obtenue en présence du catalyseur 4% poids de Pt sur une silice alumine, soit d'environ 30% avec un rendement carbone en alcane de 1 ,2%. Le rendement carbone en composés C5-C6 est donc d'environ 0,4%. The patent application WO2004 / 039918 describes a process for producing C1 -C6 alkanes from water-soluble oxygenated hydrocarbons in the presence of a catalyst containing a group 8 element. Li et al. (ChemSusChem 2010, 3, 1 154-1 157) studied the conversion of sorbitol in aqueous medium in the presence of a catalyst comprising 4% by weight of Pt on a silica alumina. Thus at 245 ^, at an hourly space velocity of 3 hours ~ \ with an aqueous feed containing 5% by weight sorbitol, they observed after 36 hours of test a specific selectivity C5- C6 alkanes of 34% and a carbon yield alkanes of 10% (hence a carbon yield of C5-C6 compounds of the order of 3.4%). These same authors also studied the performance of a catalyst having 4% weight of Pt on a support WO x / Zr0 2 under the same conditions; they observe a specific selectivity (the specific selectivity for alkane Ci being defined as the ratio of the carbon contained in the alkane Ci to the sum of the carbon contained in the alkanes detected in the gas phase) to C5-C6 alkanes equivalent to that obtained in presence of the catalyst 4% by weight of Pt on a silica alumina, ie of approximately 30% with an alkane carbon yield of 1, 2%. The carbon yield of C5-C6 compounds is thus about 0.4%.
L'utilisation de catalyseurs bimétalliques supportés sur matériaux carbonés est également connue. Par exemple un catalyseur contenant 5% poids Pt, 5% poids Re sur un support carbone, permet d'obtenir un mélange de C02 (correspondant à environ 30% du carbone introduit), d'alcanes et de composés oxygénés (environ 70% du carbone introduit). Le rapport carbone entre les produits hydrocarbonés et les composés oxygénés varie avec les conditions opératoires (Kunkes et al., Science 2008, 332, 417). The use of bimetallic catalysts supported on carbonaceous materials is also known. For example a catalyst containing 5% by weight Pt, 5% by weight Re on a carbon support, makes it possible to obtain a mixture of CO 2 (corresponding to approximately 30% of the introduced carbon), of alkanes and of oxygenated compounds (approximately 70% carbon introduced). The carbon ratio between the hydrocarbon products and the oxygenated compounds varies with the operating conditions (Kunkes et al., Science 2008, 332, 417).
Plus récemment, il a été décrit dans le document US 201 1 /0160482 la mise en œuvre d'un catalyseur trimétallique (Pt- Ru- Sn) sur un support zircone ou dioxyde de titane pour la conversion d'hydrocarbures oxygénés en des produits oxygénés de poids moléculaire plus faible. More recently, it has been described in US 201 1/0160482 the implementation of a trimetallic catalyst (Pt-Ru- Sn) on a support zirconia or titanium dioxide for the conversion of oxygenated hydrocarbons to oxygenates of lower molecular weight.
Un des buts de l'invention est donc de fournir un procédé de conversion d'une charge aqueuse contenant au moins un polyol permettant de transformer sélectivement les polyols en hydrocarbures et en composés mono-oxygénés contenant un nombre d'atomes de carbone supérieur ou égal à 5. One of the aims of the invention is therefore to provide a process for converting an aqueous feedstock containing at least one polyol which makes it possible to selectively transform the polyols into hydrocarbons and mono-oxygen compounds containing a number of carbon atoms greater than or equal to at 5.
Résumé de l'invention Summary of the invention
La présente invention concerne donc un procédé de conversion en milieu aqueux d'une charge comprenant au moins un polyol de formule CnH2n+20n avec 3 < n < 6 en hydrocarbures et en composés mono-oxygénés contenant un nombre d'atomes de carbone supérieur ou égal à 5, dans lequel on met en contact la charge à une température comprise entre 180 et 350 °C et à une pression comprise entre 0,5 et 20 MPa avec un catalyseur, ledit catalyseur comprenant au moins un métal choisi parmi les groupes 7 à 1 1 du tableau périodique des éléments et un support, ledit support comprenant un oxyde de titane sur lequel est déposé du tungstène avec une teneur en élément tungstène comprise entre 1 et 50% poids par rapport au poids total de catalyseur. The present invention therefore relates to a process for converting into an aqueous medium a feedstock comprising at least one polyol of formula C n H 2 n + 20n with 3 <n <6 in hydrocarbons and in mono-oxygen compounds containing a number of atoms. of carbon greater than or equal to 5, wherein the charge is contacted at a temperature between 180 and 350 ° C and at a pressure between 0.5 and 20 MPa with a catalyst, said catalyst comprising at least one metal selected from groups 7 to 11 of the periodic table of elements and a support, said support comprising a titanium oxide on which is deposited tungsten with a tungsten element content of between 1 and 50% by weight relative to the total weight of catalyst.
De façon surprenante, il a été découvert qu'un catalyseur spécifique présentant la combinaison des caractéristiques dans les gammes de valeurs mentionnées ci-dessus et mis en œuvre dans les conditions opératoires indiquées ci-dessus, permet de réaliser une conversion sélective des polyols en hydrocarbures et composés mono-oxygénés contenant un nombre d'atomes de carbone supérieur ou égal à 5. Surprisingly, it has been discovered that a specific catalyst having the combination of the characteristics in the ranges of values mentioned above and implemented under the operating conditions indicated above makes it possible to selectively convert the polyols into hydrocarbons. and mono-oxygenated compounds containing a number of carbon atoms greater than or equal to 5.
En effet le procédé selon l'invention permet de réaliser une conversion totale du polyol et d'obtenir une sélectivité spécifique d'au moins 30% C en hydrocarbures et composés mono- oxygénés ayant un nombre d'atomes de carbone supérieur ou égal à 5. La sélectivité spécifique est définie comme étant le rapport du carbone contenu dans l'hydrocarbure ou le composé mono-oxygéné sur la somme du carbone total contenu dans la phase gaz et dans la phase liquide. De manière préférée, la réaction de conversion est réalisée à une température comprise entre 200 et 270 ^ et à une pression comprise entre 2 et 8 MPa.  Indeed, the process according to the invention makes it possible to carry out a total conversion of the polyol and to obtain a specific selectivity of at least 30% C in hydrocarbons and mono-oxygenated compounds having a number of carbon atoms greater than or equal to 5 The specific selectivity is defined as the ratio of the carbon contained in the hydrocarbon or the mono-oxygenated compound to the sum of the total carbon contained in the gas phase and in the liquid phase. In a preferred manner, the conversion reaction is carried out at a temperature of between 200 and 270 ° C. and at a pressure of between 2 and 8 MPa.
Selon un mode de réalisation préférée, la réaction de conversion est réalisée sous atmosphère réductrice ou sous atmosphère inerte. De façon avantageuse la réaction de conversion est réalisée sous atmosphère de dihydrogène et dans lequel le rapport molaire dihydrogène / polyols est compris entre 1 et 400 mol/mol. According to a preferred embodiment, the conversion reaction is carried out under a reducing atmosphere or under an inert atmosphere. Advantageously, the conversion reaction is carried out under a dihydrogen atmosphere and in which the dihydrogen / polyol molar ratio is between 1 and 400 mol / mol.
La teneur de chaque métal choisi parmi les groupes 7 à 1 1 du tableau périodique des éléments est de préférence comprise entre 0,01 et 10% poids par rapport au poids total de catalyseur. The content of each metal chosen from groups 7 to 11 of the periodic table of the elements is preferably between 0.01 and 10% by weight relative to the total weight of catalyst.
La teneur en élément tungstène est comprise de préférence entre 2 et 30% poids par rapport au poids total de catalyseur. The content of tungsten element is preferably between 2 and 30% by weight relative to the total weight of catalyst.
Selon un mode de réalisation préférentielle, le catalyseur a subi une étape de traitement thermique sous atmosphère réductrice à une température comprise entre 100 et 600 'Ό avant sa mise en œuvre dans la réaction de conversion. Le catalyseur mis en œuvre dans le procédé peut être sous toute forme connue de l'Homme du métier, telle que par exemple sous forme de billes, d'extrudés ou de pastilles. According to a preferred embodiment, the catalyst has undergone a heat treatment step under a reducing atmosphere at a temperature of between 100 and 600 ° C. before being used in the conversion reaction. The catalyst used in the process may be in any form known to those skilled in the art, such as for example in the form of beads, extrudates or pellets.
Le procédé selon l'invention convient particulièrement bien pour la conversion des polyols sélectionnés parmi le glycérol, l'érythritol, le thréitol, l'arabitol, le xylitol, le ribitol, le mannitol, le sorbitol, le dulcitol, le fucitol, l'iditol, l'inositol, Tisonnait, le maltitol, le lactitol, le polyglycitol. De manière préférée, le polyol est le sorbitol, le xylitol ou le mannitol. The process according to the invention is particularly suitable for the conversion of polyols selected from glycerol, erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, dulcitol, fucitol, iditol, inositol, pounding, maltitol, lactitol, polyglycitol. Preferably, the polyol is sorbitol, xylitol or mannitol.
De façon avantageuse le polyol est issu du traitement de la biomasse. Ainsi par exemple le polyol peut être obtenu par transformation de plantes sucrières, de plantes amylacées ou par transformation de biomasse lignocellulosique telle que le bois ou les déchets végétaux. Advantageously, the polyol is derived from the treatment of biomass. For example, the polyol can be obtained by transformation of sugar plants, starch plants or by transformation of lignocellulosic biomass such as wood or vegetable waste.
Description détaillée de l'invention Detailed description of the invention
L'invention concerne un procédé de conversion en milieu aqueux d'une charge comprenant au moins un polyol de formule CnH2n+20n avec 3 < n < 6 en hydrocarbures et en composés monooxygénés contenant un nombre d'atomes de carbone supérieur ou égal à 5, dans lequel on met en contact la charge à une température comprise entre 180 et 350 °C et à une pression comprise entre 0,5 et 20 MPa avec un catalyseur, ledit catalyseur comprenant au moins un métal choisi parmi les groupes 7 à 1 1 du tableau périodique des éléments et un support, ledit support comprenant un oxyde de titane sur lequel est déposé du tungstène avec une teneur en élément tungstène comprise entre 1 et 50% poids par rapport au poids total de catalyseur. Ainsi par exemple lors de la mise en œuvre du procédé selon l'invention avec une charge contenant un polyol à 6 atomes de carbone comme le sorbitol ou le mannitol, il est possible d'obtenir un mélange de différents produits comprenant notamment du dioxyde de carbone, du dihydrogène, des composés poly-oxygénés comme l'isosorbide, des hydrocarbures et des composés monooxygénés contenant un nombre d'atomes de carbone inférieur ou égal à six, avec majoritairement des hydrocarbures et des composés mono-oxygénés contenant un nombre d'atomes de carbone supérieur ou égal à 5. La solution obtenue en fin de conversion contient par exemple du méthane, de l'éthane, du propane, du butane, du pentane, de l'hexane, du cyclopentane et du méthylcyclopentane comme exemples non limitatifs d'hydrocarbures ; de l'hexanol, du pentanol, du butanol, du propanol, de l'éthanol et du méthanol comme exemples non limitatifs de composés mono alcools ; de l'hexanone, du pentanone, du butanone, du propanone, de l'acétone comme exemples non limitatifs de mono-cétones et ainsi que des acides carboxyliques. Les composés polyoxygénés comme les diols, les diones contenant une chaîne carbonée de 1 à 6 atomes de carbone peuvent également être obtenus. La longueur de chaîne carbonée maximale des produits obtenus dépend de celle du polyol de départ ; par exemple six atomes de carbone pour le sorbitol et le mannitol, cinq pour le xylitol etc.. The invention relates to a process for converting into a aqueous medium a feedstock comprising at least one polyol of formula C n H 2 n + 20n with 3 <n <6 in hydrocarbons and in monooxygen compounds containing a higher number of carbon atoms. or equal to 5, wherein the charge is brought into contact at a temperature of between 180 and 350 ° C. and at a pressure of between 0.5 and 20 MPa with a catalyst, said catalyst comprising at least one metal chosen from the groups 7 to 11 of the periodic table of the elements and a support, said support comprising a titanium oxide on which is deposited tungsten with a tungsten element content of between 1 and 50% by weight relative to the total weight of catalyst. Thus, for example, during the implementation of the process according to the invention with a filler containing a 6-carbon polyol such as sorbitol or mannitol, it is possible to obtain a mixture of different products including in particular carbon dioxide. , dihydrogen, poly-oxygenated compounds such as isosorbide, hydrocarbons and monooxygen compounds containing a number of carbon atoms of less than or equal to six, with predominantly hydrocarbons and mono-oxygen containing compounds containing a number of atoms The solution obtained at the end of conversion contains, for example, methane, ethane, propane, butane, pentane, hexane, cyclopentane and methylcyclopentane as non-limiting examples of hydrocarbons; hexanol, pentanol, butanol, propanol, ethanol and methanol as non-limiting examples of mono-alcohol compounds; hexanone, pentanone, butanone, propanone, acetone as non-limiting examples of mono-ketones and also carboxylic acids. Polyoxygenated compounds such as diols and diones containing a carbon chain of 1 to 6 carbon atoms can also be obtained. The maximum carbon chain length of the products obtained depends on that of the starting polyol; for example six carbon atoms for sorbitol and mannitol, five for xylitol etc.
Sans être lié à aucune théorie, la sélectivité observée est probablement due au fait que le catalyseur favorise les réactions de rupture C-0 comparativement à celles de rupture C-C.  Without being bound by any theory, the selectivity observed is probably due to the fact that the catalyst favors the C-0 rupture reactions compared with those of C-C rupture.
Le procédé selon l'invention permet d'obtenir des conversions élevées du polyol et des sélectivités importantes, en particulier des rendements élevés en produits comprenant des hydrocarbures et des composés mono-oxygénés contenant un nombre d'atomes de carbone supérieur ou égal à 5, tout en limitant la formation de composés à chaîne courte comme le dioxyde de carbone. The process according to the invention makes it possible to obtain high conversions of the polyol and important selectivities, in particular high yields of products comprising hydrocarbons and mono-oxygen compounds containing a number of carbon atoms greater than or equal to 5, while limiting the formation of short-chain compounds such as carbon dioxide.
Ces conversions et sélectivités sont obtenues en conditions hydrothermales, c'est-à-dire en présence d'eau liquide. L'atmosphère de réaction peut être une atmosphère neutre ou une atmosphère réductrice. La réaction de conversion catalytique est de préférence réalisée en continu en phase condensée. These conversions and selectivities are obtained in hydrothermal conditions, that is to say in the presence of liquid water. The reaction atmosphere may be a neutral atmosphere or a reducing atmosphere. The catalytic conversion reaction is preferably carried out continuously in the condensed phase.
La charge Load
La charge contient au moins un polyol. Le terme polyol désigne un composé répondant à la formule chimique CnH2n+20n avec 3 < n < 6. The filler contains at least one polyol. The term polyol refers to a compound having the chemical formula C n H 2 n + 20n with 3 <n <6.
La charge peut contenir un ou plusieurs polyols choisis parmi le glycérol, l'érythritol, le thréitol, l'arabitol, le xylitol, le ribitol, le manitol, le sorbitol, le dulcitol, le fucitol, l'iditol, l'inositol, Tisonnait, le maltitol, le lactitol, le polyglycitol. De manière préférée, la charge contient du sorbitol (n=6), du mannitol (n=6) et/ou du xylitol (n=5). De manière très préférée, la charge contient du sorbitol. La charge peut également contenir des impuretés liées par exemple au procédé d'obtention de polyols, en particulier à partir de biomasse. A titre d'exemple la charge peut contenir des sucres monomériques comme le glucose ou le xylose, des composés minéraux ou organiques. La teneur en impuretés est de préférence inférieure à 10% poids de la charge.  The filler may contain one or more polyols chosen from glycerol, erythritol, threitol, arabitol, xylitol, ribitol, manitol, sorbitol, dulcitol, fucitol, iditol, inositol, Pounded, maltitol, lactitol, polyglycitol. Preferably, the feed contains sorbitol (n = 6), mannitol (n = 6) and / or xylitol (n = 5). Most preferably, the filler contains sorbitol. The filler may also contain impurities related, for example, to the process for obtaining polyols, in particular from biomass. For example, the feed may contain monomeric sugars such as glucose or xylose, inorganic or organic compounds. The impurity content is preferably less than 10% by weight of the filler.
La charge à traiter contient de l'eau dont la teneur est comprise entre 1 % et 99% poids par rapport au poids de la charge, de préférence entre 30% et 99%, de manière encore préférée entre 40% et 98% poids d'eau par rapport au poids de la charge. The feedstock to be treated contains water, the content of which is between 1% and 99% by weight relative to the weight of the filler, preferably between 30% and 99%, more preferably between 40% and 98% by weight. water relative to the weight of the load.
La concentration en polyol(s) dans la charge est généralement comprise entre 1 % et 99%, de préférence entre 1 % et 70% poids, de manière très préférée entre 2% et 60% poids par rapport au poids de la charge. Le(s) polyol(s) contenu(s) dans la charge est (sont) de préférence d'origine biosourcée. Les polyols peuvent ainsi être produits, par exemple, par transformation de plantes sucrières comme la betterave ou la canne à sucre, par transformation de plantes amylacées comme le blé, maïs, pomme de terre, manioc ou par transformation de biomasse lignocellulosique. La matière première lignocellulosique peut être constituée de bois ou de déchets végétaux. D'autres exemples non limitatifs de matière biomasse lignocellulosique sont les résidus d'exploitation agricole (paille, herbes, tiges, noyaux, coquilles...), les résidus d'exploitation forestière (produits de première éclaircie, écorces, sciures, copeaux, chutes...), les produits d'exploitation forestière, les cultures dédiées (taillis à courte rotation), les résidus de l'industrie agro-alimentaire (résidus de l'industrie du coton, bambou, sisal, banane, maïs, panicum virgatum, noix de coco, bagasse...), les déchets organiques ménagers, les déchets des installations de transformation du bois, les bois usagés de construction, du papier, recyclé ou non. L'obtention de polyols à partir de plantes sucrières ou de plantes amylacées met en jeu des étapes d'hydrolyse et d'hydrogénation. En revanche, l'obtention de polyols à partir de biomasse lignocellulosique brute est plus complexe et requiert plusieurs étapes simultanées ou successives, à savoir : The concentration of polyol (s) in the filler is generally between 1% and 99%, preferably between 1% and 70% by weight, very preferably between 2% and 60% by weight relative to the weight of the filler. The polyol (s) contained in the feed is (are) preferably of biobased origin. The polyols can thus be produced, for example, by transformation of sugar plants such as sugar beet or sugar cane, by transformation of starchy plants such as wheat, corn, potato, cassava or by transformation of lignocellulosic biomass. 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, cores, shells, etc.), logging residues (first-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, coconut, bagasse ...), household organic waste, waste from wood processing facilities, used timber from construction, paper, recycled or not. Obtaining polyols from sugar plants or starch plants involves steps of hydrolysis and hydrogenation. On the other hand, obtaining polyols from raw lignocellulosic biomass is more complex and requires several simultaneous or successive steps, namely:
• un prétraitement de la biomasse lignocellulosique,  • pretreatment of lignocellulosic biomass,
· une hydrolyse de la partie carbohydrate (cellulose et hemicellulose) et  · A hydrolysis of the carbohydrate part (cellulose and hemicellulose) and
• une hydrogénation des sucres monomériques obtenus après hydrolyse.  A hydrogenation of the monomeric sugars obtained after hydrolysis.
La charge biomasse lignocellulosique peut être utilisée sous sa forme brute, c'est-à-dire dans son intégralité avec ses trois constituants cellulose, hémicellulose et lignine. La biomasse brute se présente généralement sous forme de résidus fibreux ou poudre. En général, elle est broyée ou déchiquetée pour permettre son transport. The lignocellulosic biomass feed can be used in its raw form, that is to say in its entirety with its 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.
La biomasse subit de préférence un prétraitement afin d'augmenter la réactivité et l'accessibilité de la cellulose au sein de la biomasse avant sa transformation. Ces prétraitements sont de nature mécanique, thermochimique, thermo-mécanico-chimique et/ou biochimique et provoquent la décristallinisation de la cellulose, la solubilisation de l'hémicellulose et/ou de la lignine ou l'hydrolyse partielle de l'hémicellulose suivant le traitement.  The biomass is preferably pretreated to increase the reactivity and accessibility of the cellulose within the biomass prior to processing. These pretreatments are of a mechanical, thermochemical, thermomechanical-chemical and / or biochemical nature and cause the decystallinization of the cellulose, the solubilization of hemicellulose and / or lignin or the partial hydrolysis of the hemicellulose according to the treatment. .
La charge biomasse lignocellulosique peut également être prétraitée afin d'être sous la forme d'oligomères hydrosolubles. Ces prétraitements sont de nature mécanique, thermochimique, thermo-mécanico-chimique et/ou biochimique. Ils provoquent la décristallinisation et la solubilisation de la cellulose sous forme d'oligomères hydrosolubles. L'étape d'hydrogénation permet de transformer une partie des monosaccharides de la biomasse en polyol(s). Par exemple, elle permet de transformer en partie les hexoses comme le glucose en produit hydrogéné comme le sorbitol ou le mannitol, selon l'équation suivante :
Figure imgf000008_0001
The lignocellulosic biomass feed may also be pretreated to be in the form of water-soluble oligomers. These pretreatments are of a mechanical, thermochemical, thermomechanical-chemical and / or biochemical nature. They cause decystallinization and solubilization of cellulose in the form of water-soluble oligomers. The hydrogenation step makes it possible to transform part of the monosaccharides of the biomass into polyol (s). For example, it allows to partially transform hexoses such as glucose into a hydrogenated product such as sorbitol or mannitol, according to the following equation:
Figure imgf000008_0001
L'étape d'hydrogénation est opérée à des températures comprises entre 40 ^ et 300 °C, de préférence entre 60 'Ό et 250 °C, et à une pression de dihydrogène comprise entre 0,5 MPa et 20 MPa, de préférence entre 1 MPa et 15 MPa. The hydrogenation step is carried out at temperatures between 40 ° and 300 ° C., preferably between 60 ° C. and 250 ° C., and at a hydrogen pressure of between 0.5 MPa and 20 MPa, preferably between 1 MPa and 15 MPa.
Le catalyseur The catalyst
Selon l'invention, le catalyseur utilisé pour la transformation de polyols en hydrocarbures et en produits mono-oxygénés contenant un nombre d'atomes de carbone supérieur ou égal à 5, comprend au moins un métal choisi parmi les groupes 7 à 1 1 du tableau périodique des éléments. Le ou les métaux sont avantageusement déposés sur un support. Le support comprend un oxyde de titane sur lequel est déposé du tungstène avec une teneur en élément tungstène comprise entre 1 et 50% poids par rapport au poids total de catalyseur.  According to the invention, the catalyst used for converting polyols to hydrocarbons and mono-oxygenated products containing a number of carbon atoms greater than or equal to 5 comprises at least one metal selected from groups 7 to 11 of the table. periodic elements. The metal or metals are advantageously deposited on a support. The support comprises a titanium oxide on which tungsten is deposited with a tungsten element content of between 1 and 50% by weight relative to the total weight of catalyst.
L'oxyde de titane est préparé selon toute technique connue de l'Homme du métier comme par exemple par hydrolyse de chlorure de titane, par hydrolyse/condensation de solutions d'alkoxydes de titane etc. (Handbook of Porous Solids, Schuth, Edition Wiley-VCH, Volume 3). L'oxyde de titane de l'invention peut être sous forme cristallographique rutile, anatase, brookite pure ou en mélange. Le dépôt du tungstène sur le support d'oxyde de titane peut être réalisé selon toutes les techniques connues de l'Homme du métier, comme par exemple par imprégnation à sec, imprégnation en excès, échange ionique, dépôt en phase vapeur d'un précurseur contenant du tungstène sur ledit support ou d'un précurseur de l'oxyde de titane comme par exemple l'hydroxyde de titane Ti(OH)4. Titanium oxide is prepared according to any technique known to those skilled in the art, for example by hydrolysis of titanium chloride, by hydrolysis / condensation of titanium alkoxide solutions and the like. (Handbook of Porous Solids, Schuth, Wiley-VCH Edition, Volume 3). The titanium oxide of the invention may be in rutile crystallographic form, anatase, brookite pure or in admixture. The deposition of tungsten on the titanium oxide support can be carried out according to all the techniques known to those skilled in the art, for example by dry impregnation, excess impregnation, ion exchange, vapor phase deposition of a precursor containing tungsten on said support or a precursor of titanium oxide such as titanium hydroxide Ti (OH) 4 .
Une voie de synthèse également possible est une co-précipitation d'oxydes de tungstène et de titane. A possible synthetic route is co-precipitation of tungsten and titanium oxides.
Les précurseurs de tungstène peuvent être par exemple les oxydes de tungstène, les chlorures de tungstène, les sulfures de tungstène, les carbures de tungstène, les fluorures de tungstène, les oxychlorures de tungstène, les dérivés organiques à base de tungstène, les iso ou hétéro polyanions contenant du tungstène. De préférence, les précurseurs de tungstène sont choisis parmi l'acide tungstique, l'acide peroxotungstique, le métatungstate d'ammonium, ou les isopolyanions ou hétéropolyanions à base de tungstène. De manière préférée, les précurseurs sont le métatungstate d'ammonium ou l'acide tungstique. L'utilisation d'acide tungstique en solution dans du peroxyde d'hydrogène permet la formation d'espèces tungstène monomériques en solution, et la préparation du support tungsté par échange ionique. Après l'étape de déposition du tungstène, le support tungsté peut être soumis à un traitement thermique. Le traitement est de préférence une calcination à une température comprise entre 300 et 800 'C sous débit air. A l'issue de l'étape de calcination, le tungstène est partiellement ou totalement oxydé pour former l'espèce WOx avec x compris entre 0,5 et 5. The tungsten precursors may be, for example, tungsten oxides, tungsten chlorides, tungsten sulphides, tungsten carbides, tungsten fluorides, tungsten oxychlorides, tungsten-based organic derivatives, iso or heteroamines. polyanions containing tungsten. Preferably, the tungsten precursors are selected from tungstic acid, peroxotungstic acid, ammonium metatungstate, or isopolyanions or heteropolyanions based on tungsten. Preferably, the precursors are ammonium metatungstate or tungstic acid. The use of tungstic acid in solution in hydrogen peroxide allows the formation of monomeric tungsten species in solution, and the preparation of tungsten support by ion exchange. After the deposition step of tungsten, the tungsten support can be subjected to a heat treatment. The treatment is preferably a calcination at a temperature between 300 and 800 ° C under air flow. At the end of the calcination step, the tungsten is partially or completely oxidized to form the species WO x with x between 0.5 and 5.
Par exemple, une méthode de préparation du support oxyde de titane tungsté consiste à imprégner à sec une solution de métatungstate d'ammonium (NhU^I-^W^C o sur un support d'oxyde de titane suivie d'une calcination sous débit d'air. For example, a method for preparing the tungsten titanium oxide support is to dry-impregnate an ammonium metatungstate solution (NH 4 C 2 O) on a titanium oxide support followed by underflow calcination. air.
Selon l'invention la teneur en tungstène du catalyseur est comprise généralement entre 1 et 50% poids par rapport au poids du catalyseur, de préférence entre 2% et 30% poids, de manière encore préférée entre 2 et 25 % poids.  According to the invention, the tungsten content of the catalyst is generally between 1 and 50% by weight relative to the weight of the catalyst, preferably between 2% and 30% by weight, more preferably between 2 and 25% by weight.
Les catalyseurs utilisés dans l'invention contiennent en outre au moins un métal choisi dans les groupes 7 à 1 1 de la classification périodique (selon la nouvelle notation de la classification périodique des éléments : Handbook of Chemistry and Physics, 76ième édition, 1995-1996). Ainsi le ou les métaux peuvent être choisis parmi : Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Re, Au ou Ag. De manière préférée, le ou les métaux sont choisis parmi : Ru, Rh, Pd, Pt, Ni, Cu, Ir, Re. De manière encore plus préférée le métal choisi est le platine. The catalysts used in the invention also contain at least one metal selected from Groups 7 to 11 of the Periodic Table (according to the new notation of the Periodic Table of Elements: Handbook of Chemistry and Physics, 76th Edition, 1995-1996 ). Thus, the metal or metals may be chosen from: Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Re, Au or Ag. Preferably, the metal or metals are chosen from: Ru, Rh, Pd, Pt, Ni, Cu, Ir, Re. Even more preferably, the metal chosen is platinum.
Le dépôt dudit métal choisi parmi les groupes 7 à 1 1 de la classification périodique fait généralement intervenir un précurseur du métal. Par exemple il peut s'agir de complexes organiques métalliques, de sels de métaux comme les chlorures métalliques, les nitrates métalliques. The deposition of said metal chosen from groups 7 to 11 of the periodic table generally involves a precursor of the metal. For example, it may be metal organic complexes, metal salts such as metal chlorides, metal nitrates.
La teneur de chaque élément métallique introduit est avantageusement comprise entre 0,01 et 10% poids, et préférentiellement entre 0,05 et 5% poids par rapport au poids du catalyseur. The content of each introduced metal element is advantageously between 0.01 and 10% by weight, and preferably between 0.05 and 5% by weight relative to the weight of the catalyst.
L'introduction du métal peut être réalisée par toute technique connue de l'Homme du métier comme par exemple l'échange ionique, l'imprégnation à sec, l'imprégnation par excès, le dépôt en phase vapeur, etc. L'introduction du métal peut être réalisée avant ou après la mise en forme du support sur lequel est déposé le tungstène. Cependant il est à noter qu'il est également possible de déposer d'abord le métal sur le support à base d'oxyde de titane avant le dépôt de tungstène. Après l'étape d'introduction de l'élément métallique et du tungstène, on peut procéder à une étape de traitement thermique du catalyseur. Le traitement thermique est avantageusement réalisé entre 250 ^ et 800 °C. L'étape de traitement thermique peut être suivie d'un traitement de réduction en température. Le traitement thermique réducteur est avantageusement réalisé à une température comprise entre 100°C et 600 'Ό sous flux ou atmosphère de dihydrogène.The introduction of the metal can be carried out by any technique known to those skilled in the art such as ion exchange, dry impregnation, excess impregnation, vapor phase deposition, etc. The introduction of the metal can be carried out before or after the shaping of the support on which the tungsten is deposited. However, it should be noted that it is also possible to first deposit the metal on the support based on titanium oxide before the deposition of tungsten. After the step of introducing the metal element and tungsten, it is possible to carry out a step of heat treatment of the catalyst. The heat treatment is advantageously carried out between 250 ° and 800 ° C. 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 100 ° C. and 600 ° C. under a flow or dihydrogen atmosphere.
L'étape de réduction peut être réalisée in situ c'est-à-dire dans le réacteur où se déroule la réaction, avant l'introduction de la charge réactionnelle. La réduction peut également être réalisée ex situ. Les catalyseurs utilisés dans la présente invention peuvent être sous forme de poudre, d'extrudés, de billes ou de pastilles. Lors de la préparation du catalyseur selon l'invention, l'oxyde de titane peut être sous la forme de poudre ou mis en forme par exemple de billes, d'extrudés, de pastilles ou toute autre forme communément utilisée. La mise en forme peut être réalisée avant ou après le dépôt de l'oxyde de tungstène et avant ou après l'introduction du métal. The reduction step can be carried out in situ, that is to say in the reactor where the reaction takes place, before the introduction of the reaction charge. The reduction can also be performed ex situ. The catalysts used in the present invention may be in the form of powder, extrudates, beads or pellets. When preparing the catalyst according to the invention, the titanium oxide may be in the form of powder or shaped, for example, balls, extrudates, pellets or any other form commonly used. The shaping can be carried out before or after the deposition of the tungsten oxide and before or after the introduction of the metal.
Le catalyseur présente de préférence une surface spécifique comprise entre 15 et 450 m2/g et un volume poreux compris entre 0,05 et 2,0 mL/g. Procédé de transformation The catalyst preferably has a specific surface area of between 15 and 450 m 2 / g and a pore volume of between 0.05 and 2.0 ml / g. Process of transformation
Le procédé de transformation de polyol(s) selon l'invention comprend la réaction dans un milieu contenant de l'eau en présence d'un catalyseur décrit plus haut.  The process for converting polyol (s) according to the invention comprises the reaction in a medium containing water in the presence of a catalyst described above.
Le procédé de conversion de polyols selon l'invention est réalisé avantageusement sous atmosphère réductrice ou sous atmosphère inerte comme le diazote ou l'argon. De préférence, la réaction est réalisée sous atmosphère de dihydrogène. Le dihydrogène peut être utilisé pur ou en mélange. Par exemple le rapport molaire dihydrogène/polyols peut être compris entre 1 et 400, de manière préférée entre 5 et 300 mol/mol. Le procédé est opéré à une température comprise entre Ι δΟ 'Ό et 350 °C, de préférence entre 200 ^ et 270 °C, et à une pression totale comprise entre 0,5 MPa et 20 MPa, de préférence entre 2 MPa et 8 MPa. The polyol conversion process according to the invention is advantageously carried out under a reducing atmosphere or under an inert atmosphere such as dinitrogen or argon. Preferably, the reaction is carried out under a dihydrogen atmosphere. The dihydrogen can be used pure or in mixture. For example, the dihydrogen / polyol molar ratio may be between 1 and 400, preferably between 5 and 300 mol / mol. The process is carried out at a temperature of between Ι δΟ 'Ό and 350 ° C, preferably between 200 ° and 270 ° C, and at a total pressure of between 0.5 MPa and 20 MPa, preferably between 2 MPa and 8 ° C. MPa.
La réaction est opérée en continu, par exemple en lit fixe. La vitesse massique horaire (débit massique de polyol / masse de catalyseur) est comprise entre 0,01 et 10 h"1 , de préférence entre 0,05 et 3 h"1. Exemples The reaction is carried out continuously, for example in a fixed bed. The hourly mass velocity (mass flow rate of polyol / mass of catalyst) is between 0.01 and 10 h -1 , preferably between 0.05 and 3 h -1 . Examples
Exemple 1 : Préparation du catalyseur C1 (conforme à l'invention) : 1 ,2% poids Pt/TiOp-WC 50 g de Ti02-WOx sont préparés par échange anionique d'oxyde de titane de phase cristallographique rutile avec 150 ml_ d'acide tungstique en solution (0,25 mol/L) dans du peroxyde d'hydrogène à 30% volume. La solution obtenue est filtrée et le solide récolté est séché à 1 10 °C pendant 18 heures. Le solide résultant est ensuite calciné sous débit d'air sec à la température de 600 'C pendant 3 heures. EXAMPLE 1 Preparation of Catalyst C1 (in Accordance with the Invention): 1.2% wt. Pt / TiOp-WC 50 g of TiO 2 -WO x are prepared by anionic exchange of titanium oxide of rutile crystallographic phase with 150 ml. of tungstic acid in solution (0.25 mol / L) in 30% volume hydrogen peroxide. The resulting solution is filtered and the collected solid is dried at 110 ° C. for 18 hours. The resulting solid is then calcined under a flow of dry air at a temperature of 600 ° C. for 3 hours.
Le solide S1 obtenu contient en poids 1 1 ,7 % de tungstène. La surface spécifique du solide S1 est de 106 m2/g et le volume poreux de 0,4 mIJg. The solid S1 obtained contains, by weight, 1.17% of tungsten. The specific surface area of the solid S 1 is 106 m 2 / g and the pore volume 0.4 m 2 / g.
Le catalyseur C1 est préparé par imprégnation à sec du solide S1 avec une solution aqueuse d'acide hexachloroplatinique H2PtCl6.6H20. La solution aqueuse est préparée à 25°C par dilution de 1 ,6 g de H2PtCl6.6H20 dans de l'eau déminéralisée à un volume qui correspond au volume poreux du solide S1 . Cette solution est ensuite imprégnée sur 50 g du solide S1 préalablement préparé. Catalyst C1 is prepared by dry impregnation of solid S1 with an aqueous solution of hexachloroplatinic acid H 2 PtCl 6 .6H 2 0. The aqueous solution is prepared at 25 ° C. by dilution of 1.6 g of H 2 PtCl 6 .6H 2 0 in demineralised water at a volume which corresponds to the pore volume of the solid S1. This solution is then impregnated with 50 g of the previously prepared solid S1.
Le solide obtenu est séché à 120 ^ pendant 12 h, puis calciné sous débit d'air sec à la température de 550 °C pendant 2 h.  The solid obtained is dried at 120 ° C. for 12 h and then calcined under a flow of dry air at a temperature of 550 ° C. for 2 hours.
Le catalyseur C1 ainsi obtenu contient 1 ,2% poids de platine et 1 1 ,6% poids de tungstène. Catalyst C1 thus obtained contains 1.2% by weight of platinum and 1.16% by weight of tungsten.
Exemple 2 : Préparation du catalyseur C2 (non conforme à l'invention) : 1 ,2% poids de Pt/
Figure imgf000011_0001
50 g de poudre de Zr02-WOx (MEL Chemicals) sont mélangés avec de l'hydroxyde de zirconium (Zr(OH)4, MEL Chemicals) et mis sous forme d'extrudés. Le solide obtenu est calciné sous débit d'air sec à la température de 700 ^ pendant 3 heures. EXAMPLE 2 Preparation of Catalyst C2 (Not in Accordance with the Invention): 1.2% wt% Pt /
Figure imgf000011_0001
50 g of Zr0 2 -WO x powder (MEL Chemicals) are mixed with zirconium hydroxide (Zr (OH) 4 , MEL Chemicals) and put into the form of extrudates. The solid obtained is calcined under a flow of dry air at a temperature of 700 ° C. for 3 hours.
Le solide S2 contient ainsi en poids 9,7% de tungstène. La surface spécifique du solide S2 est de 73 m2/g et le volume poreux de 0,2 mIJg. The solid S2 thus contains by weight 9.7% of tungsten. The specific surface area of the solid S 2 is 73 m 2 / g and the pore volume 0.2 m 2 / g.
Le catalyseur C2 est préparé par imprégnation à sec du solide S2 avec une solution aqueuse d'acide hexachloroplatinique H2PtCI6.6H20. Une solution aqueuse est préparée à 25^ par dilution de 1 ,6 g de H2PtCI6.6H20 dans de l'eau déminéralisée à un volume qui correspond au volume poreux du solide S2. Cette solution est ensuite imprégnée sur 50 g du solide S2 préalablement préparé. Le solide obtenu est séché à 1 20 ^ pendant 1 2 h, puis calciné sous débit d'air sec à la température de 550 °C pendant 2 h. Catalyst C2 is prepared by dry impregnation of solid S 2 with an aqueous solution of hexachloroplatinic acid H 2 PtCl 6 .6H 2 O. An aqueous solution is prepared at 25 ° by dilution of 1.6 g of H 2 PtCl 6 . 6H 2 O in deionized water to a volume which corresponds to the pore volume of the solid S2. This solution is then impregnated with 50 g of the previously prepared solid S2. The solid obtained is dried at 120 ° C. for 12 hours and then calcined under a dry air flow at a temperature of 550 ° C. for 2 hours.
Le catalyseur C2 obtenu contient 1 ,2% poids de platine et 9,6% poids de tungstène. Exemple 3 : préparation d'un catalyseur C3 (non conforme à l'invention) : 1 ,2% poids Pt/ SiO?-  The catalyst C2 obtained contains 1.2% by weight of platinum and 9.6% by weight of tungsten. Example 3 Preparation of a Catalyst C3 (Not in Accordance with the Invention): 1.2% by Weight Pt / SiO 2
50 g de catalyseur C3 sont préparés par imprégnation à sec d'une alumine silicée (30% Si02 / 70% Al203, Siralox 30, de la société Sasol) avec une solution aqueuse d'acide hexachloroplatinique H2PtCl6.6H20. Une solution aqueuse est préparée à 25°C par dilution de 1 ,6 g de H2PtCl6.6H20 dans de l'eau déminéralisée à un volume qui correspond au volume poreux de l'alumine silicée Siralox 30. Cette solution est ensuite imprégnée sur 50 g du solide préalablement préparé. 50 g of catalyst C3 are prepared by dry impregnation with a silica alumina (30% SiO 2 /70% Al 2 O 3 , Siralox 30, from Sasol) with an aqueous solution of hexachloroplatinic acid H 2 PtCl 6 . 6H 2 0. An aqueous solution is prepared at 25 ° C by dilution of 1.6 g of H 2 PtCl 6 .6H 2 O in demineralized water to a volume which corresponds to the pore volume of the silica alumina Siralox 30 This solution is then impregnated with 50 g of the previously prepared solid.
Le solide obtenu est séché à 1 20 ^ pendant 1 2 h, puis calciné sous débit d'air sec à la température de 550 °C pendant deux heures.  The solid obtained is dried at 120 ° C. for 12 hours and then calcined under a flow of dry air at a temperature of 550 ° C. for two hours.
Le catalyseur C3 obtenu contient 1 ,2% poids de platine.  The catalyst C3 obtained contains 1.2% by weight of platinum.
Exemple 4 : préparation d'un catalyseur C4 (conforme à l'invention) : 1 ,2% poids Pt/TiOp-WOy 50 g de catalyseur C4 sont préparés par imprégnation à sec d'extrudés d'oxyde de titane de phase cristallographique anatase avec une solution aqueuse contenant 3,4 g de métatungstate d'ammonium dans de l'eau déminéralisée à un volume qui correspond au volume poreux du support. Le solide est ensuite calciné 2 h à 500 °C sous débit d'air. Le solide S4 contient ainsi en poids 4,5% de tungstène. La surface spécifique du solide S4 est de 90 m2/g et le volume poreux de 0,35 mL/g. EXAMPLE 4 Preparation of a C4 Catalyst (in Accordance with the Invention): 1.2% by weight of Pt / TiOp-WOy 50 g of C4 catalyst are prepared by dry impregnation of anatase crystallographic phase titanium oxide extrudates with an aqueous solution containing 3.4 g of ammonium metatungstate in demineralised water at a volume which corresponds to the pore volume of the support. The solid is then calcined for 2 hours at 500 ° C. under a flow of air. The solid S4 thus contains by weight 4.5% of tungsten. The specific surface of the solid S4 is 90 m 2 / g and the pore volume of 0.35 ml / g.
Une solution aqueuse est préparée à 25 ^ par dilution de 1 ,6 g de H2PtCI6.6H20 dans de l'eau déminéralisée à un volume qui correspond au volume poreux du solide S4. Cette solution est ensuite imprégnée sur 50 g du solide préalablement préparé. An aqueous solution is prepared at 25 ° by dilution of 1.6 g of H 2 PtCl 6 .6H 2 O in deionized water to a volume which corresponds to the pore volume of the S4 solid. This solution is then impregnated on 50 g of the previously prepared solid.
Le solide obtenu est séché à 1 20 ^ pendant 1 2 h, puis calciné sous débit d'air sec à la température de 550 °C pendant 2 h.  The solid obtained is dried at 120 ° C. for 12 hours and then calcined under a dry air flow at a temperature of 550 ° C. for 2 hours.
Le catalyseur C4 obtenu contient 1 ,2% poids de platine et 4,4% poids de tungstène. Exemple 5 : Transformation d'une solution contenant du sorbitol mettant en œuyre les catalyseurs préparés dans les exemples 1 à 4 Cet exemple concerne la conversion d'une charge contenant 10% poids de sorbitol dans de l'eau par les catalyseurs C1 , C2, C3 et C4 pour la production de produits hydrocarbonés et monofonctionnels contenant au moins 5 atomes de carbone. The catalyst C4 obtained contains 1.2% by weight of platinum and 4.4% by weight of tungsten. EXAMPLE 5 Transformation of a Solution Containing Sorbitol Using the Catalysts Prepared in Examples 1 to 4 This example relates to the conversion of a feed containing 10% by weight of sorbitol in water by the catalysts C1, C2, C3 and C4 for the production of hydrocarbon and monofunctional products containing at least 5 carbon atoms.
Le déroulement d'un test catalytique standard est le suivant. 4 g de catalyseur broyé et tamisé à la granulométrie 150-355μηι sont chargés dans le réacteur. Le catalyseur est ensuite séché et réduit sous dihydrogène in situ pendant 2 h, à 450 °C. Après refroidissement à 50 °C, de l'eau dégazée est envoyée dans le réacteur. La pression du réacteur monte progressivement jusqu'à la valeur fixée de 3,8 MPa. Le réacteur est ensuite chauffé à la température de test de 240 ^. Le rapport débit massique de charge / masse de catalyseur est fixé à 2 h"1. Le débit d'hydrogène est réglé pour avoir un rapport molaire H2/sorbitol de 75. The course of a standard catalytic test is as follows. 4 g of crushed catalyst and sieved to the particle size 150-355μηι are loaded into the reactor. The catalyst is then dried and reduced under dihydrogen in situ for 2 hours at 450 ° C. After cooling to 50 ° C., degassed water is sent to the reactor. The reactor pressure rises gradually to the set value of 3.8 MPa. The reactor is then heated to the test temperature of 240 ° C. The mass flow rate / catalyst mass ratio is set at 2 h -1 The flow rate of hydrogen is set to have an H 2 / sorbitol molar ratio of 75.
Quand les conditions de pression et de température sont stabilisées, la charge de sorbitol dissous dans l'eau (10% poids) remplace l'eau pure. En sortie de réacteur, les produits présents en phase liquide et en phase gazeuse sont analysés périodiquement. Les produits obtenus et leur mode d'analyse  When the pressure and temperature conditions are stabilized, the sorbitol charge dissolved in the water (10% weight) replaces the pure water. At the outlet of the reactor, the products present in the liquid phase and in the gas phase are analyzed periodically. The products obtained and their method of analysis
En sortie de réacteur, les produits de la réaction sont analysés selon plusieurs techniques. Les produits de la réaction contenus dans la phase gazeuse, comme par exemple CO, C02, le dihydrogène, les hydrocarbures contenant un à six atomes de carbone ainsi que certains composés oxygénés légers, sont analysés par chromatographie en phase gazeuse. At the outlet of the reactor, the products of the reaction are analyzed according to several techniques. The reaction products contained in the gas phase, for example CO, CO 2 , dihydrogen, hydrocarbons containing one to six carbon atoms, as well as certain light oxygenated compounds, are analyzed by gas chromatography.
Les produits de la réaction contenus dans la phase liquide sont analysés par chromatographie en phase gazeuse, par chromatographie liquide à haute performances (HPLC). Les produits analysés par ces deux techniques contiennent les familles suivantes : The reaction products contained in the liquid phase are analyzed by gas chromatography, by high performance liquid chromatography (HPLC). The products analyzed by these two techniques contain the following families:
- des polyols, des mono alcools : en particulier le sorbitol, le xylitol, le glycérol, l'isosorbide, l'anhydrosorbitol, l'hexanol, le pentanol, le butanol, le propanol, l'isopropanol, l'éthanol et le méthanol, l'hexanediol, le pentanediol, de butanediol, le propylène glycol, l'éthylène glycol, l'hexanetriol, le butanetriol, le pentanetriol,  polyols, monoalcohols: in particular sorbitol, xylitol, glycerol, isosorbide, anhydrosorbitol, hexanol, pentanol, butanol, propanol, isopropanol, ethanol and methanol; , hexanediol, pentanediol, butanediol, propylene glycol, ethylene glycol, hexanetriol, butanetriol, pentanetriol,
- des cétones, comme par exemple l'hexanone, l'hexanedione, le pentanone, le pentanedione, le butanone, le propanone l'acétone,  ketones, for example hexanone, hexanedione, pentanone, pentanedione, butanone, propanone and acetone,
- des acides carboxyliques et leurs esters, des lactones, comme par exemple l'acide formique, l'acide acétique, l'acide lactique, l'acide lévulinique, les lévulinates d'alkyles, l'acide lactique, l'acide pentanoïque, l'acide hexanoïque, la 3-hydroxybutyrolactone, la γ- butyrolactone,  carboxylic acids and their esters, lactones, for example formic acid, acetic acid, lactic acid, levulinic acid, alkyl levulinates, lactic acid, pentanoic acid, hexanoic acid, 3-hydroxybutyrolactone, γ-butyrolactone,
des éthers cycliques : par exemple le tétrahydrofurane (THF), le méthyltétrahydrofurane (MTHF), le diméthyltétrahydrofurane, le 5- (hydroxyméthyl)furfural, l'acétylfurane, le tétrahydropyrane, - des composés hydrocarbonés comme par exemple l'hexane, le pentane, le méthylcyclopentane, le cyclopentane, le butane. cyclic ethers: for example tetrahydrofuran (THF), methyltetrahydrofuran (MTHF), dimethyltetrahydrofuran, 5- (hydroxymethyl) furfural, acetylfuran, tetrahydropyran, hydrocarbon compounds such as, for example, hexane, pentane, methylcyclopentane, cyclopentane or butane.
La somme du carbone contenu dans les produits de réaction solubles dans l'eau est déterminée par l'analyse COT (Carbone Organique Total). The sum of the carbon contained in the water-soluble reaction products is determined by the TOC analysis (Total Organic Carbon).
Conversion, sélectivité et rendement Conversion, selectivity and yield
Conversion du sorbitol Sorbitol conversion
La conversion du sorbitol à un instant t est calculée selon la formule suivante : The conversion of sorbitol at a time t is calculated according to the following formula:
Conversion Sorbitol (t) = (Qm sorbitol charge - Qm sorbitol (t)) / Qm sorbitol charge Sorbitol conversion (t) = (Qm sorbitol charge - Qm sorbitol (t)) / Qm sorbitol charge
Avec Qm sorbitol charge = débit massique de sorbitol en entrée, en g/h With Qm sorbitol load = mass flow rate of sorbitol input, in g / h
Qm sorbitol (t) = débit massique de sorbitol en sortie, en g/h  Qm sorbitol (t) = mass flow rate of sorbitol output in g / h
Sélectivités et rendements des fractions d'hydrocarbures HC, de CO? et de composés mono- oxygénés  Selectivities and yields of HC hydrocarbon fractions, CO? and mono-oxygenated compounds
L'efficacité d'un catalyseur pour la réaction de transformation du sorbitol s'exprime en terme de sélectivité et de rendement des différentes familles de produits obtenus, soit en particulier les hydrocarbures (notés HC), les composés mono-oxygénés (monoalcools, monocétones et éthers cycliques) et le C02. The effectiveness of a catalyst for the sorbitol transformation reaction is expressed in terms of selectivity and yield of the various families of products obtained, in particular hydrocarbons (denoted HC), mono-oxygenated compounds (monoalcohols, monocetones). and cyclic ethers) and C0 2 .
Le rendement carbone en composé C, (Rdtc C) et la sélectivité carbone en composé C, (Sc C) sont définis comme suit : The carbon yield of compound C (R c C) and the carbon selectivity of compound C (S c C) are defined as follows:
Rdtc Ci = Qc Ci/Qc sorbitol Rdtc Ci = Q c Ci / Qc sorbitol
Sc Ci = Rdtc Ci/Conversion sorbitol S c Ci = Rdt c Ci / Sorbitol conversion
avec : Qc (sorbitol) = fraction carbone du sorbitol x Qm (sorbitol) = 0,40 x Qm (sorbitol), en gC/h Qc C,= débit carbone du composé C, = fraction carbone du composé Ci x Qm (Ci), en gC/h with: Q c (sorbitol) = carbon fraction of sorbitol x Q m (sorbitol) = 0.40 x Q m (sorbitol), in gC / h Q c C = carbon flow rate of compound C, = carbon fraction of compound C x Q m (Ci), in gC / h
Qm (sorbitol): débit massique du sorbitol en entrée, en g/h Q m (sorbitol): mass flow rate of sorbitol input, in g / h
Qm (Ci): débit massique du composé Ci en sortie, en g/h Q m (Ci): mass flow rate of the compound Ci at the outlet, in g / h
Par exemple,  For example,
Qc (n-hexane) = fraction carbone n-hexane x Qm (n-hexane) = 0,84 x Qm (n-hexane), en gC/h Q c (n-hexane) = carbon fraction n-hexane x Q m (n-hexane) = 0.84 x Q m (n-hexane), in gC / h
Qc (CQ2) = fraction carbone CQ2 x Qm (CQ2) = 0,37 x Qm (CQ2), en gC/h Les résultats obtenus après 40 heures de test sous charge réactionnelle sont regroupés dans le Tableau 1 . On notera qu'à 240 'Ό, la conversion du sorbitol est totale de sorte que le rendement est égal à la sélectivité. Q c (CQ 2 ) = carbon fraction CQ 2 x Q m (CQ 2 ) = 0.37 x Q m (CQ 2 ), in gC / h The results obtained after 40 hours of test under a reaction charge are summarized in Table 1. It will be noted that at 240 'Ό, the conversion of sorbitol is complete so that the yield is equal to the selectivity.
Figure imgf000015_0001
Figure imgf000015_0001
Tableau 1 : Conversion d'une charge contenant 10% poids de sorbitol par les catalyseurs C1 , C2, C3 et Table 1: Conversion of a feed containing 10% by weight of sorbitol by catalysts C1, C2, C3 and
C4, au bout de 40 h de test, à 240Ό, PPH = 2 h"1 C4, after 40 h of test, at 240Ό, PPH = 2 hr -1
Sans catalyseur, le sorbitol n'est pas converti et aucun produit de réaction n'est détecté. Without catalyst, the sorbitol is not converted and no reaction product is detected.
En présence du catalyseur 03 qui contient 1 ,2% poids Pt sur un support S1O2-AI2O3, (non conforme à l'invention), on assiste à une conversion totale du sorbitol. Le rendement en composés hydrocarbures et mono-oxygénés contenant 5 et 6 atomes de carbone produits représente 27,1 % du carbone introduit, d'où une sélectivité en ces composés égale à 27,1 % C . Le rendement en hydrocarbures C5-C6 et en C02 est respectivement de 7,7% C et 19,4% C. In the presence of the catalyst 03 which contains 1.2% by weight Pt on a support S102-Al2O3 (not in accordance with the invention), there is a total conversion of sorbitol. The yield of hydrocarbon and mono-oxygen compounds containing 5 and 6 carbon atoms produced represents 27.1% of the carbon introduced, resulting in a selectivity of these compounds equal to 27.1% C. The yield of C5-C6 and C0 2 hydrocarbons is 7.7% C and 19.4% C.
Lorsque le catalyseur C2 qui comprend 1 ,2% poids Pt sur un support Zr02-WOx (non conforme à l'invention) est utilisé, on observe également une conversion de 100% du sorbitol. L'analyse de la phase liquide montre que le rendement en composés hydrocarbures et mono-oxygénés en C5-C6 représente 24,0% du carbone introduit (d'où une sélectivité de 24,0% C). La quantité d'hydrocarbures C5-C6 représente 3,9% du carbone et le C02 17,0%. Ainsi l'utilisation d'un catalyseur contenant une zircone dopée avec du tungstène et un métal Pt ne permet pas d'améliorer significativement la sélectivité en composés C5-C6. When the catalyst C2 which comprises 1.2% by weight Pt on a support Zr0 2 -WO x (not in accordance with the invention) is used, a conversion of 100% of the sorbitol is also observed. analysis of the liquid phase shows that the yield of C5-C6 hydrocarbon and mono-oxygen compounds represents 24.0% of the introduced carbon (hence a selectivity of 24.0% C). The quantity of C5-C6 hydrocarbons represents 3.9% of the carbon and the C0 2 17.0%. Thus the use of a catalyst containing a zirconia doped with tungsten and a Pt metal does not significantly improve the selectivity of C5-C6 compounds.
En utilisant les catalyseurs C1 et C4 qui comprennent 1 ,2% poids Pt sur un support Ti02-WOx (conformes à l'invention), le sorbitol est également totalement converti. Les rendements (identiques aux sélectivités) en composés hydrocarbures et mono-oxygénés en C5-C6 produits représentent 32,1 % et 31 ,5% du carbone introduit. La sélectivité en composés C5-C6 du procédé est donc améliorée avec l'utilisation d'un catalyseur contenant du platine déposé sur un support à base d'oxyde de titane tungsté. By using catalysts C1 and C4 which comprise 1.2% by weight Pt on TiO 2 -WO x support (according to the invention), sorbitol is also completely converted. The yields (identical to the selectivities) of the C5-C6 hydrocarbon and mono-oxygenated compounds produced represent 32.1% and 31.5% of the carbon introduced. The selectivity to C5-C6 compounds of the process is thus improved with the use of a platinum-containing catalyst deposited on a support based on tungsten titanium oxide.
La quantité d'hydrocarbures C5-C6 représente 1 1 ,1 % du carbone et le C02 15,1 % du carbone pour le catalyseur C1 . En utilisant le catalyseur C4 on constate que la quantité d'hydrocarbures C5-C6 représente 9,2% du carbone et le C02 14,0% du carbone. L'utilisation du catalyseur C1 selon l'invention permet d'augmenter de 40% le rendement carbone en hydrocarbures C5-C6 en comparaison au catalyseur de référence C3 (Pt sur Si02-Al203). Le rendement carbone sous forme de C02, produit non désiré, est diminué par rapport aux catalyseurs de l'art antérieur. The amount of the C5-C6 hydrocarbons is 1 1, 1% carbon and 15.1% C0 2 carbon for the catalyst C1. Using the catalyst C4 it is found that the amount of C5-C6 hydrocarbons is 9.2% of the carbon and the CO 2 14.0% of the carbon. The use of the catalyst C1 according to the invention makes it possible to increase by 40% the carbon yield of C5-C6 hydrocarbons in comparison with the reference catalyst C3 (Pt on SiO 2 -Al 2 O 3 ). The carbon yield in CO 2 form , undesired product, is decreased compared to the catalysts of the prior art.
Ainsi, ces exemples démontrent que l'utilisation de catalyseurs hétérogènes contenant au moins un élément métallique choisi dans les groupes 7 à 1 1 de la classification périodique déposé sur un support constitué d'oxyde de titane sur lequel est déposé du tungstène permet de transformer sélectivement les polyols en produits hydrocarbures et en produits mono- oxygénés contenant un nombre d'atomes de carbone supérieur ou égal à 5. Thus, these examples demonstrate that the use of heterogeneous catalysts containing at least one metal element selected from groups 7 to 11 of the periodic table deposited on a support consisting of titanium oxide on which tungsten is deposited makes it possible to transform selectively polyols to hydrocarbon products and mono-oxygenated products containing a number of carbon atoms greater than or equal to 5.

Claims

REVENDICATIONS
1 . Procédé de conversion en milieu aqueux d'une charge comprenant au moins un polyol de formule CnH2n+20n avec 3 < n < 6 en hydrocarbures et en composés mono-oxygénés contenant un nombre d'atomes de carbone supérieur ou égal à 5, dans lequel on met en contact la charge à une température comprise entre 180 et 350 ^ et à une pression comprise entre 0,5 et 20 MPa avec un catalyseur, ledit catalyseur comprenant au moins un métal choisi parmi les groupes 7 à 1 1 du tableau périodique des éléments et un support, ledit support comprenant un oxyde de titane sur lequel est déposé du tungstène avec une teneur en élément tungstène comprise entre 1 et 50% poids par rapport au poids total de catalyseur. 1. A process for converting into a water medium a feedstock comprising at least one polyol of the formula C n H 2 n + 20n with 3 <n <6 in hydrocarbons and mono-oxygen compounds containing a number of carbon atoms greater than or equal to 5, wherein the charge is contacted at a temperature between 180 and 350 ° and at a pressure between 0.5 and 20 MPa with a catalyst, said catalyst comprising at least one metal selected from groups 7 to 11 of the periodic table of the elements and a support, said support comprising a titanium oxide on which is deposited tungsten with a tungsten element content of between 1 and 50% by weight relative to the total weight of catalyst.
2. Procédé selon la revendication 1 , dans lequel la réaction de conversion est réalisée à une température comprise entre 200 et 270 °C et à une pression comprise entre 2 et 8 MPa. 2. The process according to claim 1, wherein the conversion reaction is carried out at a temperature between 200 and 270 ° C and at a pressure of between 2 and 8 MPa.
3. Procédé selon l'une des revendications précédentes, dans lequel la réaction de conversion est réalisée sous atmosphère réductrice ou sous atmosphère inerte. 3. Method according to one of the preceding claims, wherein the conversion reaction is carried out under a reducing atmosphere or under an inert atmosphere.
4. Procédé selon la revendication 3, dans lequel la réaction de conversion est réalisée sous atmosphère de dihydrogène et dans lequel le rapport molaire dihydrogène / polyols est compris entre 1 et 400 mol/mol. 4. Process according to claim 3, in which the conversion reaction is carried out under a dihydrogen atmosphere and in which the dihydrogen / polyol molar ratio is between 1 and 400 mol / mol.
5. Procédé selon l'une des revendications précédentes, dans lequel la teneur de chaque métal choisi parmi les groupes 7 à 1 1 du tableau périodique des éléments est comprise entre 0,01 et 10% poids par rapport au poids total de catalyseur. 5. Method according to one of the preceding claims, wherein the content of each metal selected from groups 7 to 1 1 of the periodic table of elements is between 0.01 and 10% by weight relative to the total weight of catalyst.
6. Procédé selon l'une des revendications précédentes dans lequel la teneur en élément tungstène est comprise entre 2 et 30% poids par rapport au poids total de catalyseur. 6. Method according to one of the preceding claims wherein the tungsten element content is between 2 and 30% by weight relative to the total weight of catalyst.
7. Procédé selon la revendication 6, dans lequel la teneur en élément tungstène est comprise entre 2 et 25% poids par rapport au poids total de catalyseur. 7. The method of claim 6, wherein the content of tungsten element is between 2 and 25% by weight relative to the total weight of catalyst.
8. Procédé selon l'une des revendications précédentes, dans lequel le métal choisi parmi les groupes 7 à 1 1 du tableau périodique des éléments est choisi parmi le Ru, Rh, Pd, Pt, Ni, Cu, Ir ou Re. 8. Method according to one of the preceding claims, wherein the metal selected from groups 7 to 11 of the periodic table of elements is selected from Ru, Rh, Pd, Pt, Ni, Cu, Ir or Re.
9. Procédé selon l'une des revendications précédentes, dans lequel le catalyseur a subi une étape de traitement thermique sous atmosphère réductrice à une température comprise entre 100 et 600 'Ό avant sa mise en œuvre dans la réaction de conversion. 9. Method according to one of the preceding claims, wherein the catalyst has undergone a heat treatment step under a reducing atmosphere at a temperature between 100 and 600 'Ό before its implementation in the conversion reaction.
10. Procédé selon l'une des revendications précédentes, dans lequel le catalyseur est sous forme de billes, d'extrudés ou de pastilles. 10. Method according to one of the preceding claims, wherein the catalyst is in the form of beads, extrudates or pellets.
1 1 . Procédé selon l'une des revendications précédentes, dans lequel le polyol est sélectionné parmi le glycérol, l'erythritol, le thréitol, l'arabitol, le xylitol, le ribitol, le mannitol, le sorbitol, le dulcitol, le fucitol, l'iditol, l'inositol, Tisonnait, le maltitol, le lactitol, le polyglycitol. 1 1. Process according to one of the preceding claims, wherein the polyol is selected from glycerol, erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, dulcitol, fucitol, iditol, inositol, pounding, maltitol, lactitol, polyglycitol.
12. Procédé selon la revendication 1 1 , dans lequel le polyol est sélectionné parmi le sorbitol, le xylitol et le mannitol. The process according to claim 11, wherein the polyol is selected from sorbitol, xylitol and mannitol.
13. Procédé selon l'une des revendications précédentes, dans lequel le polyol est issu du traitement de la biomasse. 13. Method according to one of the preceding claims, wherein the polyol is derived from the treatment of biomass.
PCT/FR2013/051166 2012-05-30 2013-05-27 Method for converting polyols in an aqueous phase in the presence of a catalyst containing titanium oxide and tungsten WO2013178920A1 (en)

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