EP2598239A1 - Process for converting lignocellulosic or cellulose biomass via solid lewis acid catalysts based on tungsten oxide and on a metal chosen from groups 8 to 11 - Google Patents
Process for converting lignocellulosic or cellulose biomass via solid lewis acid catalysts based on tungsten oxide and on a metal chosen from groups 8 to 11Info
- Publication number
- EP2598239A1 EP2598239A1 EP11749209.0A EP11749209A EP2598239A1 EP 2598239 A1 EP2598239 A1 EP 2598239A1 EP 11749209 A EP11749209 A EP 11749209A EP 2598239 A1 EP2598239 A1 EP 2598239A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- cellulose
- biomass
- lignocellulosic biomass
- tungsten
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
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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
- 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
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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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0209—Impregnation involving a reaction between the support and a fluid
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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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/60—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in six-membered rings
Definitions
- the invention relates to a process for converting lignocellulosic biomass or cellulose directly into valuable products containing three carbon atoms using heterogeneous catalysts.
- lignocellulosic biomass or lignocellulose encompasses several products present in varying amounts depending on its origin: cellulose, hemicellulose and lignin. Hemicellulose and cellulose constitute the carbohydrate part of lignocellulose. They are polymers of sugars (pentoses and hexoses). Lignin is a macromolecule rich in phenolic motifs.
- lignocellulosic biomass we mean, for example, forest products and agricultural by-products such as straw as well as certain plants with high agricultural yield.
- the production of chemicals from lignocellulosic biomass can both reduce energy dependence on oil and preserve the environment by reducing greenhouse gas emissions without using resources for food uses.
- Direct transformation is the transformation into a biomass stage valoris scratchess containing three carbon atoms, such as hydroxyacetone and propylene glycol.
- Hydroxyacetone or acetol has the chemical formula C 3 H 6 0 2 and its structure is reflected in its systematic name, 1-hydroxy-propanone. Hydroxyacetone is used, for example, as a chemical intermediate and as a monomer for the synthesis of polyols, but also as a chemical solvent.
- hydroxyacetone can be done chemically or biologically.
- the chemical routes for producing hydroxacetone known to those skilled in the art are via the transformation of petrochemical intermediates such as the hydration of propylene.
- the oxidation of biologically produced 1,2-propanediol can also lead to the formation of hydroxyacetone.
- Propylene glycol, or propan-1, 2-diol has the chemical formula C 3 H 8 O 2 and its structure is reflected in its systematic name, 1,2-dihydroxypropane.
- the applications of propylene glycol are numerous and diverse: for example, its use as a food additive, emulsifier, intermediate of unsaturated polyesters, but also that of coolant or its use in the textile industry.
- propylene glycol is industrially implemented by hydration of propylene oxide.
- the applicants have discovered a process for the direct conversion of cellulose present in the lignocellulosic biomass, optionally pretreated, into recoverable products containing three carbon atoms, using heterogeneous catalysts based on tungsten oxide dispersed on a support of oxide (s) and containing a metal-state element selected from Groups 8 to 11 of the Periodic Table.
- the invention relates to a process for converting lignocellulosic biomass or cellulose into hydroxyacetone and propylene glycol, in which the lignocellulosic biomass or the cellulose is brought into contact, under hydrothermal conditions, under a reducing atmosphere, with a heterogeneous catalyst based on tungsten oxide dispersed on an oxide-based support and containing at least one element in the metallic state selected from Groups 8 to 11 of the Periodic Table, said catalyst having Lewis acid sites.
- the process according to the invention makes it possible selectively to obtain a mixture of products comprising hydroxyacetone and propylene glycol, in a large quantity.
- a mixture of different products including glucose, sorbitol, lactic acid, formic acid, levulinic acid, acetic acid, and the like.
- the process achieves high conversions of the reagent and high selectivities, particularly high yields of hydroxyacetone and propylene glycol, while limiting the formation of oligosaccharides or water-soluble polymers.
- These conversions and selectivities are obtained only under hydrothermal conditions (presence of water), that operating under a reducing atmosphere, and that in the presence of tungsten oxide catalysts having Lewis-type acid properties and containing a metal-state element chosen from groups 8 to 11.
- solid catalysts predominantly having a Bronsted acidity favor the production of soluble and / or soluble polymer oligosaccharides having a lower selectivity for the desired chemical intermediates.
- tungsten oxide catalysts having Lewis-type and non-metal-containing acidic properties do not result in the formation of the desired chemical intermediates, but allow selectively lactic acid to be obtained.
- the molar yield of hydroxyacetone and propylene glycol is greater than the yield of each of the other products obtained during the transformation of the lignocellulosic biomass, and is also greater than the sum of the yields of the various products taken as a whole.
- Said oxide support (s) is preferably selected from the group consisting of aluminum oxides and / or zirconium and / or titanium and / or niobium.
- the Lewis acid site content of the catalyst is preferably greater than 50%.
- the use of these catalysts makes it possible to obtain directly valuable products containing three carbon atoms, in particular hydroxacetone and propylene glycol, in high selectivity while limiting the production of soluble oligosaccharides and polymers.
- the method according to the present invention also makes it possible to improve the conversion of the cellulose present in the lignocellulosic biomass.
- Lignocellulosic biomass consists essentially of three natural constituents present in varying amounts according to its origin: cellulose, hemicellulose and lignin.
- Cellulose (C 6 H 10 O 5 ) n represents the major part (40-60%) of the composition of lignocellulosic biomass. It is a semi-crystalline linear homopolymer of glucose. Cellulose is insoluble in water at ambient temperature and pressure.
- Hemicellulose is the second carbohydrate in quantity after cellulose and constitutes 20 to 40% by weight of lignocellulosic biomass. Unlike cellulose, this polymer consists mainly of pentose monomers (five-atom rings) and hexoses (six-atom rings). Hemicellulose is an amorphous heteropolymer with a degree of polymerization lower than that of cellulose (30-100), and which is generally soluble in water.
- Lignin is an amorphous macromolecule present in lignocellulosic compounds in variable proportions depending on the origin of the material (straw ⁇ 15%, wood: 20-26%). Its function is mechanical strengthening, hydrophobization and plant support. This macromolecule rich in phenolic units can be described as resulting from the combination of three monomer units of propyl-methoxy-phenol type. Its molar mass varies from 5000 g / mol to 10000 g / mol for hardwoods and reaches 20000 g / mol for softwoods.
- 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 food industry (cotton industry residue, bamboo, sisal, banana, corn, panicum) virgatum, alfalfa, coconut, bagasse ...), household organic waste, waste wood processing facilities, used wood building, paper, recycled or not.
- the filler used in the process according to the invention is lignocellulosic biomass or cellulose.
- the cellulose used may be crystalline or amorphous.
- the lignocellulosic biomass load can be used in its raw form, that is to say in its entirety of these three constituents cellulose, hemicellulose and lignin.
- the raw biomass is generally in the form of fibrous residues or powder. In general, it is crushed or shredded to allow its transport.
- the lignocellulosic biomass feed can also be used in its pretreated form, that is to say in a form containing at least one cellulosic part after extraction of lignin and / or hemicellulose.
- 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, thermomechanico-chemical and / or biochemical nature and cause the crystallistisation of cellulose, the solubilization of hemicellulose and / or lignin or the partial hydrolysis of 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.
- Mechanical treatments go beyond simple shredding because they modify the chemical structure of the constituents. They improve the accessibility and the reactivity of cellulose by decrystallinization and by increasing the exchange surface.
- the mechanical treatments include the reduction of the size of the elementary fibers or particles, for example by chipping the biomass using a cutting machine, by grinding the biomass (adjustment of the particle size), destructuring the chips on the press or abrasive grinding of the chips, after preheating.
- Mechanical treatments can be operated in decentralized mode near the production of biomass or in centralized mode directly feeding the transformation.
- Thermochemical treatments include the baking of biomass at high temperature (150-170 ° C) in dilute acid medium (mainly sulfuric acid, but also phosphoric acid, acetic acid or formic acid), in alkaline medium (sodium hydroxide, sulphites, lime. ..) or in an oxidizing medium (oxidation in air or oxygen, peroxide in alkaline medium, peracetic acid).
- dilute acid medium mainly sulfuric acid, but also phosphoric acid, acetic acid or formic acid
- alkaline medium sodium hydroxide, sulphites, lime. ..
- an oxidizing medium oxidation in air or oxygen, peroxide in alkaline medium, peracetic acid.
- Other thermochemical treatments include solvent treatments (hot ethanol) or roasting which can be defined as pyrolysis at moderate temperature and controlled residence time as it is accompanied by partial destruction of the lignocellulosic material.
- the known technologies for roasting are for example the rotary furnace, the moving bed, the fluid
- Thermo-mechanico-chemical treatments include steam treatments (steam explosion, still called flash hydrolysis or “steam-explosion”), ammonia fiber explosion (AFEX) treatment with ammonia or twin-screw extrusion with various chemical reagents.
- steam treatments steam explosion, still called flash hydrolysis or "steam-explosion”
- AFEX ammonia fiber explosion
- Pretreatment prepares the lignocellulosic biomass by separating the carbohydrate portion of the lignin and adjusting the size of the biomass particles to be treated.
- the size of the biomass particles after pretreatment is generally less than 5 mm, preferably less than 500 microns.
- the catalysts used for the transformation of the lignocellulosic biomass or of the cellulose according to the present invention are based on tungsten oxide dispersed on the surface of an oxide support (s) and contain an element in the chosen metallic state. in groups 8 to 11 of the Periodic Table.
- the acidity of a catalyst is the result of two types of acidity combined: a Lewis acidity, characterized by the presence of a gap electron atom, and Bronsted acidity, characterized by an ability to yield a proton.
- a Lewis acidity characterized by the presence of a gap electron atom
- Bronsted acidity characterized by an ability to yield a proton.
- the nature of the acidic sites can be characterized by pyridine adsorption followed by IR spectroscopy according to the method described in [M. Guisnet, P. Ayrault, C. Coutanceau, MF Alvarez, J. Datka, J. Chem. Soc, Faraday Trans. 93, 1661 (1997)].
- the solids used in the process according to the invention are characterized by superficial acid properties, mainly Lewis type.
- the catalyst has a Lewis acid site content of greater than 50%.
- the Lewis acid sites are associated with the presence of coordinatively unsaturated tungsten species but also with the characteristic species of the support: Al 3+ , Zr + , Ti 4+ , Nb 5+ . It is known that the coordination of tungsten surface species (tetrahedral / octahedral) depends on their dispersion, the tungsten content, the nature of the precursors and the heat treatments.
- Tungsten zirconia type catalysts ZrW, associated or not with a metal phase, are described to be active in many applications such as paraffin hydroisomerization (US-6,124,232) or olefin dimerization (US Pat. No. 5,453,556).
- Tungsten zirconia is conventionally prepared by impregnation or coprecipitation: the zirconia-supported tungsten oxides have been described for the first time by Hino and Arata (J. Chem Soc, Chem Commun, 1148 (1979)). This solid is obtained by impregnation of zirconia with ammonium metatungstate, followed by decomposition under air at 800-850 ° C.
- US-5,510,309 discloses a solid obtained by co-precipitation of ammonium metatungstate and ZrOCI 2, followed by calcination at a temperature above 700 ° C.
- the catalysts used in the invention contain, in addition to the tungsten oxide dispersed on the surface of the support, a particular metal, in the metallic state, selected from groups 8 to 11 of the periodic table.
- the catalysts based on tungsten oxide dispersed on the surface of an oxide support (s) used in the process according to the present invention can be synthesized by ion exchange or impregnation followed by a heat treatment.
- the solids obtained have the advantages of being mesoporous and stable, thermally and in hydrothermal conditions.
- the tungsten content is between 2 and 30% by weight, preferably between 10 and 20%, the percentages being expressed as% by weight of metal relative to the total mass of the catalyst.
- the tungsten precursors are selected from tungstic acid, peroxotungstic acid, ammonium meta tungstate, or isopolyanions or heteropolyanions based on tungsten.
- Ammonium meta tungstate is the usual precursor.
- the use of tungstic acid in solution in hydrogen peroxide is preferred because this method promotes the formation of monomeric tungsten species in solution, exchangeable species at acidic pH with Zr, Ti, Al and / or Nb according to the patent application WO 2004/004893.
- a method of preparation consists of anion exchange between a solution of tungstic acid in hydrogen peroxide and zirconium hydroxide and / or titanium and / or aluminum and / or niobium, followed by calcination according to US 2006/0091045.
- the presence of tungsten on the oxide support results in the formation of tungsten oxide.
- the element in the metallic state present in the catalyst used according to the present invention is a metal chosen from a metal from groups 8 to 11 of the periodic table. It is selected from Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt or Cu, Au, Ag. Preferably, the element is selected from Pt, Ni, Ru, Cu. In a very preferred manner, it is platinum.
- the precursors of metal may be, without limiting the origin, metal organic complexes, metal salts.
- metal salts metal chlorides, metal nitrates.
- the introduction of the metal can be carried out by any technique known to those skilled in the art, such as, for example, ion exchange, dry impregnation, impregnation with excess, vapor deposition, etc.
- the introduction of metal can be carried out before or after shaping the catalyst based on tungsten oxide dispersed on a support based on oxides.
- the weight content of the metal element introduced is advantageously between 0.01 and 10% by weight, and preferably between 0.05 and 5% by weight relative to the total mass of the catalyst.
- the step of introducing the metallic element is followed by a heat treatment step.
- the heat treatment is advantageously carried out between 300 ° C. and 700 ° 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 200 ° C. and 600 ° C. under a stream or atmosphere of hydrogen.
- 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 size of the metal particles of the catalyst used in the process according to the invention is preferably less than 10 nm.
- the catalysts used in the present invention may be in the form of powder, extrudates, beads or pellets.
- the shaping can be carried out before or after the introduction of the metal.
- the catalysts used in the present invention are characterized by techniques known to those skilled in the art. For example, in order to characterize the metallic phase, transmission microscopy is mentioned.
- the process for converting lignocellulosic biomass or cellulose according to the invention comprises the reaction in a medium containing water in the presence of the catalytic composition according to the invention.
- medium containing water means conventional liquid media (such as for example ethanol or water) and non-conventional media such as ionic liquids or liquid-type density supercritical media.
- the mass content of water in the medium is generally greater than 1%.
- the medium is water.
- the process for converting lignocellulosic biomass or cellulose according to the invention is carried out under a reducing atmosphere, preferably under a hydrogen atmosphere.
- Hydrogen can be used pure or as a mixture.
- the process is carried out at temperatures between 160 ° C and 250 ° C, preferably between 175 ° C and 230 ° C, and at a pressure between 0.5 MPa and 20 MPa, preferably between 2 MPa and 10 MPa .
- the reaction can be performed according to different embodiments.
- the reaction can be carried out batchwise or continuously, for example in a fixed bed. It can operate in closed reactor or semi-open reactor.
- the catalyst is introduced into the reactor in an amount corresponding to a weight ratio biomass / catalyst of between 1 and 1000, preferably between 1 and 500, preferably between 1 and 100, preferably between 1 and 50 and more preferably between 1 and 25.
- the catalyst introduced into the reactor can undergo a reducing heat treatment step before the introduction of the reaction charge.
- the reducing heat treatment is carried out at a temperature of between 200 ° C. and 600 ° C. under a flow or atmosphere of hydrogen.
- the biomass is introduced into the process in an amount corresponding to a mass ratio (medium containing water) / biomass of between 1 and 1000, preferably between 1 and 500, and even more preferably between 5 and 100.
- a mass ratio (medium containing water) / biomass of between 1 and 1000, preferably between 1 and 500, and even more preferably between 5 and 100.
- the dilution of the biomass is from 1: 1 to 1: 1000, preferably from 1: 1 to 1: 500 and more preferably from 1: 5 to 1: 100.
- the hourly mass velocity (mass feed rate / mass of catalyst) is between 0.01 and 5 h -1 , preferably between 0.02 and 2 h -1 .
- reaction medium is removed and centrifuged.
- reaction liquid is then analyzed by high pressure liquid chromatography (HPLC) using refractometry to determine the conversion product content of the aqueous solution.
- HPLC high pressure liquid chromatography
- the products of the reaction are soluble in water. They consist of monosaccharides and their derivatives, oligosaccharides, but also soluble polymers formed by successive combinations of monosaccharide derivatives.
- monosaccharides is meant simple sugars (hexoses, pentoses) produced by complete depolymerization of cellulose and / or hemicellulose, in particular, glucose, mannose, xylose, fructose ....
- Derivatives of monosaccharides are those products which can be obtained by dehydration, isomerization, reduction or oxidation:
- Alcohol sugars, alcohols and polyols in particular sorbitol, xylitol, glycerol, ethylene glycol, propylene glycol, ethanol, hydroxyacetone ... - ketones, hexane-diones: 2,5-hexanedione, hydroxyacetone ...
- carboxylic acids and their esters, lactones formic acid, levulinic acid, alkyl levulinates, lactic acid, alkyl lactates, glutaric acid, alkyl glutarates, 3-hydroxypropanoic acid, 3- hydroxybutyrolactone, ⁇ -butyrolactone,
- oligosaccharide is meant a carbohydrate having the composition (C 6 H 5 O 5 ) n where n is greater than 1, obtained by partial hydrolysis of the cellulose, or hemicellulose, or starch.
- soluble polymers denotes all the products resulting from the condensation between monosaccharides, oligosaccharides and / or monosaccharide derivatives.
- the amount of water-soluble reaction products is determined by TOC (Total Organic Carbon) analysis, which consists of measuring carbon in solution.
- TOC Total Organic Carbon
- the amount of monosaccharides and their derivatives is determined by HPLC analyzes.
- the conversion is defined as the percentage solubilization of biomass or cellulose is calculated according to the following equation:
- Ub iiise represents the amount of solubilized carbon analyzed by TOC (mg) and Cmitiai the amount of carbon at the beginning of the reaction contained in the biomass or solid cellulose.
- the molar yields of glucose derivatives are calculated by means of HPLC analysis. Each compound is corrected for the number of carbon atoms contained in the glucose unit.
- nC p represents the number of carbon atoms of the derivative i
- Pi the number of moles of the product P
- Glu 0 the number of moles of glucose units contained in the biomass or the cellulose at the beginning of the reaction.
- oligosaccharides and soluble polymers corresponds to a loss of carbon. This carbon loss is deduced from the TOC and HPLC analyzes. The yield of soluble oligosaccharides and polymers is calculated according to the following equation:
- Rdtoûg C - ⁇ rdt.
- C represents the conversion of cellulose et ⁇ rdt, the sum of the molar yields of all monosaccharides and their derivatives analyzed by HPLC.
- Tungsten zirconia has been synthesized in accordance with the teachings of US2006 / 0091045.
- Zirconium hydroxide obtained from a solution of zirconyl chloride and an ammonia solution is dried and then ion-exchanged for 15 minutes using 0.25 M tungstic acid solution. 30% hydrogen peroxide (150 mL). The solid obtained is filtered and then dried at 80 ° C. for 24 hours. It is then calcined under a flow rate of dry air at the temperature of 700 ° C. for 3 hours.
- the tungsten zirconia obtained contains, by weight, 11.7% of tungsten.
- the nature of the acid sites of this catalyst is characterized by pyridine adsorption followed by IR spectroscopy: more than 65% of the acidic sites of this tungsten catalytic formulation are Lewis acid sites.
- Tungsten alumina is prepared using as raw material aluminum hydroxide (boehmite) and tungstic acid. 10 g of hydroxide of aluminum are anionically exchanged with tungstic acid in solution (0.25M) in 150 ml of 30% hydrogen peroxide. The exchange lasts 15 minutes at room temperature. The solid obtained is then filtered and then dried at 80 ° C. for 24 hours.
- the solid is calcined under a flow of dry air at a temperature of 700 ° C. for 3 hours.
- the tungstated alumina obtained contains 18% by weight of tungsten.
- the catalyst C2 obtained contains 1.9% by weight of platinum with a mean platinum particle diameter of 1.1 nm.
- Example 3 Preparation of a Catalyst C3 (not in Accordance with the Invention): Platinum Supported on Silica
- the raw material used is the Si0 2 Alfa Aesar commercial support with a surface area of 300m 2 / g.
- an aqueous solution of platinum tetramine (1.3 mL, 0.171 g) is added at room temperature to the silica (1 g) previously desorbed under vacuum (1 h, 100 ° C.). The mixture is stirred for one hour and is then evaporated. The solid obtained is then dried in an oven at 110 ° C. for 24 hours. Then the catalyst is calcined under a dry nitrogen flow at the temperature of 500 ° C for two hours and then reduced under hydrogen flow at 300 ° C for two hours.
- the catalyst C3 obtained contains 1.6% by weight of platinum with a mean platinum particle diameter of 4.6 nm.
- This example relates to the conversion of cellulose from catalysts C1, C2 and C3 for the production of valuable C3 products, and in particular hydroxyacetone and propylene glycol.
- the amount of hydroxyacetone formed represents 7 mol% of the amount of starting cellulose.
- the amount of hydroxyacetone and polypropylene glycol produced is 8 mol%.
- the cellulose conversion is 28%.
- the amount of hydroxyacetone formed represents 28 mol% of the amount of starting cellulose, with 48 mol% of hydroxyacetone and propylene glycol molecules (70% selectivity). The conversion is 70%. The propylene glycol yield is 20%.
- the amount of hydroxyacetone formed represents 28 mol% of the amount of starting cellulose, with 36 mol% of molecules of hydroxyacetone and propylene glycol molecules (65% selectivity). The conversion is 59%.
- the combination of platinum and a tungsten support is effective in comparison with a tungsten catalyst without metal phase.
- An increase in total conversion of 15% and selectivity in C 3 oxygenated molecules of 13% is observed in the case of tungsten alumina in the presence or absence of platinum.
- a difference in selectivity is observed when adding platinum. In the absence of platinum, a high selectivity is obtained in lactic acid. In the presence of platinum, a high selectivity of hydroxacetone and propylene glycol is obtained.
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Abstract
Description
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1003180A FR2963346B1 (en) | 2010-07-29 | 2010-07-29 | PROCESS FOR TRANSFORMING LIGNOCELLULOSIC BIOMASS OR CELLULOSE THROUGH SOLID ACID CATALYSTS OF LEWIS BASED ON TUNGSTEN OXIDE AND A METAL SELECTED IN GROUPS 8 TO 11 |
PCT/FR2011/000424 WO2012022853A1 (en) | 2010-07-29 | 2011-07-19 | Process for converting lignocellulosic or cellulose biomass via solid lewis acid catalysts based on tungsten oxide and on a metal chosen from groups 8 to 11 |
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EP2598239A1 true EP2598239A1 (en) | 2013-06-05 |
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EP11749209.0A Withdrawn EP2598239A1 (en) | 2010-07-29 | 2011-07-19 | Process for converting lignocellulosic or cellulose biomass via solid lewis acid catalysts based on tungsten oxide and on a metal chosen from groups 8 to 11 |
Country Status (6)
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US (1) | US8877982B2 (en) |
EP (1) | EP2598239A1 (en) |
BR (1) | BR112013002207A2 (en) |
CA (1) | CA2806941C (en) |
FR (1) | FR2963346B1 (en) |
WO (1) | WO2012022853A1 (en) |
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JP5928894B2 (en) * | 2012-08-30 | 2016-06-01 | 国立大学法人大阪大学 | Polyhydric alcohol hydrocracking catalyst, and method for producing 1,3-propanediol using the catalyst |
JP6446807B2 (en) * | 2014-03-26 | 2019-01-09 | 三菱ケミカル株式会社 | Method for producing organic compound using microorganism |
CN111054337B (en) * | 2018-10-16 | 2023-01-31 | 中国石油化工股份有限公司 | Catalyst for preparing ethylene glycol from biomass |
CN111054320B (en) * | 2018-10-16 | 2022-10-11 | 中国石油化工股份有限公司 | Catalyst for preparing ethylene glycol from biomass |
CN111054330A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing ethylene glycol from biomass and preparation method thereof |
CN111054339B (en) * | 2018-10-16 | 2023-05-02 | 中国石油化工股份有限公司 | Catalyst composition for preparing ethylene glycol |
CN111054336A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing biomass-based ethylene glycol and preparation method thereof |
CN111054335A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing biomass-based ethylene glycol |
CN114423728B (en) * | 2019-09-25 | 2023-09-19 | 国际壳牌研究有限公司 | Pretreatment of lignocellulosic feedstock for diol production |
CN115974646A (en) * | 2021-10-14 | 2023-04-18 | 中国科学院大连化学物理研究所 | Method for preparing ethanol by catalyzing carbohydrate with monatomic catalyst |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2488722A (en) * | 1946-11-14 | 1949-11-22 | Hamit H Gurkan | Catalytic hydrogenation of cellulose to produce oxygenated compounds |
US5510309A (en) | 1994-05-02 | 1996-04-23 | Mobil Oil Corporation | Method for preparing a modified solid oxide |
US5453556A (en) | 1994-06-22 | 1995-09-26 | Mobil Oil Corporation | Oligomerization process for producing synthetic lubricants |
US6124232A (en) | 1996-10-16 | 2000-09-26 | Mobil Oil Corporation | Method for preparing an acidic solid oxide |
US6841085B2 (en) | 2001-10-23 | 2005-01-11 | Battelle Memorial Institute | Hydrogenolysis of 6-carbon sugars and other organic compounds |
FR2841797B1 (en) | 2002-07-03 | 2005-08-05 | Centre Nat Rech Scient | CATALYSTS BASED ON TUNGSTEN |
BRPI0708416A2 (en) | 2006-03-01 | 2011-05-31 | Univ Hokkaido Nat Univ Corp | catalyst for cellulose hydrolysis and / or reduction of hydrolysis products, and method of production of sugar alcohols |
CN101768050B (en) * | 2009-12-25 | 2012-12-05 | 北京大学 | Method for preparing ethylene glycol and 1,2-propylene glycol |
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2010
- 2010-07-29 FR FR1003180A patent/FR2963346B1/en not_active Expired - Fee Related
-
2011
- 2011-07-19 BR BR112013002207A patent/BR112013002207A2/en not_active Application Discontinuation
- 2011-07-19 EP EP11749209.0A patent/EP2598239A1/en not_active Withdrawn
- 2011-07-19 US US13/812,921 patent/US8877982B2/en not_active Expired - Fee Related
- 2011-07-19 CA CA2806941A patent/CA2806941C/en not_active Expired - Fee Related
- 2011-07-19 WO PCT/FR2011/000424 patent/WO2012022853A1/en active Application Filing
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BR112013002207A2 (en) | 2016-05-24 |
US8877982B2 (en) | 2014-11-04 |
US20130184496A1 (en) | 2013-07-18 |
FR2963346A1 (en) | 2012-02-03 |
CA2806941A1 (en) | 2012-02-23 |
WO2012022853A1 (en) | 2012-02-23 |
FR2963346B1 (en) | 2013-03-15 |
CA2806941C (en) | 2018-03-20 |
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