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    • 专利摘要:
    The invention relates to a process for converting a filler chosen from sugars or sugar alcohols, alone or as a mixture, into mono- or polyoxygenated compounds, in which the filler is brought into contact with at least one heterogeneous catalyst comprising a carrier. chosen from among the perovskites of formula ABO3 in which A is chosen from the elements Mg, Ca, Sr and Ba, and B is chosen from Fe, Mn, Ti and Zr elements, and the oxides of the elements chosen from lanthanum and neodymium. , yttrium, cerium, alone or as a mixture, said oxides being dopable by at least one element selected from alkali metals, alkaline earths and rare earths, under a reducing atmosphere, and at a temperature of between 100 ° C. C and 300 ° C, and at a pressure of between 0.1 MPa and 50 MPa.
    公开号:FR3037951A1
    申请号:FR1555966
    申请日:2015-06-26
    公开日:2016-12-30
    发明作者:Emilie Brule；Etienne Girard；Amandine Cabiac；Damien Delcroix；Marc Jacquin
    申请人:IFP Energies Nouvelles IFPEN；
    IPC主号:
    专利说明:

    [0001] FIELD OF THE INVENTION The invention relates to the conversion of bio-sourced compounds into chemical intermediates and the use of hydrothermally stable basic supports without adding additional base for the conversion of sugars and sugars alcohols to mono- or polyoxygenated compounds. PRIOR ART The conversion of sugar and sugar alcohols into mono- or polyoxygenated compounds is conventionally carried out in a basic medium by combining a base consisting of an oxide or a salt of an alkaline or alkaline-earth metal with a heterogeneous catalyst consisting of a hydrogenating metal deposited on a support in the presence of a hydrogen pressure.
    [0002] For example, the patent application WO 2015/055315 of Biochemtex claims the combination of NaOH with Ru deposited on carbon, alumina or zirconia, to transform sorbitol and xylitol, alone or as a mixture, at 200 ° C. under 60 bar ( 25 ° C) of hydrogen to ethylene glycol, propylene glycol and glycerol. US Patent 4,366,332 to Hydrocarbon Research claims the combination of Ca (OH) 2 with Ni supported on silica or alumina to convert sorbitol at 240 ° C under 120 bar (25 ° C) hydrogen to ethylene 4ycol, propylene glycol and glycerol. The disadvantage of the use of a base in combination with the heterogeneous catalyst is the formation of organic salts which must be neutralized and separated from the reaction medium. Work has been done in the prior art to work without additional basis.
    [0003] For example, Mu et al. describe in Catalysis Communications, 2013, 39, 86-89 the transformation of sorbitol at 200 ° C. under 40 bar of hydrogen (25 ° C.) into glycols and glycerol in the presence of a single heterogeneous catalyst composed of Ni deposited on an oxide magnesium Ni / MgO with a 3/7 ratio between Ni and Mg. The hydrothermal stability of this support is poor and results in a loss of activity and selectivity. More than 10% of non-oxygenated gaseous products are furthermore obtained at a partial conversion of sorbitol of about 70%. US Patent 4,496,780 to UOP claims transformation of polyols including glucose, fructose and sorbitol by hydrocracking to lighter polyols including glycerol, ethylene glycol and propylene glycol in the presence of a single heterogeneous catalyst comprising a metal. Group VIII noble of the periodic table deposited on a solid support doped with an alkaline earth metal oxide. For example, the transformation of sorbitol in water at 180 ° C. under 220 bar of hydrogen in the presence of a catalyst comprising ruthenium deposited on a titanated alumina doped with barium oxide (Ru / TiO 2 -Al 2 O 3). BaO) makes it possible to obtain ethylene glycol, propylene glycol and glycerol. In hydrothermal conditions, the ruthenium particles on alumina aggregate, which results in a loss of activity and selectivity and makes it necessary to regenerate the catalyst.
    [0004] These catalytic systems therefore make it possible to convert the sugar alcohols into polyoxygenated products without adding additional base but are not hydrothermally stable. There is therefore a need for hydrothermally stable basic supports for the conversion of sugars and sugar alcohols into mono- and polyoxygenated compounds without adding additional base. The large surface area of the supports used for depositing the hydrogenating metal causes, under hydrothermal conditions, the modification of the textural properties of the support which can lead to the aggregation of the supported metal particles and thus the deactivation of the catalyst, necessitating regular regeneration steps. There is therefore a need for hydrothermally stable supports for the conversion of sugars and sugar alcohols to mono- and polyoxygenated compounds. The present invention therefore proposes the use of novel heterogeneous catalysts consisting of a hydrogenating metal deposited on a hydrothermally stable basic support, without adding additional base. In recent years, there has been a keen interest in the incorporation of products of renewable origin into the fuel and chemical sectors, in addition to or in substitution for products of fossil origin. Lignocellulosic biomass is an abundant source of renewable carbon. The cellulose and hemicellulose constituting the lignocellulosic biomass can easily be depolymerized into glucose and xylose. These sugars can be catalytically hydrogenated in their equivalent sugar alcohols, sorbitol and xylitol, for example. The hydrogenolysis of these sugars and sugar alcohols under basic conditions gives access to polyoxygenated chemical intermediates which are very important industrially, such as ethylene glycol, propylene glycol and glycerol. Under the same hydrogenolysis conditions, equally important monooxygenated chemical intermediates such as methanol, ethanol or propanol can also be obtained.
    [0005] The hydrogenolysis of sugars and sugar alcohols into mono- or polyoxygenated compounds is conventionally carried out in an aqueous medium, basic by combining a base consisting of an alkali or alkaline earth metal oxide or salt with a heterogeneous catalyst consisting of hydrogenating metal deposited on a support in the presence of hydrogen pressure and at temperatures above 100 ° C. It is not described in the prior art of a catalytic system that allows a transformation of sugars or sugar alcohols without adding additional base and using a heterogeneous catalyst consisting of a hydrothermally stable basic support on which the hydrogenating metal is deposited. We therefore propose to transform a charge selected from sugars and sugar alcohols, alone or as a mixture, by bringing said charge into contact with at least one heterogeneous catalyst comprising a hydrothermally stable basic support chosen from among the perovskites of structure ABO3. and the oxides of the elements chosen from lanthanum, neodymium, yttrium and cerium, alone or as a mixture, said oxides being doped with an alkali metal and / or an alkaline earth metal and / or a rare earth element of the type described in the present invention without addition of additional base. The work of the applicant has made it possible to demonstrate that the contacting of a filler chosen from sugars and sugar alcohols, alone or as a mixture, without addition of additional base, with at least one hydrothermally stable heterogeneous catalyst, such as that claimed, in a reaction chamber operating under specific operating conditions, allowed to obtain mono- or polyoxygenated products as claimed. OBJECT OF THE INVENTION It is therefore an object of the present invention to provide a process for converting a filler selected from sugar and sugar alcohols, alone or in admixture, into mono- or polyoxygenated compounds, wherein said filler is contacting with at least one heterogeneous catalyst in the presence of at least one solvent, said solvent being water, an alcohol, a diol or another solvent, under a reducing atmosphere, and at a temperature of between 100 ° C. and 300 ° C, and at a pressure of between 0.1 MPa and 50 MPa, without addition of additional base, wherein said at least one heterogeneous catalyst (s) comprises at least one metal selected from Group 8 metals to 11 of the Periodic Table and a support selected from the perovskites of formula ABO3 wherein A is selected from Mg, Ca, Sr and Ba, and B is selected from Fe, Mn, Ti and Zr, and oxides of the elements selected from lanthanum, neodymium, yttrium, cerium, alone or as a mixture, said oxides being dopable by at least one element selected from alkali metals, alkaline earths and rare earths, alone or in admixture, said process operating without adding additional catalyst.
    [0006] In the present invention, reference is made to the new notation of the Periodic Table of Elements: Handbook of Chemistry and Physics, 76th Edition, 1995-1996.
    [0007] Heterogeneous catalyst means a catalyst which is not soluble in the reaction operating conditions. An advantage of the present invention is to make it possible to obtain mono- or polyoxygenated recoverable products from sugars or sugar alcohols, alone or as a mixture, in the presence of a hydrothermally stable heterogeneous catalyst and without addition of additional base. By hydrothermal stability is meant a conservation of the support structure and of the heterogeneous catalyst, observable by X-ray diffraction, and a preservation of the texture of the support and of the heterogeneous catalyst, observable by nitrogen desorption adsorption for example. Preferably, the specific surface of the support and the heterogeneous catalyst is retained. The specific surface of the support and of the heterogeneous catalyst after reaction is preferably reduced by at most 30% relative to that of the support and the heterogeneous catalyst before reaction and very preferably decreased by at most 20% relative to that of the support. and heterogeneous catalyst before reaction. DETAILED DESCRIPTION OF THE INVENTION The filler The filler treated in the process according to the invention is a filler selected from sugars and sugar alcohols, alone or in admixture. By sugar is meant any soluble oligosaccharide or monosaccharide under the reaction conditions contemplated by the invention.
    [0008] Monosaccharides more particularly denotes carbohydrates of general formula C x (H 2 O) x or C x H 2 x O x with an integer of between 3 and 6 inclusive. Preferred monosaccharides used as filler in the present invention are selected from dihydroxyacetone (x = 3), erythrose (x = 4), xylose (x = 5), arabinose (x = 5), glucose (x = 6), mannose (x = 6) and fructose (x = 6), taken alone or as a mixture. Preferably, the sugar feed used in the process according to the invention is chosen from cellobiose, dihydroxyacetone, erythrose, xylose, fructose and glucose, taken alone or as a mixture. Very preferably, said filler is chosen from xylose, fructose and glucose, taken alone or as a mixture.
    [0009] Oligosaccharide more particularly denotes a carbohydrate having the empirical formula C6nH1On + 205n + 1 or C5nH8n + 204n + 1 where n is an integer greater than 1, the monosaccharide units making up said oligosaccharide being identical or different, and a hydrate of carbon having the formula (C6.1-110m + 205m + 1) (C5nH8n + 204n + 1) where m and n are integers greater than or equal to 1, the monosaccharide units making up said oligosaccharide being identical or different. The oligosaccharides are preferably chosen from oligomers of pentoses and / or hexoses with a degree of polymerization enabling them to be soluble in the reaction conditions envisaged by the invention. They may be obtained by partial hydrolysis of polysaccharides derived from renewable resources such as starch, inulin, cellulose or hemicellulose, possibly derived from lignocellulosic biomass. For example, the steam explosion of lignocellulosic biomass is a process of partial hydrolysis of cellulose and hemicellulose contained in lignocellulosic biomass producing a flux of oligo- and monosaccharides. The preferred oligosaccharides used as filler in the present invention are selected from sucrose, lactose, maltose, isomaltose, inulobiose, melibiose, gentiobiose, trehalose, cellobiose, cellotriose, cellotetraose, and the like. oligosaccharides resulting from the hydrolysis of said polysaccharides resulting from the hydrolysis of starch, inulin, cellulose or hemicellulose, taken alone or as a mixture. By sugar alcohol, is meant more particularly the molecules obtained by hydrogenation of oligosaccharide sugars and monosaccharides previously defined. In the case where the alcohol sugars are obtained by hydrogenation of the oligosaccharide sugars, said alcohol sugars advantageously correspond to either the general formula C6nH1on + 405n ± 1 or C5n1-18n + 404n ± 1 where n is an integer greater than 1, or following general formula (C6mH10m + 205m + 1) (C5nH8n + 204n + 1) H2 where m and n are integers greater than or equal to 1. The preferred alcohol sugars used as filler in the present invention obtained by hydrogenation of the oligosaccharide sugars are chosen among lactitol, maltitol, isomaltitol, inulobitol, melibitol, gentiobitol, cellobitol, cellotritol and cellotetritol, alone or as a mixture. The sugar alcohols obtained by hydrogenation of the monosaccharide sugars advantageously have the following general formula Cx (H 2 O) xH 2 or C x H 2 x + 20x with an integer of between 3 and 6 inclusive. The preferred alcohol sugars used as filler in the present invention obtained by hydrogenation of the monosaccharide sugars are chosen from glycerol (x = 3), erythritol (x = 4), xylitol (x = 5), arabinitol (x = 5), sorbitol (x = 6) and mannitol (x = 6), alone or as a mixture.
    [0010] Thus, the sugar alcohol charge used in the process according to the invention is chosen from lactitol, maltitol, isomaltitol, inulobitol, melibitol, gentiobitol, cellobitol, cellotritol, cellotetritol and glycerol. erythritol, xylitol, arabinitol, sorbitol, mannitol, alone or as a mixture.
    [0011] Preferably, the sugar alcohol charge used in the process according to the invention is chosen from cellobitol, glycerol, erythritol, xylitol, sorbitol, mannitol, taken alone or as a mixture.
    [0012] Most preferably, said filler is selected from xylitol, sorbitol and mannitol, alone or in admixture. The catalysts According to the invention, said filler is contacted in the process according to the invention with only at least one heterogeneous catalyst as defined below in the presence of at least one solvent, said solvent being water, an alcohol, a diol or other solvent, under a reducing atmosphere, and at a temperature of between 100 ° C. and 300 ° C., and at a pressure of 0.1 MPa and 50 MPa.
    [0013] According to the invention, said heterogeneous catalyst or catalysts comprise at least one metal chosen from metals of groups 8 to 11 of the periodic table and a support chosen from perovskites of formula ABO3 in which A is chosen from Mg elements, Ca, Sr and Ba, and B is selected from the elements Fe, Mn, Ti and Zr, and the oxides of the elements selected from lanthanum (La), neodymium (Nd), yttrium (Y), cerium (Ce), alone or as a mixture, said oxides being dopable by at least one element selected from alkali metals, alkaline earths and rare earths, alone or as a mixture.
    [0014] In the case where several heterogeneous catalysts as defined above are used in the process according to the invention, said catalysts may be identical or different. In a preferred embodiment, a single heterogeneous catalyst as defined above is used in the process according to the invention.
    [0015] Said metals chosen from the metals of groups 8 to 11 of the periodic classification of the heterogeneous catalyst (s) according to the invention are preferably chosen from the following metals: Fe, Ru, Os, Co, Rh, Ir , Ni, Pd, Pt, Cu, Ag, Au, taken alone or in admixture.
    [0016] Preferably, said metal is selected from Ru, Rh, Ir, Ni, Pd, Pt, Cu metals, taken alone or as a mixture. Very preferably, said metal is selected from metals Ru, Ni, Pt, taken alone or as a mixture. In the case where the metal of said one or more heterogeneous catalysts is chosen from the following noble metals: Ru, Os, Rh, Pd, Pt, Ag, Au, the content of noble metal on said heterogeneous catalyst or catalysts is advantageously between 0, 1% 15 and 10% by weight and preferably between 0.1% and 5% by weight relative to the total mass of said heterogeneous catalyst or catalysts. In the case where the metal of said one or more heterogeneous catalysts is chosen from non-noble metals, the content of non-noble metal on said heterogeneous catalyst or catalysts is advantageously between 0.1% and 40% by weight and preferably between 0% and 40% by weight. , 1% and 30% by weight relative to the total mass of said one or more heterogeneous catalysts. The metal (s) of the heterogeneous catalyst (s) according to the invention are advantageously deposited on a support. According to the invention, said heterogeneous catalyst or catalysts comprise a support chosen from perovskites of formula ABO3 in which A is chosen from Mg, Ca, Sr and Ba elements, and B is chosen from elements Fe, Mn, Ti and Zr, and the oxides of the elements chosen from lanthanum (La), neodymium (Nd), yttrium (Y), cerium (Ce), alone or as a mixture, said oxides being dopable by at least 30% by weight an element selected from alkali metals, alkaline earths and rare earths, alone or as a mixture. Non-limiting examples of perovskite are: BaTiO3, SrTiO3, BaZrO3, CaZrO3, SrZrO3, CaMnO3. In the case where said support is chosen from doped oxides, the doping element is chosen from alkali metals, alkaline earths and rare earths, alone or as a mixture.
    [0017] In the case where said support is chosen from oxides doped with at least one element chosen from alkali metals, said doping element is advantageously chosen from Li, Na, K, Rb and Cs elements and preferably from Li, Na, K.
    [0018] In the case where said support is chosen from oxides doped with at least one element selected from alkaline earth, said doping element is advantageously chosen from Be, Mg, Ca, Sr, Ba, and preferably from Ca, Sr, Ba. In the case where said support is chosen from oxides doped with at least one element chosen from rare earths, said doping element is advantageously chosen from La, Ce, Sm, Gd, Y, Pr. Preferably, the content of element Dopant chosen from alkali metals, alkaline earths and rare earths, alone or as a mixture is advantageously between 0.1% and 30% by weight and preferably between 1 and 20% by weight relative to the total mass of said support. Preferably, the support of said heterogeneous catalyst (s) is chosen from perovskites.
    [0019] In another preferred embodiment, the carrier of said heterogeneous catalyst (s) is dopable cerium oxide.
    [0020] The BET specific surface area of the support is advantageously less than 200 m 2 / g, preferably less than 150 m 2 / g, preferably less than 100 m 2 / g, preferably less than 70 m 2 / g, and more preferably more preferred less than 50 m2 / g. Said support is according to the invention hydrothermally stable, ie stable under conditions combining water and temperature.
    [0021] By hydrothermal stability is meant a conservation of the structure of the support, observable by X-ray diffraction, and a preservation of the texture of the support observable by adsorption nitrogen desorption for example. Preferably the specific surface of the support is also preserved. The specific surface area of the support after reaction is preferably at least 30% less than that of the support before reaction and very preferably at most 20% less than that of the support before reaction. Thus, the support can advantageously undergo a treatment step prior to its use in the process according to the invention for improving its stability under the hydrothermal conditions of the reaction. For example, surface passivation, carbon film deposition, oxide deposition may be mentioned. The deposition of the metal (s) chosen from groups 8 to 11 of the periodic table on said support of the heterogeneous catalyst (s) according to the invention generally involves a precursor of the metal (s). For example, it may be metal organic complexes, metal salts such as metal chlorides, metal nitrates, metal carbonates. The introduction of the metal or metals may advantageously be carried out by any technique known to those skilled in the art, such as, for example, ion exchange, dry impregnation, excess impregnation, vapor phase deposition, etc. The introduction of metal can be carried out before or after the shaping of the support. The introduction step of the metal or metals can advantageously be followed by a heat treatment step. The heat treatment is advantageously carried out between 300 ° C. and 700 ° C. under an oxygen or air atmosphere. The thermal 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. Preferably, said one or more heterogeneous catalysts also undergo an in situ reduction step, that is to say in the reactor where the reaction takes place, before the introduction of the reaction charge. Said reduction step may also advantageously be carried out ex-situ. The heterogeneous catalyst (s) 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 BET specific surface area of the heterogeneous catalyst is advantageously less than 200 m 2 / g, preferably less than 150 m 2 / g, more preferably less than 100 m 2 / g, preferably less than 70 m 2 / g, and more preferred less than 50 m 2 / g. Said heterogeneous catalyst is according to the invention hydrothermally stable, ie stable under conditions combining water and temperature.
    [0022] By hydrothermal stability is meant a conservation of the structure of the heterogeneous catalyst, observable by X-ray diffraction, and a preservation of the texture of the heterogeneous catalyst, observable by nitrogen desorption adsorption for example. Preferably, the surface area of the heterogeneous catalyst is also conserved. The specific surface area of the heterogeneous catalyst after reaction is preferably decreased by at most 30% relative to that of the heterogeneous catalyst before reaction and very preferably decreased by at most 20% relative to that of the heterogeneous catalyst before reaction. By hydrothermal stability is also meant a preservation of the chemical composition of the heterogeneous catalyst, observable by elemental analysis. Preferably the elemental chemical composition of the heterogeneous catalyst is retained. The chemical composition of each element of the heterogeneous catalyst after reaction is thus preferably at most 30% lower than that of the heterogeneous catalyst before reaction, very preferably at most 20% less than that of the catalyst. heterogeneous before reaction. The heterogeneous catalyst (s) used in the present invention are characterized by techniques known to those skilled in the art. For example, to characterize the metal phase, transmission microscopy, to characterize the structure of the heterogeneous catalyst, X-ray diffraction, to characterize the texture of the heterogeneous catalyst, adsorption nitrogen desorption, to measure the chemical composition of the heterogeneous catalyst, X-ray fluorescence.
    [0023] According to the invention, said process operates without the addition of additional catalyst. In particular, said process according to the invention operates without the addition of additional basic catalyst. Preferably, said process according to the invention operates without the addition of a basic catalyst chosen from oxides, hydroxides and alcoholates of alkali or alkaline-earth metals, hydrated or not, having the general formula MmXn.n'H2O in which the metal M is a metal selected from metals of groups 1 and 2 of the Periodic Table, m is an integer from 1 to 2, n is an integer from 1 to 2 and n 'is a number from 0 to 20 and X is chosen from oxygen, the hydroxyl group or the alcoholic groups of general formula OR with R an alkyl group.
    [0024] In accordance with the invention, the process for converting the filler chosen from sugars and sugar alcohols, alone or as a mixture, is carried out in a reaction vessel in the presence of at least one solvent, said solvent being water, an alcohol, a diol, alone or as a mixture, under a reducing atmosphere, and at a temperature of between 100 ° C. and 300 ° C., and at a pressure of between 0, and 1 MPa and 50 MPa.
    [0025] The process is therefore carried out in a reaction vessel comprising at least one solvent and wherein said feedstock is placed in the presence of the heterogeneous catalyst according to the invention. According to the invention, the process according to the invention operates in the presence of at least one solvent, said solvent being water, an alcohol, a diol, alone or as a mixture. The diols are advantageously chosen from ethylene glycol and propylene glycol. The alcohols are advantageously chosen from methanol, ethanol and propanols. In the case where said process according to the invention operates in the presence of water, the solvent mixture comprises a mass content of water greater than 5% by weight and preferably greater than 30% and very preferably greater than 50%. relative to the total mass of said mixture. According to another embodiment, the method according to the invention operates only in the presence of water.
    [0026] According to the invention, the process for converting said feedstock is carried out under a reducing atmosphere, preferably under a hydrogen atmosphere. Hydrogen can be used pure or as a mixture. Hydrogen may advantageously come from the reforming of mono- or polyoxygenated compounds derived from renewable resources by any reforming method known to those skilled in the art. Preferably, said process according to the invention operates at a temperature of between 100 ° C. and 300 ° C. and preferably between 50 ° C. and 250 ° C. and at a pressure of between 0.1 MPa and 50 MPa. preferably between 0.5 and 30 MPa. Generally the method can be operated according to different embodiments.
    [0027] Thus, the process may advantageously be carried out batchwise or continuously, for example in a fixed bed. It can be carried out in a closed reaction chamber or in a semi-open reactor. The heterogeneous catalyst or catalysts are introduced into the reaction chamber in the amount of a mass ratio heterogeneous charge (s) / catalyst (s) of between 1 and 1000, preferably between 1 and 500, preferably between 1 and 100, preferably between 1 and 50 and more preferably between 1 and 25. The heterogeneous catalyst (s) introduced into the reactor can undergo a reducing heat treatment step beforehand. the introduction of the reaction charge. The reducing heat treatment is preferably carried out at a temperature of between 100 ° C. and 600 ° C. under a stream or a hydrogen atmosphere. The feedstock is introduced into the process in an amount corresponding to a solvent to filler mass ratio of between 0.1 and 200, preferably between 0.3 and 100 and more preferably between 1 and 50. If If a continuous process is chosen, the hourly mass velocity (mass load rate / mass of heterogeneous catalyst (s)) is between 0.01 hr-1 and 5 hr-1, preferably between 0.02 hr- 1 and 21-1-1.
    [0028] The products obtained and their mode of analysis The products of the reaction of the transformation process according to the invention are mono- or polyoxygenated compounds. Said mono- or polyoxygenated compounds are soluble in water, in alcohols and in diols. Said mono- or polyoxygenated compounds are advantageously constituted by alcohols, polyols, aldehydes, ketones, carboxylic acids and their esters.
    [0029] By alcohol is meant methanol, ethanol, propanols, butanols, pentanols and hexanols. The term "polyols" denotes: diols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 2,3-butanediol, 1,4-butanediol and pentanediols , hexanediols. triols such as glycerol, 1,2,3-butanetriol, 1,2,4-butanetriol, pentanetriols and hexanetriols. tetrols such as erythritol, pentanetetrols and hexanetetrols. For example, aldehyde refers to glycolaldehyde or glyceraldehyde. By ketone is meant, for example, hydroxyacetone.
    [0030] Carboxylic acids and their esters are, for example, formic acid, lactic acid, alkyl formates and alkyl lactates. At the end of the reaction, the reaction medium is analyzed by high pressure liquid chromatography (HPLC) using refractometry to determine the content of conversion products of the solution and by gas phase chromatography (GC).
    [0031] In the case of a transformation in which the solvent is water, the amount of the water-soluble reaction products is determined by the TOC (Total Organic Carbon) analysis, which consists of the measurement of carbon in solution. EXAMPLES In the examples below, the perovskite supports of the heterogeneous catalysts are commercial. The carrier of heterogeneous catalysts containing cerium oxide is commercial. In the tables of results, EG represents ethylene glycol and PG represents propylene glycol. In the tables of results, the yield of monoalcohols represents the sum of the yields obtained in methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1 hexanol, 2-hexanol, 3-hexanol.
    [0032] Example 1: Preparation of Catalyst C1 Comprising 0.7 wt.% Pt on Cerium Oxide Support A 1.9% by weight aqueous solution of hexachloroplatinic acid H 2 PtCl 4 .xH 2 O (25 mL, 0.475 g) was added at room temperature. The mixture is stirred for one hour and then evaporated, the solid obtained is then dried in an oven at 110 ° C. for 24 hours. The solid is calcined under dry nitrogen at a temperature of 150 ° C. for 1 hour, then at 250 ° C. for 1 hour, then at 350 ° C. for 3 hours and finally at 420 ° C. for 4 hours. Hydrogen at 500 ° C. for two hours, the Cl Pt (0.7%) / CeO 2 catalyst is thus obtained.
    [0033] The BET specific surface area of Catalyst C1 is 45 m 2 / g. EXAMPLE 2 Preparation of the catalyst C2 comprising 10% by weight Ni on a perovskite-type support An aqueous solution of nickel nitrate Ni (NO3) 2.6H2O at 10% by weight (25 ml, 2.4 g) is added at room temperature ambient to the BaZrO3 perovskite type support (24 g) previously desorbed under vacuum (1 h, 100 ° C.). The mixture is stirred for one hour and then evaporated. The solid obtained is then dried in an oven at 110 ° C. for 24 hours. The solid is calcined under a dry nitrogen flow rate at a temperature of 150 ° C. for 1 h, then at 250 ° C. for 1 hour, then at 350 ° C. for 3 hours and finally at 420 ° C. for 4 hours. It is then reduced under hydrogen flow at 500 ° C for two hours. The catalyst C2 Ni (10%) / BaZrO 3 is thus obtained.
    [0034] The BET specific surface area of Catalyst C2 is 3 m 2 / g. Example 3 Preparation of C3 Ni-MqO Catalyst (Non-Compliant) An aqueous solution containing nickel nitrate Ni (NO3) 2.6H2O and magnesium nitrate Mg (NO3) 2.6H2O, with a Ni metal concentration of 0, 3 M and 0.7 M Mg is added at a flow rate of 1 mL / min to a solution of sodium carbonate Na2CO3 at 1.2 mol / L at room temperature. After stirring overnight, the precipitates are recovered and vacuum-washed to pH <8 of the filtrate and dried at 110 ° C for 12 h. They are then calcined at 500 ° C. for 3 h in static air and then reduced under hydrogen at 500 ° C. for 3 h. Catalyst C3 is thus obtained. The BET specific surface of catalyst C3 is 107 m 2 / g.
    [0035] EXAMPLE 4 Transformation of Sorbitol Using Catalyst C1 (Compliant) Example 4 relates to the conversion of sorbitol in the presence of the heterogeneous catalyst C1 described in Example 1 for the production of mono- and polyoxygenated products. In a 100 ml autoclave, 25 ml of water, 0.65 g of sorbitol and 0.275 g of catalyst C1 are introduced under a nitrogen atmosphere.
    [0036] The heterogeneous catalyst is introduced into the reaction chamber in an amount corresponding to a heterogeneous charge / catalyst mass ratio = 2.4. The sorbitol is introduced into the autoclave in an amount corresponding to a mass ratio solvent / sorbitol = 38. The autoclave is heated to 230 ° C. and a pressure of 2.5 MPa of hydrogen is introduced. After 6 hours of reaction, a sample of the reaction medium is carried out. It is analyzed by high pressure liquid chromatography (HPLC) using refractometry to determine the content of conversion products of the aqueous solution and gas phase chromatography (GC). The results obtained are listed in Table 1 Table 1: Transformation of sorbitol into mono- and polyoxygenated products Conversion (%) Yield EG (%) Yield PG (%) Yield Monoalcohols (%) 90 1.5 12 4 3037951 Example 5: Transformation of Xylitol Using Catalyst Cl (Conform) Example 5 relates to the conversion of xylitol in the presence of catalyst C1 described in Example 1 for the production of mono- and polyoxygenated products.
    [0037] In a 100 ml autoclave, 25 ml of water, 0.65 g of xylitol and 0.275 g of catalyst C1 are introduced under a nitrogen atmosphere. The heterogeneous catalyst is introduced into the reaction chamber in an amount corresponding to a heterogeneous charge / catalyst mass ratio = 2.4. The sorbitol is introduced into the autoclave in an amount corresponding to a weight ratio solvent / xylitol = 38.
    [0038] The autoclave is heated to 230 ° C and a pressure of 2.5 MPa of hydrogen is introduced. After 6 hours of reaction, a sample of the reaction medium is carried out. It is analyzed by high pressure liquid chromatography (HPLC) using refractometry to determine the content of conversion products of the aqueous solution and by gas phase chromatography (GC).
    [0039] The results obtained are listed in Table 2. Table 2: Transformation of xylitol into mono- and polyoxygenated products Conversion (%) Yield EG (%) Yield PG (%) Yield Monoalcohols (%) 73 6 7 4 25 3037951 Example 6: Transformation of the Xylitol using the Catalyst C2 (10% wt.% H / 1.03) ((in conformity) Example 6 relates to the conversion of the xylitol in the presence of the catalyst C2 described in Example 2 for the production of mono- and polyoxygenated products In a 100 ml autoclave, 25 ml of water, 0.65 g of xylitol and 0.275 g of catalyst C 2 are introduced under a nitrogen atmosphere.
    [0040] The heterogeneous catalyst is introduced into the reaction chamber in an amount corresponding to a heterogeneous charge / catalyst mass ratio = 2.4. The xylitol is introduced into the autoclave in an amount corresponding to a weight ratio solvent / xylitol = 38.
    [0041] The autoclave is heated to 230 ° C and a pressure of 2.5 MPa of hydrogen is introduced. After 6 hours of reaction, a sample of the reaction medium is carried out. It is analyzed by high pressure liquid chromatography (HPLC) using refractometry to determine the content of conversion products of the aqueous solution and by gas phase chromatography (GC).
    [0042] The results obtained are listed in Table 3 Table 3: Transformation of xylitol into mono- and polyoxygenated products Conversion (%) Yield EG (%) Yield PG (%) Yield Monoalcohols (%) 70 1.5 1.5 2, EXAMPLE 7 Transformation of Sorbitol Using Catalyst C2 (Compliant) Example 7 relates to the conversion of sorbitol in the presence of the heterogeneous catalyst C2 described in Example 2 for the production of mono- and polyoxygenated products . In a 100 ml autoclave, 25 ml of water, 0.64 g of sorbitol and 0.275 g of catalyst C 2 are introduced under a nitrogen atmosphere.
    [0043] The heterogeneous catalyst is introduced into the reaction chamber in an amount corresponding to a heterogeneous charge / catalyst mass ratio = 2.3. The sorbitol is introduced into the autoclave in an amount corresponding to a mass ratio solvent / sorbitol = 39. The autoclave is heated to 230 ° C. and a pressure of 2.5 MPa of hydrogen is introduced. After 6 hours of reaction, a sample of the reaction medium is carried out. It is analyzed by high pressure liquid chromatography (HPLC) using refractometry to determine the content of conversion products of the aqueous solution and gas phase chromatography (GC). The results obtained are listed in Table 4. Table 4: Transformation of Sorbitol into Mono- and Polyoxygenated Products Conversion (%) Yield EG (%) Yield PG (%) Yield Monoalcohols (%) 95 5.5 4.5 8 3037951 EXAMPLE 8 Transformation of Glucose Using Catalyst C1 (Compliant) Example 8 relates to the conversion of glucose in the presence of the heterogeneous catalyst C1 described in Example 1 for the production of mono- and polyoxygenated products. In a 100 ml autoclave, 25 ml of water, 0.64 g of glucose and 0.275 g of catalyst C1 are introduced under a nitrogen atmosphere.
    [0044] The heterogeneous catalyst is introduced into the reaction chamber in an amount corresponding to a heterogeneous charge / catalyst mass ratio = 2.3. The glucose is introduced into the autoclave in an amount corresponding to a mass ratio solvent / glucose = 39. The autoclave is heated to 230 ° C. and a pressure of 2.5 MPa of hydrogen is introduced. After 6 hours of reaction, a sample of the reaction medium is carried out. It is analyzed by high pressure liquid chromatography (HPLC) using refractometry to determine the content of conversion products of the aqueous solution and gas phase chromatography (GC). The results obtained are listed in Table 5 Table 5: Transformation of glucose into mono- and polyoxygenated products Conversion (%) Yield EG (%) Yield PG (%) Yield Monoalcohols (%) 98 4 13 16 3037951 24 Example 9: Transformation of a mixture of xylose and glucose using catalyst C2 10% -weight Ni / BaZrO 3 compliant Example 9 relates to the conversion of a mixture of xylose and glucose in the presence of catalyst C2 described in FIG. Example 2 for the production of mono- and polyoxygenated products. In a 100 ml autoclave, 25 ml of water, 0.32 g of xylose, 0.32 g of glucose and 0.275 g of catalyst C 2 are introduced under a nitrogen atmosphere.
    [0045] The heterogeneous catalyst is introduced into the reaction chamber in an amount corresponding to a heterogeneous charge / catalyst mass ratio = 2.3. Xylose and glucose are introduced into the autoclave in an amount corresponding to a mass ratio solvent / (xylose + glucose) = 39.
    [0046] The autoclave is heated to 230 ° C and a pressure of 2.5 MPa of hydrogen is introduced. After 6 hours of reaction, a sample of the reaction medium is carried out. It is analyzed by high pressure liquid chromatography (HPLC) using refractometry to determine the content of conversion products of the aqueous solution and by gas phase chromatography (GC). The results obtained are listed in Table 6. Table 6: Conversion of a mixture of xylose and glucose to mono- and polyoxygenated products Conversion (%) Yield EG (%) Yield PG (%) Yield Monoalcohols (%) 98 EXAMPLE 10 Transformation of a mixture of xylitol and sorbitol using the ir catalyst. Cl 0.7 (X) cp :: (conform) Pt / Ce02 conforming Example 10 relates to the conversion of a mixture of xylitol and sorbitol in the presence of the catalyst C1 described in Example 1 for the production of products mono- and polyoxygenated. In a 100 ml autoclave, 25 ml of water, 0.325 g of xylitol, 0.325 g of sorbitol and 0.275 g of catalyst C1 are introduced under a nitrogen atmosphere.
    [0047] The heterogeneous catalyst is introduced into the reaction chamber in an amount corresponding to a heterogeneous charge / catalyst mass ratio = 2.4. The xylitol and sorbitol are introduced into the autoclave in an amount corresponding to a mass ratio solvent / (xylitol + sorbitol) = 38. The autoclave is heated to 230 ° C. and a pressure of 2.5 MPa hydrogen is introduced. After 6 hours of reaction, a sample of the reaction medium is carried out. It is analyzed by high pressure liquid chromatography (HPLC) using refractometry to determine the content of conversion products of the aqueous solution and gas phase chromatography (GC). The results obtained are given in Table 7. Table 7: Conversion of a mixture of xylitol and sorbitol into mono- and polyoxygenated products Conversion (%) Yield EG (%) Yield PG (%) Yield Monoalcohols (%) 96 10 EXAMPLE 11 Transformation of Sorbitol Using Catalyst C3 Ni-MgO (Non-Conforming) Example 11 relates to the conversion of sorbitol in the presence of the heterogeneous catalyst C3 described in Example 3 for the production of mono- and polyoxygenated products. In a 100 ml autoclave, 25 ml of water, 0.64 g of sorbitol and 0.275 g of catalyst C 3 are introduced under a nitrogen atmosphere.
    [0048] The heterogeneous catalyst is introduced into the reaction chamber in an amount corresponding to a heterogeneous charge / catalyst mass ratio = 2.3. The sorbitol is introduced into the autoclave in an amount corresponding to a mass ratio solvent / sorbitol = 38. The autoclave is heated to 230 ° C. and a pressure of 2.5 MPa of hydrogen is introduced. After 6 hours of reaction, a sample of the reaction medium is carried out. It is analyzed by high pressure liquid chromatography (HPLC) using refractometry to determine the content of conversion products of the aqueous solution and gas phase chromatography (GC). The results obtained are listed in Table 8 Table 8: Transformation of sorbitol into mono- and polyoxygenated products Conversion (%) Yield EG (%) Yield PG (%) Yield Monoalcohols (%) 68 18 22 6 3037951 27 Example 12: analysis of the catalysts C1, C2 and C3 after reaction The BET specific surface of the fresh heterogeneous catalyst Cl is 45 m 2 / g, the BET specific surface area of the catalyst C1 after reaction is 40 m 2 / g, it is therefore reduced by 12% by relative to the fresh heterogeneous catalyst. The structure of the spent heterogeneous catalyst C1 analyzed by XRD is identical to that of the fresh heterogeneous Cl catalyst. The compositional analysis shows that less than 20% of the elements have been leached. The BET specific surface area of the fresh heterogeneous C2 catalyst is 3 m 2 / g, the BET specific surface area of the catalyst C2 after reaction is 3 m 2 / g, it is therefore identical with respect to the fresh heterogeneous catalyst. The structure of the spent heterogeneous catalyst C2 analyzed by XRD is identical to that of the fresh heterogeneous catalyst C2. The compositional analysis shows that less than 20% of the elements have been leached. The BET specific surface area of the fresh C3 heterogeneous catalyst is 107 m 2 / g, the BET specific surface area of the C3 catalyst after reaction is 54 m 2 / g, it is therefore reduced by 50% relative to the fresh heterogeneous catalyst. The structure of the spent heterogeneous C3 catalyst analyzed by XRD shows the formation of new MgO, MgNiO2 and MgCO3 phases corresponding to a degradation of the catalyst. The compositional analysis shows that 28% of the elements have been leached.
    [0049] The heterogeneous catalysts C1 and C2 according to the invention are therefore hydrothermally stable according to the definition of the invention. The heterogeneous catalyst C3 is therefore not hydrothermally stable according to the definition of the invention. Thus, the heterogeneous catalysts C1 and C2 can be re-engaged in a process for converting sugars and sugar alcohols to mono- and polyoxygen compounds while the catalyst C3 can not be reused.
    权利要求:
    Claims (14)
    [0001]
    REVENDICATIONS1. Process for the transformation of a filler chosen from sugars and sugar alcohols, alone or as a mixture, into mono- or polyoxygenated compounds, in which the said filler is brought into contact with at least one heterogeneous catalyst, in the same reaction chamber, in the presence of at least one solvent, said solvent being water, an alcohol, a diol or another solvent alone or in a mixture, under a reducing atmosphere, and at a temperature of between 100 ° C. and 300 ° C., and a pressure of between 0.1 MPa and 50 MPa, and wherein, said heterogeneous catalyst (s) comprise at least one metal selected from the metals of groups 8 to 11 of the periodic table and a support selected from perovskites of formula ABO3 in which A is chosen from the elements Mg, Ca, Sr and Ba, and B is chosen from Fe, Mn, Ti and Zr elements, and the oxides of the elements chosen from lanthanum, neodymium, yttrium, cerium, alone or in mixture, said oxides being dopable by at least one element selected from alkali metals, alkaline earths and rare earths, alone or as a mixture, said process operating in the absence of additional catalyst.
    [0002]
    2. Method according to claim 1, wherein said process operates in the absence of additional basic catalyst selected from oxides, hydroxides and alcoholates of alkali or alkaline earth metals, hydrated or not, having the general formula MmXn.n 'H2O in which the metal M is a metal selected from the metals of groups 1 and 2 of the periodic table, m is an integer between 1 and 2, n is an integer between 1 and 2 and n 'is a number between 0 and 20 and X is chosen from oxygen, the hydroxyl group or the alcoholic groups of general formula OR with R an alkyl group.
    [0003]
    3. Method according to claims 1 to 2, wherein the filler is a sugar selected from oligosaccharides or monosaccharides alone or in admixture. 3037951 29
    [0004]
    4. Process according to claim 3, in which the oligosaccharide is chosen from sucrose, lactose, maltose, isomaltose, inulobiose, melibiose, gentiobiose, trehalose, cellobiose, cellotriose and cellotetraose. and oligosaccharides derived from the hydrolysis of starch, inulin, cellulose or hemicellulose alone or as a mixture. A process according to claim 3 wherein the monosaccharide is selected from dihydroxyacetone, erythrose, xylose, arabinose, glucose, mannose, fructose alone or in admixture. The process according to claim 1, wherein the filler is a sugar alcohol selected from lactitol, maltitol, isomaltitol, inulobitol, melibitol, gentiobitol, cellobitol, cellotritol, cellotetritol, glycerol, erythritol, xylitol, arabinitol, sorbitol, mannitol alone or as a mixture. Process according to one of Claims 1 to 6, in which the metals of groups 8 to 11 of the periodic classification of said heterogeneous catalyst or catalysts are chosen from Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag and Au alone or in mixture. Process according to one of claims 1 to 7, wherein the perovskite of formula ABO3 is selected from BaTiO3, SrTiO3, BaZrO3, CaZrO3, SrZrO3, CaMnO3. Process according to one of Claims 1 to 8, in which, said oxides are doped with at least one dopant element chosen from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, La, Ce, Sm, Gd, Y, Pr alone or in mixture. The method of claim 9, wherein the doping element has a content of between 0.1% and 30% by weight relative to the total mass of said support. 5
    [0005]
    5. 10
    [0006]
    6. 15
    [0007]
    7. 20
    [0008]
    8. 25
    [0009]
    9. 30
    [0010]
    10. 303 7 9 5 1 30
    [0011]
    11. Method according to one of claims 1 to 10, wherein the solvent is selected from water, ethylene glycol, propylene glycol, methanol, ethanol and propanols alone or in admixture.
    [0012]
    12. The method of claim 11, wherein the solvent mixture comprises a mass content of water greater than 5% by weight and preferably greater than 30% and very preferably greater than 50% relative to the total mass of said mixture. .
    [0013]
    13. Method according to one of claims 1 to 12, wherein the temperature is between 150 ° C and 250 ° C and a pressure between 0.5 MPa and 30 M Pa.
    [0014]
    14. Process according to one of Claims 1 to 13, in which the said heterogeneous catalyst is introduced into the reaction chamber with a heterogeneous charge / catalyst mass ratio of between 1 and 500.
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    同族专利:
    公开号 | 公开日
    US10252960B2|2019-04-09|
    CN107709280A|2018-02-16|
    CN107709280B|2021-08-03|
    FR3037951B1|2019-05-10|
    WO2016206826A1|2016-12-29|
    US20180179131A1|2018-06-28|
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    FR3004182B1|2013-04-09|2015-03-27|IFP Energies Nouvelles|PROCESS FOR TRANSFORMING LIGNOCELLULOSIC BIOMASSES TO MONO OR POLY-OXYGENIC MOLECULES|
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    FR3026407B1|2014-09-26|2016-10-28|Ifp Energies Now|METHOD FOR TRANSFORMING A LOAD COMPRISING A LIGNOCELLULOSIC BIOMASS USING AN ACIDIC HOMOGENEOUS CATALYST IN COMBINATION WITH A HETEROGENEOUS CATALYST COMPRISING A SPECIFIC SUPPORT|CN107020102B|2017-04-26|2019-05-31|浙江大学|A kind of nickel-chrome acid Mg catalyst and preparation method thereof and the application in ethyl alcohol is prepared in glycerol|
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    CN109806886B|2019-03-15|2021-07-20|中国科学院山西煤炭化学研究所|Catalyst for preparing dihydroxyacetone by glycerol oxidation and preparation method and application thereof|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1555966A|FR3037951B1|2015-06-26|2015-06-26|NEW PROCESS FOR TRANSFORMING SUGARS AND SUGAR ALCOHOLS IN MONO- AND POLYOXYGEN COMPOUNDS IN THE PRESENCE OF A HETEROGENEOUS CATALYST|
    FR1555966|2015-06-26|FR1555966A| FR3037951B1|2015-06-26|2015-06-26|NEW PROCESS FOR TRANSFORMING SUGARS AND SUGAR ALCOHOLS IN MONO- AND POLYOXYGEN COMPOUNDS IN THE PRESENCE OF A HETEROGENEOUS CATALYST|
    PCT/EP2016/058820| WO2016206826A1|2015-06-26|2016-04-21|New method for the conversion of sugars and sugar alcohols into mono- and polyoxygenated compounds in the presence of a heterogeneous catalyst|
    US15/739,921| US10252960B2|2015-06-26|2016-04-21|Method for transforming sugars and sugar alcohols into mono- and poly-oxidized compounds in the presence of a heterogeneous catalyst|
    CN201680037587.0A| CN107709280B|2015-06-26|2016-04-21|Process for the conversion of sugars and sugar alcohols into mono-and poly-oxygenated compounds in the presence of a heterogeneous catalyst|
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