Heterogeneous copper bimetallic catalyst, its preparation method and its use

Abstract

The present invention relates to the use of a bimetallic supported catalyst, which comprises, on a support, copper and a metal M selected from manganese, cobalt, nickel and iron, of formula Cu-M / support, where M represents Mn, Co, Ni or Fe, respectively, in carrying out a process for the preparation of ethylene glycol from oxamide or oxamate compounds by hydrogenation of said oxamide or oxamate compounds with hydrogen (H) to give ethylene glycol.

Description

[Technical Field]

[0001] The present invention relates to a novel heterogeneous bimetallic catalyst, its preparation process and its use, in particular for the synthesis of ethylene glycol from the hydrogenation reaction of oxamide or oxamate. [Background technology]

[0002] Ethylene glycol is an important raw material in the chemical industry, used in a variety of applications as an antifreeze or refrigerant, but particularly in the production of textile fibers and polyester resins. Ethylene glycol can be used as a monomer in the production of polyesters, particularly polyethylene terephthalate (PET) in the presence of terephthalic acid. PET is a polymer widely used in the textile industry and is currently produced primarily from petroleum-based products, which generate large amounts of greenhouse gases, including carbon dioxide.

[0003] The classical process for producing ethylene glycol from naphtha is illustrated below. [ka]

[0004] Carbon dioxide CO2 capture is a major challenge for reducing greenhouse gas emissions.Another synthetic route to ethylene glycol, which has not been extensively studied, is the hydrogenation of oxamide or oxamate.

[0005] Oxamide compounds can be directly synthesized by double oxidative carbonylation of amines in the presence of a catalyst, especially palladium (Pd). Oxamate compounds can be directly synthesized by oxidative carbonylation of alcohols and amines in the presence of a catalyst, especially palladium (Pd). Thus, CO2 consumption can be achieved during the synthesis of oxamide or oxamate, precursors for the production of ethylene glycol, via catalytic hydrogenation using transition metals as homogeneous or heterogeneous catalysts, as diagrammed below:

[0006] [ka] Schema 2: Producing ethylene glycol from CO2 via intermediate oxamide or oxamate compounds

[0007] A homogeneous transition metal catalyst is a catalyst that is soluble in the reaction solvent and forms a single phase.

[0008] Heterogeneous transition metal catalysts are insoluble and operate in reactions in which two phases, such as liquid-solid, exist.

[0009] Bimetallic supported catalysts consist of a support on whose surface two metal particles are dispersed and immobilized in either the oxidized or reduced state, or a mixture of the two.

[0010] The support is advantageously an oxide such as alumina or silica.

[0011] A bimetallic catalyst of two metals, metal-1 and metal-2, is understood to comprise two metal species, metal-1 and metal-2, on a support, on a surface accessible to the substrate of the catalytic reaction.

[0012] Thus, a monometallic supported catalyst consists of a support on which a single metal particle is dispersed and immobilized, either in an oxidized or reduced state, or a mixture of the two.

[0013] The hydrogenation of oxamide or oxamate to ethylene glycol is catalyzed by metals. The oxamide hydrogenation process described in Non-Patent Document 1 is carried out using homogeneous catalysis with organometallic complexes of ruthenium or iron.

[0014] U.S. Patent No. 5,999,499 to De Boer et al. discloses a method for preparing ethylene glycol by hydrogenating oxamide in the presence of a monometallic catalyst. This application includes the use of a monometallic catalyst selected from the list of transition metal elements in Group VIII of the Periodic Table and copper (an element in Group IB), with preferred metals including platinum, palladium, rhodium, ruthenium, nickel, and copper. However, tests performed with a copper catalyst show partial conversion of oxamide having the formula NRCO-CO-NR and partial hydrogenation of oxamide with preferential selectivity to ethanolamine HOCHCHNR or amide having the formula HOCH(CO)NR. US Patent No. 5,999,949 to Chen et al. relates to a material consisting of a mixture of zirconium dioxide and manganese oxide used as a catalyst support, particularly for sugar hydrogenation or hydrolysis reactions. US Patent No. 5,999,999 to Miller et al. relates specifically to nickel supported catalysts on chromium doped zirconium dioxide supports for the hydrocracking of polyols. [Prior art documents] [Patent documents]

[0015] [Patent Document 1] US Patent Application Publication No. 2012 / 0071693 [Patent Document 2] US Patent Application Publication No. 2015 / 0331923 [Patent Document 3] US Patent Application Publication No. 2014 / 0249334 [Non-patent literature]

[0016] [Non-Patent Document 1] Dong et al. (Nature Communications, 7:12075, DOI:10.1038 / ncomms12075, 2016) [Non-patent document 2] Kudoh, Y et al. (Phys Chem Minerals 13, 233-237 (1986)) [Non-patent document 3] McCullough JD et al. (Acta Crystallographica 12 (1959) 507-511) Summary of the Invention [Problem to be solved by the invention]

[0017] There has long been a need for a low-cost, environmentally friendly route to prepare ethylene glycol. There is currently a need for a heterogeneous catalyst that is easy to prepare, that enables the efficient synthesis of ethylene glycol from oxamide or oxamate in a non-polluting manner, and that is easy to industrialize and safe.

[0018] Ethylene glycol is also a model compound for hydrogenolysis, which is the cleavage of carbon-carbon (C-C) and / or carbon-oxygen (C-O) bonds in diol groups -CHOH-CHOH- present in carbohydrate molecules (polyols) contained in biomass. Therefore, a catalyst that enables the cleavage of C-C and C-O bonds in ethylene glycol by hydrogenolysis enables the depolymerization of biomass by cleavage of C-C and / or C-O bonds in diol groups present in biomass. [Means for solving the problem]

[0019] One of the objects of the present invention is to propose a method for preparing ethylene glycol from oxamide or oxamate by a reaction using a heterogeneous bimetallic catalyst, in particular a combination of copper and another metal.

[0020] Another object of the present invention is a process for preparing ethylene glycol with efficient yield and high selectivity.

[0021] Another object of the present invention is the preparation of ethylene glycol without the use of toxic reagents.

[0022] Another object of the present invention is to prepare ethylene glycol using renewable or regenerated reagents and an efficient and reusable heterogeneous catalyst.

[0023] Another object of the present invention is to provide a process for the hydrocracking of ethylene glycol using a heterogeneous bimetallic catalyst.

[0024] Another object of the present invention is to provide a method for biomass depolymerization using a heterogeneous bimetallic catalyst.

[0025] Another object of the present invention is to provide a novel heterogeneous bimetallic catalyst on a support.

[0026] Another object of the present invention is to provide a heterogeneous catalyst that can be used in a continuous flow process.

[0027] Another object of the present invention is to provide a simple, industrialized and optimized method for preparing this catalyst.

[0028] use A first object of the present invention is the use of a bimetallic supported catalyst, comprising, on a support, copper and a metal M selected from manganese, cobalt, nickel and iron, of formula Cu-M / support, where M represents Mn, Co, Ni or Fe, respectively, in carrying out a process for the preparation of ethylene glycol from oxamide or oxamate compounds by hydrogenation of said oxamide or oxamate compounds with hydrogen (H) to give ethylene glycol.

[0029] The present inventors have unexpectedly and surprisingly observed that a bimetallic catalyst of copper and a metal M selected from Mn, Co, Ni and iron on a support catalyzes the hydrogenation of oxamide or oxalate to ethylene glycol, particularly with ethylene glycol yields of up to 80%.

[0030] Tests (see Examples 14 and 15) have shown that for copper catalysts, the presence of a second metal selected from Mn, Co, Ni and Fe makes it possible to induce or promote the catalytic properties of the catalyst by improving the selectivity for obtaining ethylene glycol and promoting the substrate conversion and / or the production yield of ethylene glycol compared to prior art monometallic catalysts.

[0031] For purposes of this invention, "oxamide" refers to an amine, NR a R b The oxamide 1,1'-oxalyldiamine derivative corresponds to the formula: [ka]

[0032] For purposes of this invention, an "oxamate" is an amine group (NR a R b ) and an alkoxide group or an alcohol group, and is represented by the following formula: [ka]

[0033] According to a particular embodiment, the present invention relates to the use of a bimetallic supported catalyst of formula Cu-M / support, as defined above, comprising, on a support, copper and a metal M selected from manganese, cobalt, nickel and iron, in which M represents Mn, Co, Ni or Fe, respectively, in carrying out a process for the preparation of ethylene glycol from oxamide or oxamate compounds by hydrogenation of the latter with hydrogen (H) to obtain ethylene glycol.

[0034] In the present invention, "hydrogen" and "dihydrogen" refer to the same H2 molecule.

[0035] According to a particular embodiment, the present invention relates to the use of a bimetallic supported catalyst of formula Cu-M / support, as defined above, comprising, on a support, copper and a metal M selected from manganese, cobalt, nickel and iron, wherein M represents Mn, Co, Ni or Fe, respectively, in carrying out a process for the preparation of ethylene glycol from oxamate compounds by hydrogenation of the latter with hydrogen (H) to obtain ethylene glycol.

[0036] According to a particular embodiment, the present invention relates to the use of a bimetallic supported catalyst as defined above, comprising, on a support, copper and a metal M selected from manganese, cobalt, nickel and iron, of formula Cu-M / support, in carrying out a process for the preparation of ethylene glycol from a mixture of oxamide and oxalate compounds by hydrogen (H) hydrogenation of the mixture to obtain ethylene glycol.

[0037] It is understood that the Cu-M / support catalyst is a heterogeneous catalyst, where the catalyst is in the solid phase and the reactants exist as liquids or gases.

[0038] The advantages of using heterogeneous catalysts are the ease of separation of the catalyst from other species participating in the reaction, ease of catalyst recovery and reuse, and reduced transition metal contamination of the product.

[0039] The use of heterogeneous catalysts also has the advantage that when operating under continuous flow, the catalyst within the reactor can be fixed in an enclosure such as a cartridge, thereby obtaining a catalyst-free product at the reactor outlet.

[0040] For purposes of this invention, "catalyst" or "supported catalyst" means a material consisting of a support on which catalytic sites are disposed. A bimetallic catalyst comprises a support and atoms of copper and metal M. The total weight of the catalyst corresponds to the weight of the support plus the weight of the two metals, i.e., copper and metal M.

[0041] According to a particular embodiment, the present invention relates to the use of a bimetallic supported catalyst as defined above, comprising, on a support, copper and a metal M selected from manganese, cobalt, nickel and iron, of formula Cu-M / support, in which M represents Mn, Co, Ni or Fe, respectively, and the support is an oxide, in particular zirconium oxide (ZrO) or aluminum oxide (γ-AlO), in carrying out a process for the preparation of ethylene glycol from oxamide or oxamate compounds by hydrogenation of the latter with hydrogen (H) to obtain ethylene glycol.

[0042] Advantageously, the support is an oxide such as zirconium dioxide ZrO2 and gamma-alumina (gamma-Al2O3).

[0043] For purposes of the present invention, "oxide" means an oxide of a transition metal that is solid and insoluble in a solvent.

[0044] Use of Cu-Mn / supported catalysts According to a particular embodiment, the present invention relates to the use of a bimetallic supported catalyst of formula Cu-Mn / support, comprising copper and manganese on a support, as defined above, in carrying out a process for the preparation of ethylene glycol from oxamide or oxamate compounds by hydrogenation of the latter with hydrogen (H) to obtain ethylene glycol.

[0045] According to a particular embodiment, the present invention relates to the use of a bimetallic supported catalyst of formula Cu-Mn / oxide, comprising copper and manganese on an oxide support, as defined above, in carrying out a process for the preparation of ethylene glycol from oxamide or oxamate compounds by hydrogenation of the latter with hydrogen (H) to obtain ethylene glycol.

[0046] According to a particular embodiment, the present invention relates to the use of a bimetallic supported catalyst of formula Cu-Mn / ZrO2, comprising copper and manganese on a zirconium dioxide support, as defined above, in carrying out a process for the preparation of ethylene glycol from oxamide or oxamate compounds by hydrogenation of the latter with hydrogen (H2) to obtain ethylene glycol.

[0047] According to a particular embodiment, the present invention relates to the use of a bimetallic supported catalyst of formula Cu—Mn / γ-Al2O3, comprising copper and manganese on a γ-alumina support, as defined above, in carrying out a process for the preparation of ethylene glycol from oxamide or oxamate compounds by hydrogenation of the latter with hydrogen (H2) to obtain ethylene glycol.

[0048] Use of Cu-Co / support catalysts According to a particular embodiment, the present invention relates to the use of a bimetallic supported catalyst of formula Cu-Co / support, comprising copper and cobalt on a support, as defined above, in carrying out a process for the preparation of ethylene glycol from oxamide or oxamate compounds by hydrogenation of the latter with hydrogen (H) to obtain ethylene glycol.

[0049] According to a particular embodiment, the present invention relates to the use of a bimetallic supported catalyst of formula Cu-Co / oxide, comprising copper and cobalt on an oxide support, as defined above, in carrying out a process for the preparation of ethylene glycol from oxamide or oxamate compounds by hydrogenation of the latter with hydrogen (H) to obtain ethylene glycol.

[0050] According to a particular embodiment, the present invention relates to the use of a bimetallic supported catalyst of formula Cu-Co / ZrO2, comprising copper and cobalt on a zirconium dioxide support, as defined above, in carrying out a process for the preparation of ethylene glycol from oxamide or oxamate compounds by hydrogenation of the latter with hydrogen (H2) to obtain ethylene glycol.

[0051] According to a particular embodiment, the present invention relates to the use of a bimetallic supported catalyst of formula Cu—Co / γ-Al2O3, comprising copper and cobalt, on a γ-alumina support, as defined above, in carrying out a process for the preparation of ethylene glycol from oxamide or oxamate compounds by hydrogenation of the latter with hydrogen (H2) to obtain ethylene glycol.

[0052] Use of Cu-Ni / supported catalyst According to a particular embodiment, the present invention relates to the use of a bimetallic supported catalyst of formula Cu-Ni / support, comprising copper and nickel on a support, as defined above, in carrying out a process for the preparation of ethylene glycol from oxamide or oxamate compounds by hydrogenation of the latter with hydrogen (H) to obtain ethylene glycol.

[0053] According to a particular embodiment, the present invention relates to the use of a bimetallic supported catalyst of formula Cu-Ni / oxide, comprising copper and nickel on an oxide support, as defined above, in carrying out a process for the preparation of ethylene glycol from oxamide or oxamate compounds by hydrogenation of the latter with hydrogen (H) to obtain ethylene glycol.

[0054] According to a particular embodiment, the present invention relates to the use of a bimetallic supported catalyst of formula Cu-Ni / ZrO2, comprising copper and nickel on a zirconium dioxide support, as defined above, in carrying out a process for the preparation of ethylene glycol from oxamide or oxamate compounds by hydrogenation of the latter with hydrogen (H2) to obtain ethylene glycol.

[0055] According to a particular embodiment, the present invention relates to the use of a bimetallic supported catalyst of formula Cu—Ni / γ-Al2O3, comprising copper and nickel on a γ-alumina support, as defined above, in carrying out a process for the preparation of ethylene glycol from oxamide or oxamate compounds by hydrogenation of the latter with hydrogen (H2) to obtain ethylene glycol.

[0056] Use of Cu-Fe / support catalyst According to a particular embodiment, the present invention relates to the use of a bimetallic supported catalyst, as defined above, comprising copper and iron on a support, of formula Cu-Fe / support, in carrying out a process for preparing ethylene glycol from oxamide or oxamate compounds by hydrogenation of the latter with hydrogen (H) to obtain ethylene glycol.

[0057] According to a particular embodiment, the present invention relates to the use of a bimetallic supported catalyst of formula Cu-Fe / oxide, comprising copper and iron on an oxide support, as defined above, in carrying out a process for the preparation of ethylene glycol from oxamide or oxamate compounds by hydrogenation of the latter with hydrogen (H) to obtain ethylene glycol.

[0058] According to a particular embodiment, the present invention relates to the use of a bimetallic supported catalyst of formula Cu-Fe / ZrO2, comprising copper and iron on a zirconium dioxide support, as defined above, in carrying out a process for the preparation of ethylene glycol from oxamide or oxamate compounds by hydrogenation of the latter with hydrogen (H2) to obtain ethylene glycol.

[0059] According to a particular embodiment, the present invention relates to the use of a bimetallic supported catalyst of formula Cu—Fe / γ-Al2O3, comprising copper and iron on a γ-alumina support, as defined above, in carrying out a process for the preparation of ethylene glycol from oxamide or oxamate compounds by hydrogenation of the latter with hydrogen (H2) to obtain ethylene glycol.

[0060] Oxamide According to a particular embodiment, the invention relates to the use as defined above, wherein said oxamide is represented by formula 1 below: [ka]

[0061] In the formula, R a and R b are independent of each other, hydrogen atoms, C1~C 20 straight or branched chain alkyl groups, C2~C 20 a straight-chain or branched-chain alkenyl group; C1~C 20 straight chain or branched chain heteroalkyl groups, C3~C 20 an aryl or heteroaryl group, C5~C 20 an alkylaryl or alkylheteroaryl group; C3~C 10 represents a cycloalkyl group, Ra group or R b at least one of the groups is different from hydrogen; R a and R b may be covalently bonded to form a ring.

[0062] According to a particular embodiment, the present invention relates to the use as defined above, wherein said oxamide is selected from oxamides prepared with diethylamine, piperidine, pyrrolidine, morpholine and aniline, preferably piperidine.

[0063] Oxamate According to a particular embodiment, the present invention relates to the use as defined above, wherein said oxamate is represented by formula 2 below: [ka]

[0064] In the formula, R a and R b is, independently, hydrogen atoms, C1~C 20 straight or branched chain alkyl groups, C2~C 20 a straight-chain or branched-chain alkenyl group; C1~C 20 straight chain or branched chain heteroalkyl groups, C3~C 20 an aryl or heteroaryl group, C5~C 20 an alkylaryl or alkylheteroaryl group; C3~C 10 represents a cycloalkyl group, R a group or R b at least one of the groups is different from hydrogen; R a and R b may be covalently bonded to form a ring, R c teeth, C1~C 10 straight or branched chain alkyl groups, C3~C 10 cycloalkyl groups, C3~C 20 an aryl or heteroaryl group, C5~C 20 It represents a group selected from alkylaryl groups or alkylheteroaryl groups.

[0065] According to a particular embodiment, the present invention relates to the use as defined above, wherein said okimate is selected from okimates prepared using diethylamine, piperidine, pyrrolidine, morpholine and aniline, preferably piperidine, and water, methanol or isopropanol.

[0066] from CO2 The oxamides used can advantageously be obtained by carbonylation of amines in the presence of CO and oxygen.

[0067] The oxamates used are advantageously obtainable by carbonylation of amines and alcohols or water in the presence of CO and oxygen.

[0068] Advantageously, the carbon monoxide CO for preparing the oxamides or oxamates is obtained from the electrolysis of carbon dioxide CO2 to carbon monoxide CO.

[0069] Therefore, the synthesis of ethylene glycol can be advantageously carried out from the recovery of CO2.

[0070] Use in catalyst preparation by soft chemistry According to a particular embodiment, the present invention relates to the use as defined above, wherein said catalyst is prepared by mixing a powdered support with an aqueous solution of a copper salt and a metal M salt, where M is selected from Mn, Co, Ni and Fe, followed by drying and calcination.

[0071] According to a particular embodiment, the invention relates to the use as defined above, wherein said catalyst is prepared by mixing the powdered support with an aqueous solution of copper salts and metal M salts, where M is selected from Mn, Co, Ni and Fe, without additives or surfactants, in particular aqueous ammonia, followed by drying and calcining the material obtained.

[0072] It is understood that the mixture of the powdered support with the aqueous solution of copper salt and metal M salt (M selected from Mn, Co, Ni and Fe) comprises contacting the aqueous solution of copper salt and metal M salt with the support, thereby resulting in impregnation of the support with the copper salt and metal M salt, i.e., deposition of copper atoms and metal M atoms on the surface of the support.

[0073] "Drying" means an operation consisting of heating a substance with ambient air in a sealed enclosure to a temperature of the order of 60-100°C for 10-24 hours in order to dry the substance, i.e. to remove water molecules, i.e. free water, surface-adsorbed water or interstitial water.

[0074] "Calining" refers to the operation of heating a solid material to high temperatures, such as 400-1,000°C, in ambient air in a sealed enclosure to activate the solid material or modify the physical properties of the support, and to remove admixed water and salts of metal precursors, such as nitrates and acetates. After calcination, the material is free of moisture.

[0075] The catalyst used is advantageously prepared according to a preparation method comprising the following steps: impregnating a powdered support with a copper salt and a metal M salt (M is selected from Mn, Co, Ni and Fe) dissolved in an aqueous solution with a volume of 5-10 mL of water, the ratio of the solution to the mass of the support being 0.6-1.0; Step A, whereby a Cu-M / support catalyst is obtained in the form of a homogeneous mixture; a step B of drying the homogeneous mixture to obtain a Cu-M / support catalyst in the form of a dry homogeneous mixture; and an activation step C, which comprises calcining the dried homogeneous mixture to obtain the catalyst.

[0076] In the present invention, the term "homogeneous mixture" refers to a homogeneous substance obtained by mixing an aqueous metal salt solution with a solid powder support, and the aqueous metal salt solution is uniformly distributed on the surfaces of the particles constituting the support and in the gaps between the particles.

[0077] The term "dry homogeneous mixture" refers to a homogeneous mixture obtained by removing most of the free water molecules adsorbed on the surface or between the support particles by drying at, for example, 60 to 100°C, particularly 80°C, to obtain a powder. According to this catalyst preparation, metal salts such as nitrates are completely removed after a calcination step at 600°C, producing the corresponding insoluble metal oxides.

[0078] In step A of the impregnation, the aqueous solution comprising the copper salt and the metal M salt (M being selected from Mn, Co, Ni and Fe) is advantageously free of additives and surfactants, i.e. the aqueous impregnation solution consists of a demineralized aqueous solution in which the copper salt and the metal M salt are dissolved.

[0079] Advantageously, the metal M salt is a nitrate and the copper salt is copper nitrate.

[0080] Therefore, the use according to the present invention is carried out by using a catalyst prepared using an aqueous solution, which is a non-hazardous and low-pollution solvent compared to the organic solvents used in the prior art.Since there is no need to add additives and surfactants in the synthesis of the catalyst, it is advantageous in that it is more cost-effective and more industrially feasible.

[0081] "Green solvents" are non-toxic, biodegradable or agriculturally based alternative solvents that have the same properties as the toxic solvents they replace.

[0082] Use of catalysts with specific surface area characteristics According to a particular embodiment, the present invention relates to the use as defined above, wherein said catalyst has a specific surface area, analyzed by BET, between 1 and 250 m 2 / g.

[0083] 1~250m 2 / g range is 1~25m 2 / g, 25-50m 2 / g, 50-75m 2 / g, 75-100m 2 / g, 100-125m 2 / g, 125-150m 2 / g, 150-175m 2 / g, 175-200m 2 / g, 200-225m 2 / g, 225-250m 2 / g range is included.

[0084] According to a particular embodiment, the present invention relates to the use as defined above, wherein said catalyst has a specific surface area, analyzed by BET, between 1 and 50 m 2 / g.

[0085] 1~50m 2 / g range is 1 to 10 m 2 / g, 10-20m 2 / g, 20-30m 2 / g, 30-40m 2 / g, 40-50m 2 / g range is included.

[0086] According to a particular embodiment, the present invention relates to the use as defined above, wherein said catalyst has a specific surface area, analyzed by BET, between 1 and 10 m 2 / g, preferably about 5m 2 / g.

[0087] 1 to 10 m 2 / g range is 1-2m 2 / g, 2-3m 2 / g, 3-4m 2 / g, 4-5m 2 / g, 5-6m 2 / g, 6-7m 2 / g, 7-8m 2 / g, 8-9m 2 / g, 9-10m 2 / g, especially about 5m2 / g range is included.

[0088] Use of catalysts on ZrO2 supports with specific crystalline structures According to a particular embodiment, the present invention relates to the use of a Cu-M / ZrO2 catalyst as defined above, said catalyst comprising a crystalline phase and being crystallized in the monoclinic system as analyzed by X-ray diffraction.

[0089] "Monoclinic" refers to a system whose symmetry point group is either 2m or 2 / m.

[0090] According to a particular embodiment, the present invention relates to the use of a Cu-M / ZrO2 catalyst as defined above, wherein said crystalline phase represents 50-90% of the total weight of the catalyst.

[0091] According to a particular embodiment, the present invention relates to the use of a Cu-M / ZrO2 catalyst as defined above, wherein said crystalline phase is baddeleyite.

[0092] According to a particular embodiment, the present invention relates to the use of a Cu-M / ZrO2 catalyst as defined above, wherein said catalyst support is natural zirconium dioxide (ZrO2) crystallized in monoclinic baddeleyite.

[0093] In the present invention, "baddeleyite" refers to natural zirconium oxide of formula ZrO2, containing 0.1% to 5% hafnium oxide, and crystallizing in the monoclinic system. The composition and crystal structure of baddeleyite, particularly its properties such as the space group with the dimensions of the crystal lattice, have been reported and are available in the prior art and are known to those skilled in the art, for example, in Non-Patent Document 2 or Non-Patent Document 3.

[0094] According to a particular embodiment, the present invention relates to the use as defined above, wherein the catalyst support of zirconium dioxide ZrO2 comprises impurities such as hafnium (Hf), rhenium (Re) and silicon (Si) atoms.

[0095] Advantageously, the mass ratio of hafnium atoms to zirconium atoms (Hf / Zr) is less than 5%.

[0096] Advantageously, the mass ratio of rhenium atoms to zirconium atoms (Re / Zr) is less than 5%.

[0097] Advantageously, the mass ratio of silicon atoms to zirconium atoms (Si / Zr) is less than 2%.

[0098] According to a particular embodiment, the present invention relates to the use as defined above, wherein said catalyst has a microstructure and is between 15 and 100 nm, preferably between 15 and 50 nm.

[0099] The crystalline structure of the catalyst can be analyzed by powder X-ray diffraction. The phases present and their structure are identified by assigning the diffraction peaks present in the resulting diffractogram in comparison with a reference file.

[0100] The baddeleyite crystalline phase of zirconium dioxide ZrO2 is shown, for example, in ICDD Reference File No. 00-037-1484.

[0101] From the diffraction pattern, the crystallite size can be estimated according to the Scherrer equation:

number

[0102] The range of 15 to 100 nanometers includes the ranges of 15 to 20 nm, 20 to 30 nm, 30 to 40 nm, 40 to 50 nm, 50 to 60 nm, 60 to 70 nm, 70 to 80 nm, 80 to 90 nm, and 90 to 100 nm.

[0103] Use of specific Cu and metal M containing catalysts According to a particular embodiment, the present invention relates to the use as defined above, wherein the total content of bimetallic elements of copper and metal M, where M is selected from Mn, Co, Ni and Fe, is between 0.5 and 25% relative to the total weight of the catalyst.

[0104] The total weight of the catalyst includes the mass of the support and the mass of the bimetallic element copper and metal M.

[0105] The range of 0.5-25% includes the ranges of 0.5-5%, 5-10%, 10-15%, 15-20%, and 20-25%.

[0106] According to a particular embodiment, the invention relates to the use as defined above, wherein the total content of bimetallic elements of copper and metal M is between 5 and 20% relative to the total weight of the catalyst.

[0107] The "total content of copper and metal M" means a content equivalent to the amount of copper element and metal M element added in the catalyst.

[0108] According to a particular embodiment, the invention relates to the use as defined above, in which the total content of elemental copper is between 1 and 25%, in particular between 1 and 10%, relative to the total weight of the catalyst.

[0109] According to a particular embodiment, the present invention relates to the use as defined above, wherein the total content of metal elements M, where M is selected from Mn, Co, Ni and Fe, is between 1 and 25%, in particular between 1 and 10%, relative to the total weight of the catalyst.

[0110] According to a particular embodiment, the present invention relates to the use as defined above, the total content of elemental copper is 1-25%, in particular 1-10%, relative to the total weight of the catalyst; The total content of the metal elements M is between 1 and 25%, in particular between 1 and 10%, relative to the total weight of the catalyst.

[0111] According to a particular embodiment, the invention relates to the use as defined above, wherein the mass of copper is greater than the mass of the metal M.

[0112] According to a particular embodiment, the invention relates to the use as defined above, wherein the mass of metal M is greater than the mass of copper.

[0113] According to a particular embodiment, the invention relates to the use as defined above, in which the weight ratio of metal M to copper is between 1:1 and 1:10, preferably between 1:1 and 1:5, in particular 1:2.

[0114] According to a particular embodiment, the invention relates to the use as defined above, wherein the catalyst has a mass composition of metal elements M (M selected from Mn, Co, Ni and Fe) and copper of M(5%)Cu(10%).

[0115] The mass composition M(5%)Cu(10%) corresponds to metal M being 5% of the total weight of the catalyst and Cu being 10% of the total weight of the catalyst, i.e., a mass ratio of metal M to Cu being 1:2.

[0116] Use of CuMn / support catalysts with Cu and Co surface properties. According to a particular embodiment, the present invention relates to the use as defined above, wherein said catalyst is CuMn / support, said catalyst having a molar amount of elemental copper in degree of oxidation (II) greater than 50% and / or elemental manganese in degrees of oxidation (II), (III) and (IV) are present.

[0117] According to a particular embodiment, the present invention relates to the use as defined above, wherein said catalyst is CuMn / ZrO2, said catalyst having a molar amount of elemental copper in degree of oxidation (II) and / or elemental manganese in degree of oxidation (II) greater than 50%.

[0118] According to a particular embodiment, the present invention relates to the use as defined above, wherein said catalyst is CuMn / γ-Al2O3, said catalyst having a molar amount of elemental copper in degree of oxidation (II) and / or elemental manganese in degree of oxidation (III) greater than 50%.

[0119] Use of CuCo / ZrO2 catalyst with surface characteristics of Cu and Co According to a particular embodiment, the present invention relates to the use as defined above, wherein said catalyst is CuCo / ZrO2 and has a molar amount of elemental copper in degree of oxidation (II) and / or elemental cobalt in degree of oxidation (II) greater than 50%.

[0120] The present inventors have unexpectedly found that a CoCu / ZrO2 bimetallic catalyst can be used directly for the hydrogenation of oxamide or oxamate to ethylene glycol after preparation by calcination in air without a prior step of hydrogen reduction of the copper and cobalt atoms before using the catalyst in the hydrogenation reaction.

[0121] Advantageously, by using a catalyst in which the majority of the copper and cobalt elements are already present in an oxidized state, the catalyst can be used without prior reduction of the copper and cobalt elements of the catalyst prior to carrying out the hydrogenation reaction of oxamide or oxamate to ethylene glycol, thereby eliminating the need to store the catalyst in an inert atmosphere to prevent oxidation of the copper and cobalt atoms.

[0122] According to a particular embodiment, the present invention relates to the use as defined above, wherein said CuCo / ZrO2 catalyst has a molar amount of elemental copper with a degree of oxidation (II) greater than 50% and a molar amount of elemental cobalt with a degree of oxidation (II) greater than 50%.

[0123] According to a particular embodiment, the present invention relates to the use as defined above, wherein said CuCo / ZrO2 catalyst has a molar amount of elemental copper with a degree of oxidation (II) greater than 70% and a molar amount of elemental cobalt with a degree of oxidation (II) greater than 65%.

[0124] According to a particular embodiment, the present invention relates to the use as defined above, wherein said CuCo / ZrO2 catalyst has elemental copper in the form of CuO with a degree of oxidation (II) of more than 50% molar amount and elemental cobalt in the form of CO2O3 or Co(OH)2 with a degree of oxidation (II) of more than 50% molar amount.

[0125] According to a particular embodiment, the present invention relates to the use as defined above, wherein said CuCo / ZrO2 catalyst has elemental copper in the form of CuO with a degree of oxidation (II) of more than 70% molar amount and elemental cobalt in the form of CO2O3 or Co(OH)2 with a degree of oxidation (II) of more than 65% molar amount.

[0126] According to a particular embodiment, the present invention relates to the use as defined above, wherein said CuCo / ZrO2 catalyst comprises: - Copper element in the metallic state with an oxidation degree of (0) or in the Cu2O state with an oxidation degree of (I) molar amount of 10-30%; - Cobalt element in metallic state with a molar amount of 10 to 35% and an oxidation degree (0).

[0127] According to a particular embodiment, the present invention relates to the use as defined above, wherein said CuCo / ZrO2 catalyst comprises: elemental copper in the form of CuO with a degree of oxidation (II) of more than 70% molar amount, - Copper element in the metallic state with an oxidation degree of (0) or in the Cu2O state with an oxidation degree of (I) molar amount of 10-30%; - Cobalt element in metallic state with a molar amount of 10-35% and an oxidation degree (0); - copper element in the form of CuO or Co(OH)2 with a molar amount of oxidation degree (II) greater than 65%;

[0128] Use of CuCo / ZrO2 catalysts with specific morphologies According to a particular embodiment, the present invention relates to the use as defined above, wherein said CuCo / ZrO2 catalyst is in the form of a fine particle population of 1 to 500 μm.

[0129] The range of 1 to 500 μm includes ranges of 1 to 50 μm, 50 to 100 μm, 100 to 200 μm, 200 to 300 μm, and 300 to 400 μm.

[0130] "Particle" means a distinguishable cluster that retains visual or mechanical coherence.

[0131] According to a particular embodiment, the present invention relates to the use as defined above, wherein said CuCo / ZrO2 catalyst is in the form of a particle mass with rounded morphology.

[0132] For the purposes of the present invention, "rounded particles" means particles that are free of edges, corners and chamfered edges.

[0133] catalyst A second subject of the invention relates to bimetallic supported catalysts of formula Cu-M / support, comprising, on a support, copper and a metal M chosen from manganese, cobalt, nickel and iron, where M represents Mn, Co, Ni or Fe, respectively.

[0134] Cu-M / γ-Al2O3 catalyst According to a particular embodiment, the present invention relates to a bimetallic supported catalyst of formula Cu-M / γ-Al2O3, comprising copper and a metal M, where M is selected from Mn, Co, Ni and Fe, on a γ-alumina support, Optionally, the catalyst has a surface area, as analyzed by BET, of 1 to 250 m 2 / g, preferably 100 to 200m 2 / g, more preferably 150 to 160m 2 / g, Optionally, the catalyst has a crystalline phase of less than 10 nm as analyzed by X-ray diffraction.

[0135] According to a particular embodiment, the present invention relates to a bimetallic supported catalyst of formula Cu-M / γ-Al2O3, comprising, on a γ-alumina support, on the surface thereof, copper and a metal M selected from Mn and Co, The catalyst has a surface area of ​​100 to 200 m as analyzed by BET.2 / g.

[0136] Cu-M / ZrO2 catalyst According to a particular embodiment, the present invention relates to a bimetallic supported catalyst of formula Cu-M / ZrO2, comprising copper and a metal M, where M is selected from Mn, Co, Ni and Fe, on a zirconium dioxide support, The catalyst has a surface area of ​​1 to 250 m as analyzed by BET. 2 / g, preferably 1 to 50m 2 / g, preferably 1 to 10m 2 / g, especially about 5m 2 / g, The catalyst is analyzed by X-ray diffraction and contains a crystalline phase crystallized in the monoclinic system, in particular the crystalline phase accounts for 50 to 90 wt % of the total weight of the catalyst, preferably the crystalline phase is baddeleyite, and the crystallite size is preferably 15 to 100 nm.

[0137] According to a particular embodiment, the present invention relates to a bimetallic supported catalyst of formula Cu-M / ZrO2, comprising copper and a metal M, where M is selected from Mn, Co, Ni and Fe, on the surface of a zirconium dioxide support.

[0138] specific surface According to a particular embodiment, the present invention relates to a bimetallic supported catalyst Cu-M / ZrO2 as defined above, said catalyst having a specific surface area, as analyzed by BET, between 1 and 50 m 2 / g.

[0139] According to a particular embodiment, the present invention relates to a bimetallic supported catalyst as defined above of formula Cu-M / ZrO2, comprising, on a zirconium dioxide support, at the surface thereof, copper and a metal M selected from Mn, Co, Ni and Fe, The catalyst has a surface area of ​​1 to 50 m as analyzed by BET. 2 / g.

[0140] According to a particular embodiment, the present invention relates to a bimetallic catalyst as defined above, wherein said zirconium dioxide support is free of manganese and / or chromium.

[0141] According to a particular embodiment, the present invention relates to a bimetallic supported catalyst Cu-M / ZrO2 as defined above, said catalyst having a specific surface area, as analyzed by BET, between 1 and 10 m 2 / g, preferably about 5m 2 / g.

[0142] According to a particular embodiment, the present invention relates to a bimetallic supported catalyst as defined above of formula Cu-M / ZrO2, comprising, on a zirconium dioxide support, at the surface thereof, copper and a metal M selected from Mn and Co, The catalyst has a surface area of ​​1 to 10 m as analyzed by BET. 2 / g, preferably about 5m 2 / g.

[0143] structure According to a particular embodiment, the invention relates to a bimetallic supported catalyst Cu-M / ZrO2 as defined above, wherein said crystalline phase represents 50-90% of the total weight of the catalyst.

[0144] According to a particular embodiment, the present invention relates to a bimetallic supported catalyst Cu-M / ZrO2 as defined above, wherein said crystalline phase is baddeleyite.

[0145] According to a particular embodiment, the present invention relates to a bimetallic supported catalyst body Cu-M / ZrO2 as defined above, wherein the catalyst support of zirconium dioxide ZrO2 contains impurities such as hafnium (Hf), rhenium (Re) and silicon (Si) atoms.

[0146] Advantageously, the mass ratio of hafnium atoms to zirconium atoms (Hf / Zr) is less than 5%.

[0147] Advantageously, the mass ratio of rhenium atoms to zirconium atoms (Re / Zr) is less than 5%.

[0148] Advantageously, the mass ratio of silicon atoms to zirconium atoms (Si / Zr) is less than 2%.

[0149] According to a particular embodiment, the present invention relates to a bimetallic supported catalyst Cu-M / ZrO2 as defined above, said catalyst having a microstructure with a crystallite size between 15 and 100 nm, preferably between 15 and 50 nm.

[0150] According to a particular embodiment, the present invention relates to a bimetallic supported catalyst Cu-M / ZrO2 as defined above, The catalyst has a surface area, as analyzed by BET, of 1 to 250 m 2 / g, especially 1-50m 2 / g, preferably 1 to 10m 2 / g, - said catalyst comprises a crystalline phase, analyzed by X-ray diffraction, crystallized in the monoclinic system;

[0151] According to a particular embodiment, the present invention relates to a zirconium dioxide support Cu-M / ZrO2 as defined above, - The catalyst has a surface area of ​​1 to 10 m as analyzed by BET. 2 / g, - the catalyst comprises a crystalline phase, analyzed by X-ray diffraction, crystallized in monoclinic baddeleyite with a crystallite size of 15 to 100 nm, preferably 15 to 50 nm; - Contains impurities such as hafnium (Hf), rhenium (Re) and silicon (Si) atoms.

[0152] According to a particular embodiment, the present invention relates to a bimetallic supported catalyst Cu-M / ZrO2 as defined above of formula Cu-M / ZrO2, comprising copper and a metal M selected from Mn, Co, Ni and Fe, on a zirconium dioxide support, The catalyst has a surface area of ​​1 to 250 m as analyzed by BET. 2 / g, preferably 1 to 50m 2 / g, preferably 1 to 10m 2 / g, especially about 5m 2 / g, The catalyst is analyzed by X-ray diffraction and contains a crystalline phase crystallized in the monoclinic system, in particular the crystalline phase accounts for 50 to 90 wt % of the total weight of the catalyst, preferably the crystalline phase is baddeleyite, and the crystallite size is preferably 15 to 100 nm.

[0153] According to a particular embodiment, the present invention relates to a bimetallic catalyst as defined above of formula Cu-M / ZrO2, comprising, on a zirconium dioxide support, at the surface, copper and a metal M selected from Mn and Co, The zirconium dioxide supported catalyst contains a crystalline phase that has been analyzed by X-ray diffraction and is crystallized in the monoclinic system.

[0154] According to a particular embodiment, the present invention relates to a bimetallic catalyst as defined above of formula Cu-M / ZrO2, comprising, on a zirconium dioxide support, at the surface, copper and a metal M selected from Mn and Co, The crystalline phase accounts for 50 to 90% by weight of the total weight of the catalyst.

[0155] The 50-90% range includes the following ranges: 50-55%, 55-60%, 60-65%, 65-70%, 70-75%, 75-80%, 80-85%, and 85-90%.

[0156] According to a particular embodiment, the present invention relates to a bimetallic catalyst as defined above of formula Cu-M / ZrO2, comprising, on a zirconium dioxide support, at the surface, copper and a metal M selected from Mn and Co, said crystalline phase being baddeleyite.

[0157] Advantageously, the catalyst according to the invention contains 50 to 90% of baddeleyite.

[0158] Advantageously, the support of the zirconium dioxide catalyst according to the invention consists of more than 50% baddeleyite, in particular 50 to 100% baddeleyite.

[0159] According to a particular embodiment, the present invention relates to a bimetallic catalyst as defined above of formula Cu-M / ZrO2, comprising, on a zirconium dioxide support, at its surface, copper and a metal M selected from Mn and Co, said catalyst comprising a crystalline layer analyzed by X-ray diffraction, with a crystallite size between 15 and 100 nm.

[0160] composition According to a particular embodiment, the present invention relates to a bimetallic catalyst Cu-M / support as defined above, where M is selected from Mn, Co, Ni and Fe, said catalyst having a total content of bimetallic elements, copper and metal M, between 0.5 and 25% relative to the total weight of the catalyst.

[0161] According to a particular embodiment, the present invention relates to a bimetallic catalyst Cu-M / supported as defined above, where M is selected from Mn, Co, Ni and Fe, said catalyst having a total content of bimetallic elements, copper and metal M, ranging from 5 to 20% relative to the total weight of the catalyst.

[0162] According to a particular embodiment, the present invention relates to a bimetallic catalyst Cu-M / support as defined above, where M is selected from Mn, Co, Ni and Fe, with a total copper content between 1 and 25%, preferably between 1 and 10%, relative to the total weight of the catalyst.

[0163] According to a particular embodiment, the present invention relates to a bimetallic catalyst Cu-M / support as defined above, where M is selected from Mn, Co, Ni and Fe, in which the total content of the metal elements M is between 1 and 25%, preferably between 1 and 10%, relative to the total weight of the catalyst.

[0164] According to a particular embodiment, the present invention relates to a bimetallic catalyst Cu-M / support as defined above, where M is selected from Mn, Co, Ni and Fe, in which the weight ratio of metal M to copper is between 1:1 and 1:10, preferably 1:2.

[0165] Cu-Mn / support, ZrO2 or γ-Al2O3: oxidation degree of Mn and Cu on the surface According to a particular embodiment, the present invention relates to a bimetallic catalyst Cu—Mn / support as defined above, said catalyst having elemental copper in degree of oxidation (II) in a molar amount greater than 50% and / or elemental manganese in degrees of oxidation (II), (III) and (IV) being present.

[0166] According to a particular embodiment, the present invention relates to a bimetallic catalyst CuMn / ZrO2 as defined above, said catalyst having a molar amount of elemental copper in degree of oxidation (II) and / or elemental manganese in degree of oxidation (II) greater than 50%.

[0167] According to a particular embodiment, the present invention relates to a bimetallic catalyst CuMn / γ-Al2O3 as defined above, said catalyst having a molar amount of elemental copper in degree of oxidation (II) and / or elemental manganese in degree of oxidation (III) in a molar amount greater than 50 mol %.

[0168] CuCo / ZrO2: Oxidation degree of Co and Cu on the surface According to a particular embodiment, the present invention relates to a bimetallic catalyst CuCo / ZrO2 as defined above, said catalyst having a molar amount of elemental copper in degree of oxidation (II) and / or elemental cobalt in degree of oxidation (II) greater than 50%.

[0169] In some cases, it may be advantageous to use a bimetallic catalyst, CuCo / ZrO, in which the majority of the copper and cobalt elements are already present in an oxidized state, without prior reduction of the copper and cobalt elements of the catalyst prior to carrying out the hydrogenative reduction of oxamide or oxamate to ethylene glycol, thereby eliminating the need to store the catalyst in an inert atmosphere to avoid oxidation of the copper and cobalt atoms.

[0170] According to a particular embodiment, the present invention relates to a CuCo / ZrO2 catalyst as defined above, said catalyst having a molar amount of elemental copper with a degree of oxidation (II) greater than 50% and elemental cobalt with a degree of oxidation (II) greater than 50%.

[0171] According to a particular embodiment, the present invention relates to a CuCo / ZrO2 catalyst as defined above, said catalyst having elemental copper in a molar amount with a degree of oxidation (II) greater than 70% and elemental cobalt in a molar amount with a degree of oxidation (II) greater than 65%.

[0172] According to a particular embodiment, the present invention relates to a CuCo / ZrO2 catalyst as defined above, said catalyst having elemental copper in the form of CuO with a molar amount of degree of oxidation (II) greater than 50% and elemental cobalt in the form of CO2O3 or Co(OH)2 with a molar amount of degree of oxidation (II) greater than 50%.

[0173] According to a particular embodiment, the present invention relates to a CuCo / ZrO2 catalyst as defined above, said catalyst having elemental copper in the form of CuO with a molar amount of degree of oxidation (II) greater than 70% and elemental cobalt in the form of CO2O3 or Co(OH)2 with a molar amount of degree of oxidation (II) greater than 65%.

[0174] According to a particular embodiment, the present invention relates to a CuCo / ZrO catalyst as defined above, said catalyst comprising: - It contains copper element in the metallic state with an oxidation degree of (0) or in the Cu2O state with an oxidation degree of (I) in a molar amount of 10-30%.

[0175] According to a particular embodiment, the present invention relates to a CuCo / ZrO catalyst as defined above, said catalyst comprising: - Copper element in the metallic state with an oxidation degree of (0) or in the Cu2O state with an oxidation degree of (I) molar amount of 10-30%; - Cobalt element in metallic state with a molar amount of 10 to 35% and an oxidation degree (0).

[0176] According to a particular embodiment, the present invention relates to a CuCo / ZrO catalyst as defined above, said catalyst comprising: elemental copper in the form of CuO with a degree of oxidation (II) of more than 70% molar amount, - Copper element in the metallic state with an oxidation degree of (0) or in the Cu2O state with an oxidation degree of (I) molar amount of 10-30%; - copper element in the form of CuO or Co(OH)2 with a molar amount of oxidation degree (II) greater than 65%;

[0177] According to a particular embodiment, the present invention relates to a CuCo / ZrO catalyst as defined above, said catalyst comprising: elemental copper in the form of CuO with a degree of oxidation (II) of more than 70% molar amount, - Copper element in the metallic state with an oxidation degree of (0) or in the Cu2O state with an oxidation degree of (I) molar amount of 10-30%; - Cobalt element in metallic state with a molar amount of 10-35% and oxidation degree (0), - copper element in the form of Cu2O3 or Co(OH)2 with a molar amount of oxidation degree (II) greater than 65%;

[0178] According to a particular embodiment, the present invention relates to a CuCo / ZrO catalyst as defined above, said catalyst comprising: - elemental copper in a molar amount with a degree of oxidation (II) of more than 50% and elemental cobalt in a molar amount with a degree of oxidation (II) of more than 50%, - 1~50m 2 / g specific surface area, - crystalline phase analyzed by X-ray diffraction and crystallized in the monoclinic system.

[0179] According to a particular embodiment, the present invention relates to a CuCo / ZrO catalyst as defined above, said catalyst comprising: elemental copper in the form of CuO with a degree of oxidation (II) of more than 70% molar amount, - Copper element in the metallic state with an oxidation degree of (0) or in the Cu2O state with an oxidation degree of (I) molar amount of 10-30%; - elemental copper in the form of CO2O3 or Co(OH)2 with a molar amount of more than 65% of oxidation degree (II), - 1~50m 2 / g, especially 1-10m analyzed by BET 2 / g specific surface area, - analyzed by X-ray diffraction and found to be monoclinic crystallized, in particular baddeleyite, and containing crystalline phases containing impurities of hafnium, rhenium and silicon, among others.

[0180] According to a particular embodiment, the present invention relates to a CuCo / ZrO catalyst as defined above, said catalyst comprising: - elemental copper in one oxidation degree (II) with a molar amount of more than 70% in the form of CuO, - Copper element in the metallic state with an oxidation degree of (0) or in the Cu2O state with an oxidation degree of (I) molar amount of 10-30%; - Cobalt element in metallic state with a molar amount of 10-35% and an oxidation degree (0); - elemental copper in the form of CO2O3 or Co(OH)2 with a molar amount of more than 65% of oxidation degree (II), - 1~50m 2 / g, especially 1-10m analyzed by BET 2 / g specific surface area, - analyzed by X-ray diffraction and found to be monoclinic crystallized, in particular baddeleyite, and containing crystalline phases containing impurities of hafnium, rhenium and silicon, among others.

[0181] Cu-M / ZrO2 catalyst morphology According to a particular embodiment, the present invention relates to a bimetallic supported catalyst Cu-M / ZrO2 as defined above, said catalyst being in the form of fine particles of 1-500 μm, preferably in the form of a cluster of rounded particles.

[0182] Cu-Mn / ZrO2 catalyst morphology According to a particular embodiment, the present invention relates to a bimetallic supported catalyst Cu—Mn / ZrO2 as defined above, said catalyst being in the form of fine particles ranging from 1 to 500 μm, preferably in the form of a cluster of rounded particles.

[0183] CuCo / ZrO2 catalyst morphology According to a particular embodiment, the present invention relates to a bimetallic supported catalyst CuCo / ZrO2 as defined above, said catalyst being in the form of fine particles ranging from 1 to 500 μm.

[0184] As a non-limiting example, morphology and average size can be assessed by scanning electron microscopy (SEM).

[0185] The micrometer size makes the catalyst easier to handle.

[0186] According to a particular embodiment, the present invention relates to a bimetallic supported catalyst CuCo / ZrO2 as defined above, wherein the total content of the bimetallic elements copper and cobalt is between 0.5 and 25% relative to the total weight of the catalyst, preferably with a weight ratio of cobalt to copper between 1:1 and 1:10, preferably between 1:1 and 1:5; and / or the catalyst has a molar amount of elemental copper with a degree of oxidation (II) of more than 50% and / or a molar amount of elemental cobalt with a degree of oxidation (II) of more than 50%, and / or The catalyst is in the form of a cluster of fine particles of 1 to 500 μm, preferably in the form of a cluster of rounded particles.

[0187] These particles consist in particular of rod aggregates with a proportion of 1 to 10 and an average thickness of 50 to 500 nm.

[0188] Cu-Mn / γ-Al2O3 catalyst morphology According to a particular embodiment, the present invention relates to a zirconium dioxide support Cu—Mn / γ-Al2O3 as defined above, said catalyst being in the form of fine particles ranging from 1 to 500 μm, preferably in the form of a cluster of rounded particles.

[0189] Catalyst properties in reducing atmospheres According to a particular embodiment, the present invention relates to a bimetallic supported catalyst as defined above, characterized in that the reduction temperature of metallic copper with a degree of oxidation (0) is in the range of 150-250°C, as analyzed by temperature-programmed reduction (TPR) carried out in a dihydrogen reducing atmosphere at a temperature range of 30-900°C.

[0190] Advantageously, at temperatures above the reduction temperature of copper metal, in particular at temperatures of at least 10° C., the copper atoms are in the metallic state at more than 80%, in particular 80-100%, preferably 100%.

[0191] The 80-100% range includes the following ranges: 80-85%, 85-90%, 90-95%, 95-96%, 96-97%, 97-98%, 98-99%, and 99-100%.

[0192] Advantageously, at temperatures above the reduction temperature of copper metal, in particular at a temperature of at least 10°C, the metal M atoms are in an oxidation state, i.e. with a degree of oxidation greater than 0, greater than 80%, in particular between 80 and 100%, preferably 100%.

[0193] At temperatures above the reduction temperature of copper metal, in particular at a temperature of at least 10° C., the metal M atoms advantageously have 0 to 20%, in particular 0 to 10%, preferably less than 5%, in the metallic state with a degree of oxidation of 0.

[0194] The range of 0-20% includes the values ​​0.0%, 0.05%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, and 20%.

[0195] Advantageously, at temperatures above the reduction temperature of copper metal, in particular at temperatures of at least 10°C, the metal M is Co and cobalt atoms, 80 to 100% in the oxidation state, or the metal M is cobalt atoms, at least 10%, preferably at least 20%, in the metallic state.

[0196] At temperatures above the reduction temperature of copper metal, in particular at temperatures of at least 10°C, the metal M atoms are Mn and manganese atoms, advantageously in an oxidation state, i.e. with an oxidation degree greater than 0, between 95 and 100%, preferably 100%.

[0197] At temperatures above the reduction temperature of copper metal, in particular at temperatures of at least 10°C, the metal M atoms are Fe and iron atoms, advantageously in an oxidation state, i.e. an oxidation degree, greater than 0, between 95 and 100%, preferably 100%.

[0198] At temperatures above the reduction temperature of copper metal, in particular at temperatures of at least 10° C., the metal M atoms are Ni and nickel atoms, advantageously in the oxidation state 95 to 100%, preferably 100%.

[0199] According to a particular embodiment, the present invention relates to a bimetallic supported catalyst as defined above, wherein said catalyst, when analyzed by temperature-programmed reduction (TPR) carried out in a dihydrogen reducing atmosphere at a temperature range of 30 to 900 °C, has a reduction temperature of metallic copper with an oxidation degree of (0) in the range of 150 to 250 °C; In particular, analyzed by TPR at a temperature at least 10°C above the reduction temperature of copper metal; copper atoms are in a metallic state at 80 to 100%, preferably 100%; The metal M atoms are characterized by being 80 to 100%, preferably 100%, in an oxidation state.

[0200] According to a particular embodiment, the present invention relates to a bimetallic supported catalyst as defined above, characterized in that said catalyst is analyzed by temperature-programmed reduction (TPR) carried out under a reducing atmosphere with a flow rate of 5 vol% H in argon, in particular 30 mL / min, at a temperature range of 30-900 °C, in particular with a heating rate of 5 °C / min, and the reduction temperature for metallic copper with an oxidation degree of (0) is in the range of 150-250 °C.

[0201] Advantageously, the catalyst is pretreated at 200° C. in an inert atmosphere, in particular under a helium atmosphere, before said analysis.

[0202] According to a particular embodiment, the present invention relates to a bimetallic supported catalyst as defined above, which comprises 80 to 100%, in particular 95 to 100%, preferably 100%, of copper metal atoms Cu(0) under a hydrogen reducing atmosphere at a pressure of 2 to 10 MPa and a temperature of 150 to 250°C, in particular 180 to 220°C, and 80 to 100% of metal M atoms with a degree of oxidation above 0, wherein preferably said metal M is not in metallic state.

[0203] Advantageously, 95%, preferably 100%, of the copper atoms are in the metallic state.

[0204] Advantageously, the metal M atoms are in an oxidation state with a degree of oxidation greater than 0, between 80 and 100%, in particular between 95 and 100%, preferably 100%.

[0205] Advantageously, the cobalt atoms in the metallic state represent 0 to 20%, in particular 0 to 15%, preferably less than 20%.

[0206] Advantageously, the manganese atoms are in an oxidation state with a degree of oxidation greater than 0, 95%, preferably 100%.

[0207] Advantageously, the iron atoms are in an oxidation state with a degree of oxidation greater than 0, 95%, preferably 100%.

[0208] Advantageously, the nickel atoms are 95%, preferably 100%, in the oxidation state.

[0209] Preparation of ethylene glycol The third object of the present invention relates to a method for preparing ethylene glycol, The process comprises the hydrogenation of oxamide or oxamate compounds with hydrogen to ethylene glycol in the presence of a bimetallic supported catalyst of formula Cu-M / support, comprising, on a support, copper and a metal M selected from manganese, cobalt, nickel and iron, where M represents Mn, Co, Ni or Fe, respectively.

[0210] According to a particular embodiment, the present invention relates to a preparation method as defined above, wherein the support is selected from oxides, in particular zirconium dioxide (ZrO2) and γ-alumina (γ-Al2O3).

[0211] According to a particular embodiment, the present invention relates to a preparation method as defined above, wherein the catalyst support is zirconium dioxide (ZrO2).

[0212] According to a particular embodiment, the present invention relates to a preparation method as defined above, wherein the catalyst support is zirconium dioxide (ZrO2) and γ-alumina (γ-Al2O3).

[0213] According to a particular embodiment, the present invention relates to a process for the preparation as defined above, wherein said oxamide is represented by formula 1 below: [ka]

[0214] In the formula, R a and R b are independent of each other, hydrogen atoms, C1~C 20 straight or branched chain alkyl groups, C2~C 20 a straight-chain or branched-chain alkenyl group; C1~C 20 straight chain or branched chain heteroalkyl groups, C3~C 20 an aryl or heteroaryl group, C5~C 20 an alkylaryl or alkylheteroaryl group; C3~C 10 represents a cycloalkyl group, R a group or R b at least one of the groups is different from hydrogen; R a and R b may form a ring.

[0215] According to a particular embodiment, the present invention relates to a process for the preparation of ethylene glycol as defined above, wherein said oxamide compound is selected from oxamides prepared with diethylamine, piperidine, pyrrolidine, morpholine and aniline, preferably piperidine.

[0216] According to a particular embodiment, the present invention relates to a method for preparing as defined above, wherein said oxamate compound is represented by formula 2 below: [ka] In the formula, R a and R b are independent of each other, hydrogen atoms, C1~C 20 straight or branched chain alkyl groups, C2~C 20 a straight-chain or branched-chain alkenyl group; C1~C 20 straight chain or branched chain heteroalkyl groups, C3~C 20 an aryl or heteroaryl group, C5~C 20 an alkylaryl or alkylheteroaryl group; C3~C 10 represents a cycloalkyl group, R a group or R b at least one of the groups is different from hydrogen; R a and R b may be covalently bonded to form a ring, R c teeth, C1~C 10 straight or branched chain alkyl groups, C3~C 10 cycloalkyl groups, C3~C 20 an aryl or heteroaryl group, C5~C20 It represents a group selected from alkylaryl groups or alkylheteroaryl groups.

[0217] According to a particular embodiment, the present invention relates to a method of preparation as defined above, ● The hydrogenation process is - the oxamide compound or oxamate compound, - dihydrogen, - said bimetallic supported catalyst of formula Cu-M / support, comprising, on a support, copper and a metal M chosen from manganese, cobalt, nickel and iron, wherein M represents Mn, Co, Ni or Fe; optionally a base, optionally a solvent, to obtain a pressurizable reaction medium, optionally, heating the reaction medium, This involves obtaining ethylene glycol.

[0218] According to a particular embodiment, the present invention relates to a process for the preparation of ethylene glycol as defined above, ● The hydrogenation process is - the oxamide compound or oxamate compound, - dihydrogen, - said bimetallic supported catalyst of formula Cu-M / support, comprising, on a support, copper and a metal M selected from manganese, cobalt, nickel and iron, wherein M represents Mn, Co, Ni or Fe, respectively; - a base, a solvent; to obtain a reaction medium, optionally, heating the reaction medium, This involves obtaining ethylene glycol.

[0219] According to a particular embodiment, the present invention relates to a method of preparation as defined above, ● The hydrogenation process is - the oxamide compound or oxamate compound, - dihydrogen, - said bimetallic supported catalyst of formula Cu-M / support, comprising, on a support, copper and a metal M selected from manganese, cobalt, nickel and iron, wherein M represents Mn, Co, Ni or Fe, respectively; - a base, a solvent; to obtain a reaction medium, heating the reaction medium, This involves obtaining ethylene glycol.

[0220] Cu-Mn / support, ZrO2 or γ-Al2O3 According to a particular embodiment, the present invention relates to a method of preparation as defined above, ● The hydrogenation process is - the oxamide compound or oxamate compound, - dihydrogen, - a bimetallic supported catalyst of the formula Cu-Mn / support, comprising copper and manganese on a support, optionally a base, optionally a solvent, to obtain a pressurizable reaction medium, Optionally, the reaction medium is heated, This involves obtaining ethylene glycol.

[0221] According to a particular embodiment, the present invention relates to a method of preparation as defined above, ● The hydrogenation process is - the oxamide compound or oxamate compound, - dihydrogen, - a bimetallic supported catalyst of the formula Cu-Mn / oxide, comprising copper and manganese on an oxide support; optionally a base, optionally a solvent, to obtain a pressurizable reaction medium, optionally, heating the reaction medium, This involves obtaining ethylene glycol.

[0222] According to a particular embodiment, the present invention relates to a method of preparation as defined above, ● The hydrogenation process is - the oxamide compound or oxamate compound, - dihydrogen, - a bimetallic supported catalyst of formula Cu-Mn / ZrO2, comprising copper and manganese on a zirconium dioxide support; optionally a base, optionally a solvent, to obtain a pressurizable reaction medium, optionally, heating the reaction medium, This involves obtaining ethylene glycol.

[0223] According to a particular embodiment, the present invention relates to a method of preparation as defined above, ● The hydrogenation process is - the oxamide compound or oxamate compound, - dihydrogen, - a bimetallic supported catalyst of formula Cu-Mn / γ-Al2O3, comprising copper and manganese on a γ-alumina support; optionally a base, optionally a solvent, to obtain a pressurizable reaction medium, optionally, heating the reaction medium, This involves obtaining ethylene glycol.

[0224] Cu-Co / body, ZrO2 or γ-Al2O3 According to a particular embodiment, the present invention relates to a method of preparation as defined above, ● The hydrogenation process is - the oxamide compound or oxamate compound, - dihydrogen, - a bimetallic supported catalyst of the formula Cu-Co / support, comprising copper and cobalt on a support, optionally a base, optionally a solvent, to obtain a pressurizable reaction medium, optionally, heating the reaction medium, This involves obtaining ethylene glycol.

[0225] According to a particular embodiment, the present invention relates to a method of preparation as defined above, ● The hydrogenation process is - the oxamide compound or oxamate compound, - dihydrogen, - a bimetallic supported catalyst of the formula Cu-Co / oxide, comprising copper and cobalt on an oxide support; optionally a base, optionally a solvent, to obtain a pressurizable reaction medium, optionally, heating the reaction medium, This involves obtaining ethylene glycol.

[0226] According to a particular embodiment, the present invention relates to a method of preparation as defined above, ● The hydrogenation process is - the oxamide compound or oxamate compound, - dihydrogen, - a bimetallic supported catalyst of formula Cu-Co / ZrO2, comprising copper and cobalt on a zirconium dioxide support; optionally a base, optionally a solvent, to obtain a pressurizable reaction medium, optionally, heating the reaction medium, This involves obtaining ethylene glycol.

[0227] According to a particular embodiment, the present invention relates to a method of preparation as defined above, ● The hydrogenation process is - the oxamide compound or oxamate compound, - dihydrogen, - a bimetallic supported catalyst of formula Cu-Co / γ-Al2O3, comprising copper and cobalt on a γ-alumina support; optionally a base, optionally a solvent, to obtain a pressurizable reaction medium, optionally, heating the reaction medium, This involves obtaining ethylene glycol.

[0228] Cu-Ni / support, ZrO2 or γ-Al2O3 According to a particular embodiment, the present invention relates to a method of preparation as defined above, ● The hydrogenation process is - the oxamide compound or oxamate compound, - dihydrogen, - a bimetallic supported catalyst of the formula Cu-Ni / support, comprising copper and nickel on a support, optionally a base, optionally a solvent, to obtain a pressurizable reaction medium, optionally, heating the reaction medium, This involves obtaining ethylene glycol.

[0229] According to a particular embodiment, the present invention relates to a method of preparation as defined above, ● The hydrogenation process is - the oxamide compound or oxamate compound, - dihydrogen, - a bimetallic supported catalyst of the formula Cu-Ni / oxide, comprising copper and nickel on an oxide support; optionally a base, optionally a solvent, to obtain a pressurizable reaction medium, optionally, heating the reaction medium, This involves obtaining ethylene glycol.

[0230] According to a particular embodiment, the present invention relates to a method of preparation as defined above, ● The hydrogenation process is - the oxamide compound or oxamate compound, - dihydrogen, - a bimetallic supported catalyst of formula Cu-Ni / ZrO2, comprising copper and nickel on a zirconium dioxide support; optionally a base, optionally a solvent, to obtain a pressurizable reaction medium, optionally, heating the reaction medium, This involves obtaining ethylene glycol.

[0231] According to a particular embodiment, the present invention relates to a method of preparation as defined above, ● The hydrogenation process is - the oxamide compound or oxamate compound, - dihydrogen, - a bimetallic supported catalyst of formula Cu-Ni / γ-Al2O3, comprising copper and nickel on a γ-alumina support; optionally a base, optionally a solvent, to obtain a pressurizable reaction medium, optionally, heating the reaction medium, This involves obtaining ethylene glycol.

[0232] Cu-Fe / support, ZrO2 or γ-Al2O3 According to a particular embodiment, the present invention relates to a method of preparation as defined above, ● The hydrogenation process is - the oxamide compound or oxamate compound, - dihydrogen, - a bimetallic supported catalyst of the formula Cu-Fe / support, comprising copper and iron on a support; optionally a base, optionally a solvent, to obtain a pressurizable reaction medium, optionally, heating the reaction medium, This involves obtaining ethylene glycol.

[0233] According to a particular embodiment, the present invention relates to a method of preparation as defined above, ● The hydrogenation process is - the oxamide compound or oxamate compound, - dihydrogen, - a bimetallic supported catalyst of the formula Cu-Fe / oxide, comprising copper and iron on an oxide support; optionally a base, optionally a solvent, to obtain a pressurizable reaction medium, optionally, heating the reaction medium, This involves obtaining ethylene glycol.

[0234] According to a particular embodiment, the present invention relates to a method of preparation as defined above, ● The hydrogenation process is - the oxamide compound or oxamate compound, - dihydrogen, - a bimetallic supported catalyst of formula Cu-Fe / ZrO2, comprising copper and iron on a zirconium dioxide support; optionally a base, optionally a solvent, to obtain a pressurizable reaction medium, optionally, heating the reaction medium, This involves obtaining ethylene glycol.

[0235] According to a particular embodiment, the present invention relates to a method of preparation as defined above, ● The hydrogenation process is - the oxamide compound or oxamate compound, - dihydrogen, - a bimetallic supported catalyst of formula Cu-Fe / γ-Al2O3, comprising copper and iron on a γ-alumina support; optionally a base, optionally a solvent, to obtain a pressurizable reaction medium, optionally, heating the reaction medium, This involves obtaining ethylene glycol.

[0236] Preparation method of ethylene glycol and conditions of catalyst used According to a particular embodiment, the present invention relates to a process for the preparation of ethylene glycol as defined above, wherein said catalyst is the catalyst of the invention as defined above.

[0237] According to a particular embodiment, the present invention relates to a process for the preparation of ethylene glycol as defined above, wherein said catalyst is prepared by mixing a powdered support with an aqueous solution of copper salt and cobalt, followed by calcination.

[0238] According to a particular embodiment, the present invention relates to a method for preparing ethylene glycol as defined above, wherein said catalyst is prepared by mixing a powdered support with an aqueous solution of copper salt and cobalt, without adding any additives or surfactants, and calcining.

[0239] Advantageously, the catalyst using Cu-M / support in a manner as defined above is prepared according to a preparation method comprising the following steps: impregnation of a powdered, in particular zirconium dioxide or γ-alumina support with copper salts and metal M salts (M being selected from Mn, Co, Ni and Fe) dissolved in an aqueous solution with a volume of 5-10 mL of water, the ratio of solution to the mass of the support being 0.6-1.0; Thus, a step A of obtaining a Cu-M / support catalyst in the form of a homogeneous mixture; a step B of drying the homogeneous mixture to obtain a Cu-M / support catalyst in the form of a dry homogeneous mixture; and an activation step C, which comprises calcining the dried homogeneous mixture to obtain the catalyst.

[0240] In step A of the impregnation, the aqueous solution comprising the copper salt and the metal M salt (M being selected from Mn, Co, Ni and Fe) is advantageously free of additives and surfactants, i.e. the aqueous impregnation solution consists of a demineralized aqueous solution in which the metal M salt and the copper salt are dissolved.

[0241] Advantageously, the metal M salt is a nitrate and the copper salt is a nitrate.

[0242] Therefore, the process for the preparation of ethylene glycol as defined above according to the present invention is advantageously carried out using a catalyst prepared in an aqueous solution and is free of additives and surfactants, which makes it more industrializable and reduces costs.

[0243] Use of Cu-M / ZrO2 catalyst According to a particular embodiment, the present invention relates to a method for preparing ethylene glycol as defined above, wherein the Cu-M / ZrO2 catalyst has a specific surface area, as analyzed by BET, of 1 to 250 m 2 / g, especially 1-50m 2 / g, preferably 1 to 10m 2 / g, more preferably about 5m 2 / g.

[0244] According to a particular embodiment, the present invention relates to a method for the preparation of ethylene glycol as defined above, wherein said Cu-M / ZrO2 catalyst comprises a crystalline phase, analyzed by X-ray diffraction, crystallized in the monoclinic system, in particular baddeleyite, Optionally, the crystalline phase of the Cu-M / ZrO catalyst comprises 50 to 90 wt. % based on the total weight of the catalyst; Optionally, the crystallite size of said crystalline phase is between 15 and 40 nm.

[0245] Conditions for ethylene glycol preparation method According to a particular embodiment, the present invention relates to a process for the preparation of ethylene glycol as defined above, wherein said catalyst is used in a proportion of copper between 0.1 and 10 mmol, in particular 4 mmol.

[0246] The range of 0.1 to 10 mmol includes ranges of 0.1 to 0.5 mmol, 0.5 to 1 mmol, 1 to 2 mmol, 2 to 3 mmol, and 3 to 4 mmol.

[0247] According to a particular embodiment, the present invention relates to a method for preparing ethylene glycol as defined above, wherein the oxamide or oxamate compound is used in a proportion of 2 to 400 molar equivalents, in particular 5 equivalents, relative to metallic Cu.

[0248] The range of 2 to 400 molar equivalents includes ranges of 2 to 3 equivalents, 3 to 4 equivalents, 4 to 5 equivalents, 5 to 10 equivalents, 10 to 50 equivalents, 50 to 100 equivalents, 100 to 200 equivalents, 200 to 300 equivalents, and 300 to 400 equivalents.

[0249] According to a particular embodiment, the present invention relates to a process for the preparation of ethylene glycol as defined above, wherein hydrogen is used under a pressure of 2 to 10 MPa, in particular 6 MPa.

[0250] The expression MPa means 10 6 It is equivalent to a pascal and is equal to 10 bar.

[0251] The expression "2.0 to 10.0 MPa" corresponds to the ranges of 2.0 to 2.5 MPa, 2.5 to 3.0 MPa, 3.0 to 3.5 MPa, 3.5 to 4.0 MPa, 4.0 to 4.5 MPa, 4.5 to 5.0 MPa, 5.0 to 5.5 MPa, 5.5 to 6.0 MPa, 6.0 to 6.5 MPa, 6.5 to 7.0 MPa, 7.0 to 7.5 MPa, 7.5 to 8.0 MPa, 8.0 to 8.5 MPa, 8.5 to 9.0 MPa, 9.0 to 9.5 MPa, and 9.5 to 10 MPa.

[0252] According to a particular embodiment, the present invention relates to a process for the preparation of ethylene glycol as defined above, wherein the solvent is selected from dioxane, xylene, mesitylene, tetrahydrofuran (THF), 2-methyltetrahydrofuran, toluene, and in particular THF.

[0253] According to a particular embodiment, the present invention relates to a process for the preparation of ethylene glycol as defined above, in which the reaction medium is placed under a pressure of between 2 and 10 MPa, in particular 6 MPa.

[0254] According to a particular embodiment, the invention relates to a process for the preparation of ethylene glycol as defined above, in which the reaction medium is heated to a temperature between 100°C and 250°C, in particular between 180°C and 200°C.

[0255] The range of 100 to 250°C includes the ranges of 100 to 110°C, 110 to 120°C, 120 to 130°C, 130 to 140°C, 140 to 150°C, 150 to 160°C, 160 to 170°C, 170 to 180°C, 180 to 190°C, 190 to 200°C, 200 to 210°C, 210 to 220°C, 220 to 230°C, 230 to 240°C, and 240 to 250°C.

[0256] According to a particular embodiment, the invention relates to a process for the preparation of ethylene glycol as defined above, in which the reaction medium is heated for a period of from 5 to 24 hours, in particular from 8 to 16 hours.

[0257] Active catalyst According to a particular embodiment, the present invention relates to a process for the preparation of ethylene glycol as defined above, Hydrogen is used under a pressure of 2 to 10 MPa, especially 6 MPa. the reaction medium is heated to a temperature of between 100 and 250°C, in particular between 180 and 220°C, optionally for a period of between 5 and 24 hours, in particular for 8 or 16 hours, During the heating step of the reaction medium, the bimetal supported catalyst is activated, and the activated catalyst comprises: metallic copper atoms Cu(0) with a degree of oxidation of 0, between 80 and 100%, in particular between 95 and 100%, preferably 100%, - A metal M atom having an oxidation degree of 80% to 100% exceeding 0, and preferably, the metal M is a metal M atom that is not in a metallic state.

[0258] Advantageously, 95%, preferably 100%, of the copper atoms are in the metallic state.

[0259] Advantageously, the metal M atoms are in an oxidation state with a degree of oxidation greater than 0, between 80 and 100%, in particular between 95 and 100%, preferably 100%.

[0260] Advantageously, the cobalt atoms in the metallic state represent 0 to 20%, in particular 0 to 15%, preferably less than 20%.

[0261] Advantageously, the manganese atoms are in an oxidation state with a degree of oxidation greater than 0, 95%, preferably 100%.

[0262] Advantageously, the iron atoms are in an oxidation state with a degree of oxidation greater than 0, 95%, preferably 100%.

[0263] Advantageously, the nickel atoms are 95%, preferably 100%, in the oxidation state.

[0264] Advantageously, embodiments of the method according to the present invention do not require preactivation of the catalyst by reduction of metal species, but rather the catalyst is activated in-situ during the process.

[0265] The catalytic species for the hydrogenation of oxamide or oxamate, i.e., metallic copper with an oxidation degree of (0), is generated in situ. The second metal element, M, is primarily in an oxidized state on the support surface and acts as a promoter on the copper to catalyze the hydrogenation of oxamide or oxamate. Thus, unlike many prior art bimetallic catalysts that are inactive due to the lack of an initial step in which the catalytic species is reduced, the bimetallic catalyst of copper and metal M can be directly introduced into the hydrogenation process of oxamide or oxamate according to the present invention and does not require prior reduction to the metallic state to initiate the hydrogenation reaction.

[0266] Flow method conditions The process according to the invention may be carried out in a flow chemistry apparatus, for example a commercially available reactor such as the "H-Cube Pro®" or "Phoenix®" reactor from ThalesNano (7 Zahony Street, Graphisoft Park, Building D, H-1031 Budapest, Hungary) or the "E-Series" or "R-Series flow chemistry systems" reactor from Vapourtec (Unit 21 / Park Farm Business Centre / Fornham Pk, Bury Saint Edmunds IP28 6TS, UK).

[0267] The continuous flow process is advantageously carried out at a temperature of between 100 and 250°C.

[0268] The continuous flow process is advantageously carried out at a pressure of 0.1 to 10 MPa.

[0269] According to a particular embodiment, the continuous flow process is carried out in a reactor in which the gas occupies 10 to 90% of the reactor volume.

[0270] The expression "10-90%" includes ranges of 10-20%, 20-30%, 30-40%, 40-50%, 50-60%, 60-70%, 70-80%, and 80-90%.

[0271] According to a particular embodiment, the continuous flow process is carried out by means that allows a contact time of the reactants of between 1 second and 2 hours, in particular between 1 second and 2 minutes.

[0272] The expression "1 second to 2 hours" corresponds to the following scales: 1 to 15 seconds, 15 to 30 seconds, 30 seconds to 1 minute, 1 to 2 minutes, 2 to 15 minutes, 15 to 30 minutes, 30 minutes to 1 hour, and 1 to 2 hours.

[0273] According to a particular embodiment, the hydrogenation reaction step of the method is carried out in a continuous flow manner and includes means for introducing a hydrogen stream into the reactor in contact with the substrate (oxamide or oxamate).

[0274] According to a particular embodiment, the present invention relates to a process for the preparation of ethylene glycol as defined above, in which the substrate, i.e. oxamide or oxamate or a mixture thereof, is circulated under flow through or in contact with said catalyst, and / or hydrogen is circulated under flow.

[0275] Catalyst Preparation Method The fourth object of the present invention is a method for preparing a Cu-M / support catalyst, comprising: impregnating a powdered support with a copper salt and a metal M salt (M is selected from Mn, Co, Ni and Fe) dissolved in an aqueous solution of 5-10 mL of additive- and surfactant-free water, the ratio of the mass of the solution to the mass of the support being 0.6-1.0; Thus, a step A of obtaining a Cu-M / support catalyst in the form of a homogeneous mixture; Step B: drying the homogeneous material at a temperature in the range of 60 to 100°C for 10 to 24 hours to obtain a Cu-M / support catalyst in the form of a dry homogeneous mixture; and an activation step C, which comprises calcining the dried homogeneous mixture in air at a temperature of 200 to 1000°C for 1 to 15 hours to obtain the Cu-M / support catalyst.

[0276] According to a particular embodiment, the present invention provides a method for preparing a Cu-M / oxide, comprising the steps of: a step A of impregnating a powdered oxide support with a copper salt and a metal M salt (M being selected from Mn, Co, Ni and Fe) dissolved in an aqueous solution of 5-10 mL of water containing no additives or surfactants, in a ratio of the solution to the mass of the support of 0.6-1.0, thereby obtaining a Cu-M / support catalyst in the form of a homogeneous mixture; Step B: drying the homogeneous material at a temperature in the range of 60 to 100°C for 10 to 24 hours to obtain a Cu-M / support catalyst in the form of a dry homogeneous mixture; and an activation step C, which comprises calcining the dried homogeneous mixture in air at a temperature of 200 to 1000°C for 1 to 15 hours to obtain the Cu-M / support catalyst.

[0277] According to a particular embodiment, the present invention provides a method for preparing a Cu-M / ZrO catalyst, comprising the steps of: impregnating a powdered zirconium dioxide support with a copper salt and a metal M salt (M is selected from Mn, Co, Ni and Fe) dissolved in an aqueous solution of 5-10 mL of additive- and surfactant-free water, the ratio of solution to support mass being 0.6-1.0; This results in step A of obtaining a Cu-M / ZrO catalyst in the form of a homogeneous mixture, The carrier is Surface area: 1 to 250 m 2 / g, especially 1-50m 2 / g, preferably 1 to 10m 2 / g, Step A, which is analyzed by X-ray diffraction and contains a crystalline phase crystallized in a monoclinic system; a step B of drying the homogeneous material at a temperature in the range of 60 to 100°C for 10 to 24 hours to obtain a Cu-M / ZrO catalyst in the form of a dry homogeneous mixture; and an activation step C of calcining the dry homogeneous mixture in air at a temperature of 200 to 1000°C for 1 to 15 hours to obtain the catalyst.

[0278] According to a particular embodiment, the present invention provides a method for preparing a Cu—Mn / ZrO catalyst, comprising the steps of: Copper salts and manganese salts dissolved in an aqueous solution of 5-10 mL of water containing no additives or surfactants are impregnated onto a powdered zirconium dioxide support, the ratio of the solution to the mass of the support being 0.6-1.0; This results in a step A of obtaining a Cu-Mn / ZrO catalyst in the form of a homogeneous mixture, The carrier is Surface area: 1 to 250 m 2 / g, especially 1-50m 2 / g, preferably 1 to 10m 2 / g, Step A, which contains a crystalline phase analyzed by X-ray diffraction and crystallized in the monoclinic system; a step B of drying the homogeneous material at a temperature in the range of 60 to 100°C for 10 to 24 hours to obtain a Cu-Mn / ZrO catalyst in the form of a dry homogeneous mixture; and an activation step C of calcining the dry homogeneous mixture in air at a temperature of 200 to 1000°C for 1 to 15 hours to obtain the catalyst.

[0279] According to a particular embodiment, the present invention provides a method for preparing a Cu—Co / ZrO catalyst, comprising the steps of: copper salts and cobalt salts dissolved in an aqueous solution of 5-10 mL of water containing no additives or surfactants are impregnated onto a powdered zirconium dioxide support, the ratio of the solution to the mass of the support being 0.6-1.0; This results in a step A of obtaining a Cu-Co / ZrO catalyst in the form of a homogeneous mixture, The carrier is Surface area: 1 to 250 m 2 / g, especially 1-50m 2 / g, preferably 1 to 10m 2 / g, Step A, which is analyzed by X-ray diffraction and contains a crystalline phase crystallized in a monoclinic system; a step B of drying the homogeneous material at a temperature in the range of 60 to 100°C for 10 to 24 hours to obtain a Cu-Co / ZrO catalyst in the form of a dry homogeneous mixture; and an activation step C of calcining the dry homogeneous mixture in air at a temperature of 200 to 1000°C for 1 to 15 hours to obtain the catalyst.

[0280] According to a particular embodiment, the present invention provides a method for preparing a Cu—Ni / ZrO catalyst, comprising the steps of: Copper salts and nickel salts dissolved in an aqueous solution of 5-10 mL of water containing no additives or surfactants are impregnated onto a powdered zirconium dioxide support, the ratio of the solution to the mass of the support being 0.6-1.0; This results in a step A of obtaining a Cu-Ni / ZrO catalyst in the form of a homogeneous mixture, The carrier is Surface area: 1 to 250 m 2 / g, especially 1-50m 2 / g, preferably 1 to 10m 2 / g, Step A, which is analyzed by X-ray diffraction and contains a crystalline phase crystallized in a monoclinic system; a step B of drying the homogeneous material at a temperature in the range of 60 to 100°C for 10 to 24 hours to obtain a Cu-Ni / ZrO catalyst in the form of a dry homogeneous mixture; and an activation step C of calcining the dry homogeneous mixture in air at a temperature of 200 to 1000°C for 1 to 15 hours to obtain the catalyst.

[0281] According to a particular embodiment, the present invention provides a method for preparing a Cu—Fe / ZrO catalyst, comprising the steps of: Copper salts and iron salts dissolved in an aqueous solution of 5-10 mL of water containing no additives or surfactants are impregnated onto a powdered zirconium dioxide support, the ratio of the solution to the mass of the support being 0.6-1.0; This results in a step A of obtaining a Cu-Fe / ZrO catalyst in the form of a uniform mixture, The carrier is Surface area: 1 to 250 m 2 / g, especially 1-50m 2 / g, preferably 1 to 10m 2 / g, Step A, which is analyzed by X-ray diffraction and contains a crystalline phase crystallized in a monoclinic system; a step B of drying the homogeneous material at a temperature in the range of 60 to 100°C for 10 to 24 hours to obtain a Cu-Fe / ZrO catalyst in the form of a dry homogeneous mixture; and an activation step C of calcining the dry homogeneous mixture in air at a temperature of 200 to 1000°C for 1 to 15 hours to obtain the catalyst.

[0282] According to a particular embodiment, the present invention provides a method for preparing a Cu-M / γ-AlO catalyst, comprising the steps of: copper salt and metal M salt (M is selected from Mn, Co, Ni and Fe) dissolved in an aqueous solution of 5-10 mL of additive- and surfactant-free water, impregnating the powdered γ-Al2O3 alumina support, the ratio of solution to support mass being 0.6-1.0; Step A: Obtaining a Cu-M / γ-AlO catalyst in the form of a homogeneous mixture; a step B of drying the homogeneous material at a temperature in the range of 60 to 100°C for 10 to 24 hours to obtain a Cu-M / γ-AlO catalyst in the form of a dry homogeneous mixture; and an activation step C, which comprises calcining the dried homogeneous mixture in air at a temperature of 200 to 1000°C for 1 to 15 hours to obtain the Cu-M / γ-Al2O3 catalyst.

[0283] According to a particular embodiment, the present invention provides a method for preparing a Cu—Mn / γ-AlO catalyst, comprising the steps of: Copper salts and manganese salts dissolved in an aqueous solution of 5-10 mL of water containing no additives or surfactants are impregnated onto a powdered γ-Al2O3 alumina support, with the ratio of the solution to the mass of the support being 0.6-1.0; Step A: Obtaining a Cu-Mn / γ-Al2O3 catalyst in the form of a homogeneous mixture; a step B of drying the homogeneous material at a temperature in the range of 60 to 100°C for 10 to 24 hours to obtain a Cu-Mn / γ-Al2O3 catalyst in the form of a dry homogeneous mixture; and an activation step C, which comprises calcining the dried homogeneous mixture in air at a temperature of 200 to 1000°C for 1 to 15 hours to obtain the Cu-Mn / γ-Al2O3 catalyst.

[0284] According to a particular embodiment, the present invention provides a method for preparing Cu—Co / γ-AlO, comprising the steps of: Copper salts and cobalt salts dissolved in an aqueous solution of 5-10 mL of water containing no additives or surfactants are impregnated onto a powdered γ-Al2O3 alumina support, with the ratio of the solution to the mass of the support being 0.6-1.0; Step A: Obtaining a Cu-Co / γ-Al2O3 catalyst in the form of a homogeneous mixture; a step B of drying the homogeneous material at a temperature in the range of 60 to 100°C for 10 to 24 hours to obtain a Cu-Co / γ-Al2O3 catalyst in the form of a dry homogeneous mixture; and an activation step C, which comprises calcining the dried homogeneous mixture in air at a temperature of 200 to 1000°C for 1 to 15 hours to obtain the Cu-Co / γ-Al2O3 catalyst.

[0285] According to a particular embodiment, the present invention provides a method for preparing a Cu—Ni / γ-AlO catalyst, comprising the steps of: Copper salts and nickel salts dissolved in an aqueous solution containing no additives or surfactants and having a volume of 5-10 mL are impregnated onto a powdered γ-Al2O3 alumina support, with the ratio of the solution to the mass of the support being 0.6-1.0; Thus, a step A of obtaining a Cu-Ni / γ-Al2O3 catalyst in the form of a homogeneous mixture; a step B of drying the homogeneous material at a temperature in the range of 60 to 100°C for 10 to 24 hours to obtain a Cu-Ni / γ-Al2O3 catalyst in the form of a dry homogeneous mixture; and an activation step C, which comprises calcining the dried homogeneous mixture in air at a temperature of 200 to 1000°C for 1 to 15 hours to obtain the Cu-Ni / γ-Al2O3 catalyst.

[0286] According to a particular embodiment, the present invention provides a method for preparing a Cu—Fe / γ-AlO catalyst, comprising the steps of: Copper salts and iron salts dissolved in an aqueous solution containing no additives or surfactants and having a volume of 5-10 mL are impregnated onto a powdered γ-Al2O3 alumina support, with the ratio of the solution to the mass of the support being 0.6-1.0; Step A: Obtaining a Cu-Fe / γ-AlO catalyst in the form of a homogeneous mixture; a step B of drying the homogeneous material at a temperature in the range of 60 to 100°C for 10 to 24 hours to obtain a Cu-Fe / γ-Al2O3 catalyst in the form of a dry homogeneous mixture; and an activation step C, which comprises calcining the dried homogeneous mixture in air at a temperature of 200 to 1000°C for 1 to 15 hours to obtain the Cu-Fe / γ-Al2O3 catalyst.

[0287] According to a particular embodiment, the present invention relates to a method as defined above for the preparation of a catalyst according to the invention, wherein in step A, said metal M salt is a nitrate and / or said copper salt is copper nitrate.

[0288] According to a particular embodiment, the present invention relates to a method as defined above for the preparation of a catalyst according to the invention, wherein in step A, said support is used in an amount ranging from 1 to 50 grams.

[0289] According to a particular embodiment, the present invention relates to a method as defined above for the preparation of a Cu-M / support catalyst according to the invention, wherein in step A the total mass content of copper and the bimetallic element of metal M is between 0.5 and 25% relative to the total weight of the catalyst.

[0290] According to a particular embodiment, the present invention relates to a method as defined above for the preparation of a Cu-M / support catalyst according to the invention, wherein in step A the total mass content of the bimetallic element of copper and metal M is between 5 and 20% relative to the total weight of the catalyst.

[0291] According to a particular embodiment, the present invention relates to a method as defined above for the preparation of a Cu-M / support catalyst according to the invention, wherein in step A the total mass content of elemental copper is between 1 and 25%, preferably between 1 and 10%, relative to the total weight of the catalyst.

[0292] According to a particular embodiment, the present invention relates to a method as defined above for the preparation of a Cu-M / support catalyst according to the invention, wherein in step A the total mass content of the metal M elements is between 1 and 25%, preferably between 1 and 10%, relative to the total weight of the catalyst.

[0293] According to a particular embodiment, the present invention relates to a method as defined above for the preparation of a Cu-M / support catalyst according to the invention, wherein in step A the weight ratio of metal M to copper is between 1:1 and 1:10, in particular between 2:10 and 5:10.

[0294] According to a particular embodiment, the present invention relates to the above-defined method of preparing a Cu-M / support catalyst according to the invention, wherein in step B, said homogeneous mixture is dried at 80° C. for 16 hours.

[0295] According to a particular embodiment, the present invention relates to a method as defined above for the preparation of a Cu-M / support catalyst according to the invention, wherein in step C, said dry mixture is calcined at 600° C. for 2 hours.

[0296] According to a particular embodiment, the present invention relates to a method as defined above for the preparation of a Cu-M / ZrO catalyst according to the invention, wherein in step A, the support has a specific surface area, as analyzed by BET, between 1 and 50 m 2 / g.

[0297] According to a particular embodiment, the present invention relates to a method as defined above for the preparation of a catalyst according to the invention, wherein in step A, the support used for the Cu-M / ZrO catalyst has a specific surface area, as analyzed by BET, between 1 and 10 m 2 / g, preferably 5 to 7 m 2 / g.

[0298] According to a particular embodiment, the present invention relates to a method as defined above for the preparation of a Cu-M / ZrO2 catalyst according to the invention, wherein in step A, the support used represents 50-90% of the total weight of the catalyst.

[0299] According to a particular embodiment, the present invention relates to a method as defined above for the preparation of a Cu-M / ZrO2 catalyst according to the invention, wherein in step A, the support used comprises baddeleyite.

[0300] According to a particular embodiment, the present invention relates to a method as defined above for the preparation of a Cu-M / ZrO2 catalyst according to the invention, wherein in step A, the support used comprises baddeleyite, with a crystallite size of 15-100 nm, preferably 15-50 nm, and optionally contains impurities of hafnium (Hf), rhenium (Re) and silicon (Si).

[0301] According to a particular embodiment, the present invention relates to a method as defined above for the preparation of a Cu-Co / ZrO2 catalyst according to the invention, wherein in step A, said support is in the form of fine particles of 1 to 500 μm.

[0302] Catalysts prepared by the method of the present invention A fifth object of the present invention relates to a bimetallic supported catalyst of formula Cu-M / support, comprising, on a support, copper and a metal M selected from Mn, Co, Ni and Fe, and which can be obtained by the process for preparing the catalyst as defined above.

[0303] According to a particular embodiment, the present invention relates to a bimetallic supported catalyst of formula Cu-M / oxide, comprising copper and a metal M selected from Mn, Co, Ni and Fe, on an oxide support, and which can be obtained by the process for preparing the catalyst as defined above.

[0304] According to a particular embodiment, the present invention relates to a bimetallic supported catalyst of formula Cu-M / ZrO2, comprising copper and a metal M selected from Mn, Co, Ni and Fe, on a zirconium dioxide support, and which can be obtained by the process for preparing the catalyst as defined above.

[0305] According to a particular embodiment, the present invention relates to a bimetallic supported catalyst of formula Cu-M / ZrO2, comprising copper and manganese on a zirconium dioxide support, and which can be obtained by the process for preparing the catalyst as defined above.

[0306] According to a particular embodiment, the present invention relates to a bimetallic supported catalyst of formula Cu-Co / ZrO2, comprising copper and cobalt on a zirconium dioxide support, and which can be obtained by the process for preparing the catalyst as defined above.

[0307] According to a particular embodiment, the present invention relates to a bimetallic supported catalyst of formula Cu—Ni / ZrO2, comprising copper and nickel on a zirconium dioxide support, and which can be obtained by the process for preparing the catalyst as defined above.

[0308] According to a particular embodiment, the present invention relates to a bimetallic supported catalyst of formula Cu-Fe / ZrO2, comprising copper and iron on a zirconium dioxide support, and which can be obtained by the process for preparing the catalyst as defined above.

[0309] According to a particular embodiment, the present invention relates to a bimetallic supported catalyst of formula Cu-M / γ-AlO, comprising copper and a metal M selected from Mn, Co, Ni and Fe, on a γ-AlO alumina support, and which can be obtained by the process for preparing the catalyst as defined above.

[0310] According to a particular embodiment, the present invention relates to a bimetallic supported catalyst of formula Cu—Mn / γ-AlO, comprising copper and manganese on a γ-AlO alumina support, and which can be obtained by the method for preparing the catalyst as defined above.

[0311] According to a particular embodiment, the present invention relates to a bimetallic supported catalyst of formula Cu—Co / γ-Al2O3, comprising copper and cobalt on a γ-Al2O3 alumina support, and which can be obtained by the method for preparing the catalyst as defined above.

[0312] According to a particular embodiment, the present invention relates to a bimetallic supported catalyst of formula Cu—Ni / γ-Al2O3, comprising copper and nickel on a γ-Al2O3 alumina support, and which can be obtained by the method for preparing the catalyst as defined above.

[0313] According to a particular embodiment, the present invention relates to a bimetallic supported catalyst of formula Cu—Fe / γ-AlO, comprising copper and iron on a γ-AlO alumina support, and which can be obtained by the method for preparing the catalyst as defined above.

[0314] Catalyst properties in reducing atmospheres According to a particular embodiment, the present invention relates to a bimetallic supported catalyst prepared according to the invention and as defined above, The catalyst, analyzed by temperature-programmed reduction (TPR) carried out in a dihydrogen reducing atmosphere at a temperature range of 30 to 900°C, is characterized in that the reduction temperature of metallic copper with an oxidation degree of (0) is in the range of 150 to 250°C, particularly 180 to 220°C.

[0315] At temperatures above the reduction temperature of copper metal, in particular at a temperature of at least 10° C., the copper atoms are advantageously 80 to 100%, in particular 95 to 100%, preferably 100%, in the metallic state.

[0316] Advantageously, at temperatures above the reduction temperature of copper metal, in particular at a temperature of at least 10°C, the metal M atoms are in an oxidation state, i.e. with a degree of oxidation greater than 0, greater than 80%, in particular between 80 and 100%, preferably 100%.

[0317] At temperatures above the reduction temperature of copper metal, in particular at a temperature of at least 10° C., the metal M atoms advantageously have 0 to 20%, in particular 0 to 10%, preferably less than 5%, in the metallic state with a degree of oxidation of 0.

[0318] Advantageously, at temperatures above the reduction temperature of copper metal, in particular at temperatures of at least 10°C, the metal M is Co and cobalt atoms, 80 to 100% in the oxidation state, or the metal M is cobalt atoms, at least 10%, preferably at least 20%, in the metallic state.

[0319] At temperatures above the reduction temperature of copper metal, in particular at temperatures of at least 10°C, the metal M atoms are Mn and manganese atoms, advantageously in an oxidation state, i.e. with an oxidation degree greater than 0, between 95 and 100%, preferably 100%.

[0320] At temperatures above the reduction temperature of copper metal, in particular at temperatures of at least 10°C, the metal M atoms are Fe and iron atoms, advantageously in an oxidation state, i.e. an oxidation degree, greater than 0, between 95 and 100%, preferably 100%.

[0321] At temperatures above the reduction temperature of copper metal, in particular at temperatures of at least 10° C., the metal M atoms are Ni and nickel atoms, advantageously in an oxidation state between 95 and 100%, preferably 100%.

[0322] According to a particular embodiment, the present invention relates to a bimetallic supported catalyst as defined above, characterized in that said catalyst has a reduction temperature of metallic copper with a degree of oxidation (0) in the range of 150 to 250°C, as analyzed by temperature-programmed reduction (TPR) carried out in a dihydrogen reducing atmosphere at a temperature range of 30 to 900°C, In particular, analyzed by RTP at a temperature at least 10°C above the reduction temperature of copper metal; copper atoms are in a metallic state at 80 to 100%, preferably 100%; The metal M atoms are characterized by being 80 to 100%, preferably 100%, in an oxidation state.

[0323] According to a particular embodiment, the present invention relates to a bimetallic supported catalyst as defined above, characterized in that said catalyst is analyzed by temperature-programmed reduction (TPR) carried out under a reducing atmosphere with a flow rate of 5 vol% H in argon, in particular 30 mL / min, at a temperature range of 30-900 °C, in particular with a heating rate of 5 °C / min, and the reduction temperature for metallic copper with an oxidation degree of (0) is in the range of 150-250 °C.

[0324] Advantageously, the catalyst is pretreated at 200° C. in an inert atmosphere, in particular under a helium atmosphere, before said analysis.

[0325] According to a particular embodiment, the present invention relates to a bimetallic supported catalyst as defined above, which is prepared by subjecting the catalyst to a hydrogen reduction reaction under a pressure of 2 to 10 MPa and at a temperature of 150 to 250°C, in particular 180 to 220°C, in a hydrogen reduction atmosphere, - 80 to 100%, in particular 95 to 100%, preferably 100% of metallic copper atoms Cu(0), - metal M atoms with a degree of oxidation of 80% to 100% greater than 0, and genus M not in the metallic state.

[0326] Advantageously, 95%, preferably 100%, of the copper atoms are in the metallic state.

[0327] Advantageously, the metal M atoms are in an oxidation state with a degree of oxidation greater than 0, between 80 and 100%, in particular between 95 and 100%, preferably 100%.

[0328] Advantageously, the cobalt atoms in the metallic state represent 0 to 20%, in particular 0 to 15%, preferably less than 20%.

[0329] Advantageously, the manganese atoms are in an oxidation state with a degree of oxidation greater than 0, 95%, preferably 100%.

[0330] Advantageously, the iron atoms are in an oxidation state with a degree of oxidation greater than 0, 95%, preferably 100%.

[0331] Advantageously, the nickel atoms are 95%, preferably 100%, in the oxidation state.

[0332] Active catalyst Another object of the present invention relates to a bimetallic active supported catalyst of formula Cu-M / support, comprising, at the surface, on a support, copper and a metal M selected from Mn, Co, Ni and Fe, - 80 to 100%, in particular 95 to 100%, preferably 100% of copper atoms are Cu(0) with an oxidation degree of 0; The metal M atoms have an oxidation state with a degree of oxidation greater than 0 of 80 to 100%, in particular 95 to 100%, preferably 100%.

[0333] "Active catalyst" means a catalyst in an active state, i.e., a state in which the chemical reaction catalyzed by the catalyst is in progress, i.e., contains catalytic species that cause the catalytic reaction.

[0334] Advantageously, more than 95%, preferably 100%, of the copper atoms are in the metallic state.

[0335] Advantageously, the cobalt atoms are in an oxidation state with a degree of oxidation greater than 0, between 80 and 100%, in particular between 95 and 100%, preferably 100%.

[0336] Advantageously, the manganese atoms are in an oxidation state with a degree of oxidation greater than 0, greater than 95%, preferably 100%.

[0337] Advantageously, the iron atoms are in an oxidation state with a degree of oxidation greater than 0, greater than 95%, preferably 100%.

[0338] Advantageously, the nickel atoms are more than 95%, preferably 100%, in the oxidation state.

[0339] Use of catalysts for hydrogenolysis of ethylene glycol or depolymerization of biomass Another object of the present invention relates to the use of a catalyst of formula Cu-M / support, comprising copper and a metal M selected from manganese, cobalt, nickel and iron, on a support, for the hydrogenolysis of ethylene glycol, where M represents Mn, Co, Ni or Fe, respectively.

[0340] According to a particular embodiment, the present invention relates to the use as defined above of a catalyst of formula Cu-Co / ZrO2, comprising copper and cobalt, on a zirconium dioxide support, for the hydrogenolysis of ethylene glycol.

[0341] Another object of the present invention relates to the use of the Cu-M / support catalyst according to the invention as defined above for the hydrogenolysis of ethylene glycol.

[0342] The inventors have unexpectedly and surprisingly observed that the Cu-M / support catalyst according to the present invention is capable of catalyzing not only the hydrogenation of oxamide or oxamate to ethylene glycol, but also the hydrogenolysis of ethylene glycol present in the mixture resulting from the hydrogenation of oxamide or oxamate. Varying the conditions, such as temperature, can be adjusted to favor the hydrogenation of oxamide or oxamate, among other things.

[0343] For purposes of the present invention, "hydrogenolysis" refers to the reaction of cleaving at least one carbon-heteroatom covalent bond, such as a carbon-carbon (CC) bond or a carbon-oxygen bond, by the action of hydrogen.

[0344] Another object of the present invention is to provide a process for the hydrogenolysis of ethylene glycol, comprising: contacting ethylene glycol in the presence of hydrogen with a heterogeneous bimetallic supported catalyst of formula Cu-M / support as defined above, comprising copper and a metal M, on a support, where M is selected from Mn, Co, Ni and Fe.

[0345] According to a particular embodiment, the present invention relates to a process for the hydrogenolysis of ethylene glycol as defined above, ethylene glycol, dihydrogen, in particular at 20 to 100 bar, preferably at 60 bar; - said supported catalyst of formula Cu-M / support, comprising, on a support, copper and a metal M selected from manganese, cobalt, nickel and iron, wherein M represents Mn, Co, Ni or Fe, respectively; in particular with zirconium dioxide or γ-alumina, optionally a solvent, in particular tetrahydrofuran (THF), optionally a base, in particular potassium tert-butylate (KOtBu), to obtain a pressurizable reaction medium, optionally, heating the reaction medium, The method involves obtaining the decomposition of ethylene glycol by cleavage of at least one carbon-carbon or carbon-oxygen covalent bond.

[0346] Another object of the invention relates to the use of a catalyst of formula Cu-M / support, comprising, on a support, copper and a metal M chosen from manganese, cobalt, nickel and iron, for depolymerizing biomass by hydrogenolysis of the ethylene glycol groups present in compounds of said biomass, wherein M represents Mn, Co, Ni or Fe, respectively.

[0347] According to a particular embodiment, the present invention relates to the use as defined above of a bimetallic supported catalyst of formula Cu-Co / ZrO2, comprising copper and cobalt on a zirconium dioxide support, for depolymerizing biomass by hydrogenolysis of the ethylene glycol groups present in the compounds that constitute said biomass.

[0348] Another object of the present invention relates to the use of the Cu-M / support catalyst according to the invention as defined above for depolymerizing biomass.

[0349] Using ethylene glycol as a model compound, the inventors have surprisingly observed that the Cu-M / support catalyst according to the present invention is able to catalyze the hydrogenolysis reaction of diol groups present in carbohydrate molecules contained in biomass by cleaving carbon-carbon (C-C) or carbon-oxygen (C-O) bonds.

[0350] In the present invention, "biomass" refers to organic matter of plant origin (including microalgae), animal, bacterial or fungal origin that can be used as a source of energy (bioenergy). Biomass includes carbohydrate molecules or polyols in which the diol group -CHOH-CHOH-, i.e., ethylene glycol groups, containing covalent bonds (C-C) and (C-O) are present.

[0351] For purposes of the present invention, "depolymerizing biomass" refers to the act of cleaving covalent carbon-carbon (CC) bonds or covalent carbon-heteroatom (CX) bonds, such as carbon-oxygen (CO) bonds, of the carbohydrate molecules contained in the biomass.

[0352] Another object of the present invention is to provide a method for decomposing biomass, comprising the steps of: - a process for hydrocracking the C-C and C-O bonds of diol groups contained in carbohydrate molecules contained in biomass in the presence of a bimetallic supported catalyst of formula Cu-M / support as defined above, comprising copper and a metal M selected from Mn, Co, Ni and Fe, on a support, in particular an oxide, preferably zirconium dioxide, or on γ-alumina. [Brief explanation of the drawings]

[0353] [Figure 1] 1 is a powder X-ray diffraction pattern of a ZrO2 support calcined at 600°C for 2 hours. [Figure 2] This is a powder X-ray diffraction pattern of a Cu(10%)Co(5%) / ZrO2 catalyst with a specific surface area of ​​approximately 5 m2 / g, prepared using a ZrO2 support. [Figure 3] A scanning electron microscope image of a ZrO2 support calcined at 600°C for 2 hours is shown. [Figure 4] This shows a scanning electron microscope image of a Cu(10%)Co(5%) / ZrO2 catalyst with a specific surface area of ​​approximately 5 m2 / g, calcined at 600°C for 2 hours. [Figure 5] This shows a scanning electron microscope image of a Cu(10%)Mn(5%) / ZrO2 catalyst with a specific surface area of ​​approximately 5 m2 / g, calcined at 600°C for 2 hours. [Figure 6] This shows a scanning electron microscope image of a Cu(10%)Mn(5%) / γ-Al2O3 catalyst with a specific surface area of ​​approximately 150 m2 / g, calcined at 600°C for 2 hours. [Figure 7] The figure shows the X-ray photoelectron spectroscopy spectrum (Spectrum A) of a Cu-Co / ZrO2 catalyst, which has a composition of 10 wt% Cu and 5 wt% Co relative to the total weight of the catalyst and was calcined at 600°C for 2 hours, and the X-ray photoelectron spectroscopy spectrum (Spectrum B) of the ZrO2 support used in preparing the catalyst, which was calcined at 600°C for 2 hours. [Figure 8] This shows the X-ray photoelectron spectroscopy spectrum (Spectrum C) of a Cu-Mn / ZrO2 catalyst, which has a composition of 10 wt% Cu and 5 wt% Mn relative to the total weight of the catalyst and was calcined at 600°C for 2 hours, and the X-ray photoelectron spectroscopy spectrum (Spectrum D) of a Cu-Mn / γ-Al2O3 catalyst, which has a composition of 10 wt% Cu and 5 wt% Mn relative to the total weight of the catalyst and was calcined at 600°C for 2 hours. [Figure 9] Figure 1 shows X-ray photoelectron spectroscopy spectra of copper (Cu2p) in Cu(10%)Mn(5%) / ZrO2 catalyst and Cu(10%)Mn(5%) / γ-Al2O3 catalyst. [Figure 10] X-ray photoelectron spectroscopy spectra of manganese Mn2p for the catalysts Cu(10%)Mn(5%) / ZrO2 and Cu(10%)Mn(5%) / γ-Al2O3 are shown. [Figure 11] The analytical curves of the catalysts are shown for temperature-programmed reduction (H2-TRP) in the temperature range of 100–500 °C under a dihydrogen flow, where part (a) is for the catalyst prepared with Cu(10%)Co(5%) / γ-Al2O3, part (b) is for the catalyst prepared with Cu(10%)Mn(5%) / γ-Al2O3, part (c) is for the catalyst prepared with Cu(10%)Co(5%) / ZrO2, and part (e) is for the catalyst prepared with Cu(10%)Mn(5%) / ZrO2. DETAILED DESCRIPTION OF THE INVENTION

[0354] The following examples and the accompanying figures illustrate the invention without limiting its scope.

[0355] Figure 1 shows the powder X-ray diffraction pattern of the ZrO2 support calcined at 600°C for 2 hours.

[0356] Figure 2 shows the specific surface area of ​​approximately 5 m2 prepared using a ZrO2 support. 2 1 shows the powder X-ray diffraction pattern of Cu(10%)Co(5%) / ZrO2 catalyst at 1000 nm / g.

[0357] Figure 3 shows a scanning electron microscope image of the ZrO2 support calcined at 600°C for 2 hours.

[0358] Figure 4 shows a sample with a specific surface area of ​​approximately 5 m2, which was fired at 600°C for 2 hours. 2 1 shows a scanning electron microscope image of a Cu(10%)Co(5%) / ZrO2 catalyst at 1000 W / g.

[0359] Figure 5 shows a sample with a specific surface area of ​​approximately 5m2, which was fired at 600°C for 2 hours. 2 1 shows a scanning electron microscope image of a Cu(10%)Mn(5%) / ZrO2 catalyst at 1000 u / g.

[0360] Figure 6 shows the specific surface area of ​​approximately 150 m2 after sintering at 600°C for 2 hours. 2 Electron microscopy images of Cu(10%)Mn(5%) / γ-Al2O3 catalysts with 1000 u / g are shown.

[0361] Figure 7 shows the X-ray photoelectron spectroscopy spectrum (Spectrum A) of a Cu-Co / ZrO2 catalyst, which has a composition of 10 wt% Cu and 5 wt% Co relative to the total weight of the catalyst and was calcined at 600°C for 2 hours, and the X-ray photoelectron spectroscopy spectrum (Spectrum B) of the ZrO2 support used in the preparation of the catalyst, which was calcined at 600°C for 2 hours.

[0362] Figure 8 shows the X-ray photoelectron spectroscopy spectrum (spectrum C) of a Cu-Mn / ZrO2 catalyst, which has a composition of 10 wt% Cu and 5 wt% Mn relative to the total weight of the catalyst and was calcined at 600°C for 2 hours, and the X-ray photoelectron spectroscopy spectrum (spectrum D) of a Cu-Mn / γ-Al2O3 catalyst, which has a composition of 10 wt% Cu and 5 wt% Mn relative to the total weight of the catalyst and was calcined at 600°C for 2 hours.

[0363] Figure 9 shows the X-ray photoelectron spectroscopy spectra of copper Cu2p for the Cu(10%)Mn(5%) / ZrO2 and Cu(10%)Mn(5%) / γ-Al2O3 catalysts.

[0364] FIG. 10 shows the X-ray photoelectron spectroscopy spectra of manganese Mn2p for the catalysts Cu(10%)Mn(5%) / ZrO2 and Cu(10%)Mn(5%) / γ-Al2O3.

[0365] Figure 11 shows the analytical curves of the catalysts in temperature-programmed reduction (H2-TRP) in the temperature range of 100–500 °C under a dihydrogen flow, where part (a) is for the catalyst prepared with Cu(10%)Co(5%) / γ-Al2O3, part (b) is for the catalyst prepared with Cu(10%)Mn(5%) / γ-Al2O3, part (c) is for the catalyst prepared with Cu(10%)Co(5%) / ZrO2, and part (e) is for the catalyst prepared with Cu(10%)Mn(5%) / ZrO2.

[0366] Example 1 - Materials and Methods

[0367] Two types of supports were used to prepare the catalyst: zirconium dioxide (ZrO2) and alumina (γ-Al2O3).

[0368] ZrO2 zirconium oxide support has a specific surface area of ​​5 to 7 m 2 / g and is supplied by Sterm Chemicals, 15 Rue de l'Atome, 67800 Bischheim, under the reference number 93-4013.

[0369] The zirconium dioxide support ZrO2, supplied by Sterm Chemicals, consists of approximately 97% by weight zirconium dioxide, 1.86% by weight hafnium dioxide (HfO2) and trace amounts of silica (SiO2) and yttrium oxide (Y2O3).

[0370] The γ-Al2O3 support was supplied by Strem Chemicals (15 Rue de l'Atome, 67800 Bischheim) under the reference number 13-2525 and had a specific surface area of ​​approximately 185 m 2 / g, and the pore volume is 0.43cc / g.

[0371] The SiO2 support (40-63 mm) was supplied by VWR chemicals under the reference number 154425P.

[0372] Copper nitrate Cu(NO3)2·3H2O, cobalt nitrate (Co(NO3)2·3H2O), manganese, nickel, and iron nitrate were supplied by Fisher.

[0373] The autoclave is supplied by Parr Instrument.

[0374] Example 2 - General procedure for the preparation of heterogeneous Cu-M catalyst / support

[0375] A metal M nitrate (M is selected from Mn, Co, Ni, and Fe) and copper nitrate Cu(NO3)2·3H2O were dissolved in a minimum volume of 5–10 mL of demineralized water to form a solution. This solution containing the metal precursor was added to an appropriate amount of the support and mixed at room temperature until a homogeneous material was obtained. The catalyst was then dried at 80°C for 16 hours and calcined in air at 600°C for 2 hours to obtain the catalyst.

[0376] Table 1 below shows the preparation conditions of the Cu-M / ZrO2 catalyst and Cu-M / γ-Al2O3 catalyst prepared according to Example 2.

[0377] [Table 1]

[0378] Example 3 - General Procedure for Heterogeneous Catalysis for Oxamide Hydrogenation in a 450 mL Reactor

[0379] A 450 mL Parr autoclave equipped with a magnetic stirrer was charged with a homogeneous catalyst of copper (4 mmol Cu) on a support and a metal M (M selected from Mn, Co, Ni, and Fe), oxamide (10 mmol), potassium tert-butylate or potassium tert-butoxide (KOtBu) (2 mmol) as a base, and toluene or THF (40–75 mL) as a solvent. The reactor was sealed, and the reaction mixture was flushed with nitrogen (5 bar) three times and with hydrogen (5 bar) twice.

[0380] The autoclave was then pressurized under 60 bar of hydrogen, and the reaction mixture was stirred at a temperature of 180-200°C for 8, 15 or 24 hours.

[0381] After the reaction was complete, the autoclave was allowed to cool to room temperature, then evacuated and flushed with nitrogen (5 bar) three times.

[0382] The resulting final mixture was diluted, an internal standard (mesitylene) was added, and the yield was calculated using GC-MS.

[0383] Example 4 - Tests performed on Cu-M catalyst / support

[0384] The test was carried out according to Example 3 according to the following reaction scheme. [ka]

[0385] Table 2 shows the conditions of the hydrogenation tests carried out on the Cu-M catalyst / support prepared according to Example 2. The hydrogenation yield was calculated using GC-MS, with mesitylene as the internal standard. The conversion of oxamide corresponds to the amount of substrate consumed during the reaction.

[0386] [Table 2-1] [Table 2-2]

[0387] Example 5 - Tests performed - Effect of hydrotreating parameters

[0388] A) Monometallic catalyst Table 3 shows the conditions for hydrogenation tests carried out using Cu / ZrO2, Co / ZrO2, and Ni / ZrO2 monometallic catalysts. The hydrogenation yield was calculated using GC-MS, with mesitylene as the internal standard. The conversion of oxamide corresponds to the amount of substrate consumed during the reaction.

[0389] These results indicate that oxamide cannot be hydrogenated to ethylene glycol over a monometallic catalyst.

[0390] [Table 3]

[0391] B) Effects of temperature and reaction time Table 4 shows the conditions for the hydrogenation tests carried out on the Cu-Co / ZrO2 catalyst prepared according to Example 2. The conversion rate of oxamide, which corresponds to the amount of substrate consumed during the reaction, is calculated using GC-MS with mesitylene as an internal standard.

[0392] [Table 4]

[0393] C) Effect of bases Table 5 shows the conditions for the hydrogenation tests carried out over the Cu-Co / ZrO2 catalyst without the introduction of a base. The yield and conversion of oxamide were calculated using GC-MS with mesitylene as the internal standard.

[0394] [Table 5]

[0395] Example 6 - BET analysis of Cu-M catalyst / support

[0396] Table 6 shows the average specific surface area, as analyzed by BET, of the Cu(10%)-Co(5%) / ZrO2, Cu(10%)-Mn(5%) / ZrO2 and Cu(10%)-Mn(5%) / γ-Al2O3 catalysts prepared according to Example 2 after calcination at 600 °C for 2 h.

[0397] [Table 6]

[0398] Example 7: Structural analysis

[0399] A. Phase Analysis Powder X-ray diffraction of the materials (catalyst or support) was performed using a MINIFLEX II diffractometer commercially available from Rigaku, with X-rays emitted through a tube and copper source (wavelength Kα 1.54 Å).

[0400] Figure 1 shows a sample with a specific surface area of ​​5.4 m2, which was fired at 600°C for 2 hours. 2 RX diffractogram of the Co(5%)Cu(10%) / ZrO2 catalyst with ZnO / g.

[0401] Figure 2 shows a sample with a specific surface area of ​​6.1 m2, which was fired at 600°C for 2 hours. 2 RX diffractogram of the ZrO2 support used is shown.

[0402] The results obtained from the various diffraction runs are shown in Tables 7 to 10 below, respectively: - Table 7 relates to the ZrO2(A) support, Table 8 relates to the Cu(10%)Co(5%) / ZrO2 catalyst: Table 9 relates to the Cu(10%)Mn(5%) / ZrO2 catalyst, Table 10 relates to the Cu(10%)Mn(5%) / γ-Al2O3 catalyst.

[0403] [Table 7]

[0404] [Table 8]

[0405] [Table 9]

[0406] [Table 10]

[0407] Zirconium dioxide ZrO2 catalyst The diffraction pattern of the catalyst on zirconium dioxide shows the presence of a crystalline phase.

[0408] XRD analysis shows that baddeleyite (ZrO2) crystalline phase exists in ZrO2, Cu(10%)Co(5%) / ZrO2 and Cu(10%)Mn(5%) / ZrO2 catalyst samples.

[0409] In the diffractogram of the Co(5%)Cu(10%) / ZrO2 sample, weak signatures reveal the presence of two additional crystalline phases: Cu2O, a Cu(I) oxide, and CuO oxide, a Cu(II) oxide.

[0410] The diffraction pattern of the Cu(10%)Mn(5%) / ZrO2 sample reveals the presence of a majority of the crystalline phase of baddeleyite and minor amounts of copper oxide, CuO, and manganese-copper oxide, CuMn2O4.

[0411] Alumina Cu(10%)Mn(5%) / γ-Al2O3 catalyst The diffraction pattern of the Cu(10%)Mn(5%) / γ-Al2O3 sample reveals the presence of crystalline phases of aluminum oxide approximating alumina, as well as copper oxide CuO, copper manganese oxide CuMn2O4, and manganese aluminum oxide.

[0412] B. Crystallinity - Microstructure: Crystallite Size Analysis Crystallite size The crystallinity of a material is manifested by the crystallite size.

[0413] To compare the ZrO2 supports of the catalysts, the crystallite size was qualitatively estimated.

[0414] The crystallite size was evaluated by the following Scherrer equation.

number

[0415] The half-width was estimated using ImageJ processing software (developed by the National Institutes of Health, USA).

[0416] Table 11 below shows the calculation of the crystallite size from the diffractogram of the Co(5%)Cu(10%) / ZrO2 catalyst.

[0417] [Table 11]

[0418] Example 8: Morphological and compositional analysis

[0419] The SEM images in Figures 3 to 6 were taken using a Zeiss SEM-FEG scanning microscope, which uses pressure control to enable observation of materials with little or no conductivity without the need for special preparation.

[0420] The samples were placed on carbon adhesive paper for SEM observation, so it should be noted that the carbon element content may be related to the use of the latter.

[0421] The results of the SEM observation and EDX analysis are summarized below.

[0422] ZrO2 calcined support SEM observation of the image in Figure 3 reveals the presence of several particle populations (round, spherical, and angular). The majority population has a rounded morphology, similar to that of the Co(5%)Cu(10%)ZrO2 sample. These particles consist primarily of zirconium (Zr), oxygen (O), and carbon (C), with traces of rhenium (Re), hafnium (Hf), and silicon (Si).

[0423] The second population of spherical particles consists mainly of zirconium (Zr), oxygen (O), carbon (C), with small amounts of hafnium (Hf) and rhenium (Re) and trace amounts of silicon (Si).

[0424] Quantitation was performed by EDX spectroscopy on two regions of support particles calcined for 2 hours at 600° C. The results are shown in Table 12 in weight percent.

[0425] [Table 12]

[0426] Co(5%)Cu(10%) / ZrO2 catalyst Inspection of the SEM image in Figure 4 reveals the presence of a population of particles with rounded morphology similar to that of calcined ZrO2 supports. These particles consist primarily of zirconium (Zr), copper (Cu), oxygen (O), carbon (C), and cobalt (Co), with small amounts of hafnium (Hf) and rhenium (Re) and trace amounts of silicon (Si). Quantitation was performed on regions of these particles by EDX spectroscopy. The results, expressed as mass %, are shown in Table 13.

[0427] [Table 13]

[0428] Cu(10%)Mn(5%) / ZrO2 catalyst Inspection of the SEM image in Figure 5 reveals the presence of a cluster of particles with a rounded, aggregated morphology similar to that of calcined ZrO2 supports. These particles consist primarily of zirconium (Zr), copper (Cu), oxygen (O), and manganese (Mn), with small amounts of hafnium (Hf) and rhenium (Re). Quantitation was performed by EDX spectroscopy in the region of these particles. The results are presented in Table 14 in weight percent.

[0429] In addition, SEM observation was performed using backscattered electron images, but no difference in chemical contrast was observed in the particles.

[0430] [Table 14]

[0431] Cu(10%)Mn(5%) / γ-Al2O3 catalyst Observation of the SEM image in Figure 6 reveals the presence of a cluster of particles with rounded morphology and varying sizes. The entire cluster is covered with tiny particles with needle-like morphology. These particles consist primarily of aluminum (Al), copper (Cu), oxygen (O), and manganese (Mn). Quantitation was performed by EDX spectroscopy in the region of these particles. The results are shown in Table 15 in mass %.

[0432] In addition, SEM observation was performed using backscattered electron images, but no difference in chemical contrast was observed in the particles.

[0433] [Table 15]

[0434] Example 9: Composition analysis by ICP-AES

[0435] The compositions of Cu(10%)Mn(%) / ZrO2 and Cu(10%)Mn(%) / γ-Al2O3 catalysts were analyzed by ICP-AES, and the results are reported in Tables 16 and 17, respectively.

[0436] The samples were mineralized in a solution of 2 mL of nitric acid (HNO3) + 1 mL of hydrofluoric acid (HF) at 100 °C for 2 h.

[0437] [Table 16]

[0438] [Table 17]

[0439] Example 10: Surface analysis by XPS

[0440] The analysis is carried out with a photoelectron spectrometer, PHI QUANTES, which is equipped with a monochromatic X-ray source (aluminum Kα radiation), a chromium X-ray source for hard XPS generation, a charge neutralization system for electrically insulating samples, and a hemispherical electron analyzer.

[0441] XPS analysis was carried out on a Co(5%)Cu(10%) / ZrO2 catalyst calcined at 600°C for 2 hours and a ZrO2 support sample calcined at 600°C for 2 hours.

[0442] FIG. 7 shows the XPS spectrum.

[0443] A. Quantifying Polar Surface Area Table 18 below shows the determination of polar surface area, expressed in wt. %, for two calcined samples of ZrO2 and Co(5%)Cu(10%) / ZrO2.

[0444] [Table 18]

[0445] Both samples have low carbon content, which is primarily responsible for air pollution. The TCo(5%)Cu(10%)ZrO2 sample consists of zirconium (Zr), oxygen (O), copper (Cu), cobalt (Co), and also contains trace amounts of silicon (Si) and sodium (Na).

[0446] The ZrO2 sample consists of zirconium (Zr), oxygen (O), and trace amounts of silicon (Si) and sodium (Na).

[0447] Table 19 below shows the determination of the polar surface area, expressed in mass %, for two samples: Cu(10%)Mn(5%) / ZrO2 and Cu(10%)Mn(5%) / γ-Al2O3.

[0448] [Table 19]

[0449] Both samples have low carbon content, which is primarily responsible for air pollution. The Cu(10%)Mn(5%) / ZrO2 sample mainly consists of zirconium (Zr), oxygen (O), and manganese (Mn) on the extreme surface.

[0450] The Cu(10%)Mn(5%) / γ-Al2O3 sample consists mainly of aluminum (Al) and oxygen (O).

[0451] B: Determination of the chemical environment of calcined ZrO2 and Co(5%)Cu(10%) / ZrO2 Table 20 below shows the results of Gaussian deconvolution of the spectra.

[0452] [Table 20]

[0453] C1s spectrum For all samples, deconvolution of the carbon C1s spectra reveals two components. The -285.0 eV component is characteristic of C-C and C-H bonds. These bonds are derived from air pollution. The -288.40 eV component is characteristic of C-O and C=O bonds, which are also representative of surface contamination.

[0454] O1s spectrum For all samples, deconvolution of the oxygen O1s spectra reveals two components. The -531.0 eV component is generally characteristic of oxides. The -531.2 eV component is characteristic of transition metal oxides.

[0455] Si2p spectrum For all samples, deconvolution of the silicon Si2p spectra reveals two components. The -103.3 eV component is characteristic of SiOx silicon oxide. The -102.0 eV component is characteristic of SiO2 silicon dioxide.

[0456] It should be noted that the characteristic components of cobalt(II) oxide CoO are at the same energy as the corresponding components of SiOx.

[0457] Na1s spectrum For all samples, deconvolution of the sodium Na1s spectrum reveals the characteristics of a single component of air pollution.

[0458] Cu2p3 / 2 spectrum For the Co(5wt%)Cu(10wt%)ZrO2 sample, deconvolution of the copper 2p3 / 2 spectrum reveals two components. The component at -934.0 eV is characteristic of copper(II) oxide, CuO.

[0459] Two strong satellite components at 943.5 eV and 963.5 eV are due to Cu 2+ Since this is a characteristic of an ion, it is a characteristic of copper(II) oxide, CuO. The component at -932.6 eV is characteristic of metallic copper or copper(I) oxide, Cu2O.

[0460] CO2p3 / 2 spectrum For the Co(5%)Cu(10%)ZrO2 sample, the cobalt 2p3 / 2 spectrum shows the characteristics of cobalt(III) oxide CO2O3 and cobalt(II) oxide CoO, as well as cobalt(II) hydroxide.

[0461] High-resolution XPS spectrum of zirconium 3d5 / 2. XPS analysis reveals the presence of predominantly zirconium oxide (ZrO2) with traces of silicon oxides (SiO2 and SiOx) and surface contamination (carbon and sodium) in all samples.

[0462] The Co(5%)Cu(10%) / ZrO2 sample shows the presence of two additional oxidation states of copper, CuO and Cu2O. XPS analysis also reveals the presence of cobalt in this sample in the form of cobalt hydroxide Co(OH)2 or cobalt(II) oxide CoO or cobalt(III) oxide CO2O3.

[0463] C. Determination of the chemical environment of Cu(10%)Mn(5%) / ZrO2 (Spectrum C) and Cu(10%)Mn(5%) / γ-Al2O3 (Spectrum D) catalysts Below we show the results of Gaussian deconvolution of the spectrum.

[0464] Carbon C1s spectrum The C1s spectra of the two samples show the presence of two contributions related to C-C / C-H and C=O bonds, which are typical of air pollution.

[0465] Oxygen O1s spectrum The O1s spectrum of Cu(10%)Mn(5%) / ZrO2 (spectrum C) shows three contributions related to copper(II) oxide CuO, zirconium oxide ZrO2, and O=C bonds, which were previously identified in the carbon spectrum.

[0466] The O1s spectrum of Cu(10%)Mn(5%) / γ-Al2O3 (spectrum D) shows four contributions, highlighting the presence of O=C bonds associated with alumina γ-Al2O3, copper(II) oxide CuO, and surface contamination.

[0467] Copper Cu2p spectrum The copper Cu2p spectrum cannot be interpreted solely by deconvolution; the oxidation degree of the elements can be determined from the positions of various peaks and the overall shape of the spectrum. The overall shape of the Cu2p spectrum of Cu(10%)Mn(5%) / ZrO2 (spectrum C) shows Cu peaks at around 943 eV and 963 eV. 2+ The typical satellite peaks of the ions are shown to be very prominent in the oxidized CuO state.

[0468] In addition, deconvolution of the Cu2p3 / 2 peak allowed us to distinguish between metallic copper and ionic Cu. + This indicates that there are a small number of

[0469] In addition, the overall shape of the Cu2p spectrum (spectrum D) of Cu(10%)Mn(5%) / γ-Al2O3 is also similar to that of Cu 2+ ions account for the majority, and Cu + This corresponds to a low proportion of ions.

[0470] Spectrum of manganese Mn2p As with copper Cu2p, the shape of the spectrum of manganese Mn2p indicates its oxidation state.

[0471] Cu(10%)Mn(5%) / ZrO2 (Spectrum C) The overall shape of the Mn2p spectrum of Cu(10%)Mn(5%) / ZrO2 is 2+ The satellite peak at around 648 eV is typical for Mn ions. By deconvolution of the Mn2p3 / 2 peak, this oxidation degree (II) is mainly due to the Mn2p3 / 2 peak present in trace amounts on the surface of the sample. 3+ ions and Mn 4+ ions are shown.

[0472] Cu(10%)Mn(5%) / γ-Al2O3 (Spectrum D) The overall shape of the Mn2p spectrum of Cu(10%)Mn(5%) / γ-Al2O3 is similar to that of Mn 2+ No satellite peaks corresponding to the ions are observed.

[0473] Deconvolution of the Mn2p3 / 2 peak revealed that for this sample, the predominant ion present at the surface was Mn 3+ It is recognized as an ion. Mn 2+ and Mn 4+ Ions are also identified at a low rate.

[0474] Spectrum of zirconium Zr3d The Zr3d spectrum of Cu(10%)Mn(5%) / ZrO2 (Spectrum C) consists of spin-orbit pairs associated with zirconium oxide ZrO2. Spectrum of aluminum Al2p The Al2p aluminum spectrum (D spectrum) of Cu(10%)Mn(5%) / γ-Al2O3 contains a single component corresponding to alumina γ-Al2O3. The shoulder observed around 77 eV corresponds to the copper 3p peak.

[0475] Spectra of silicon Si2p and sodium Na1s The Si2p silicon spectrum (C spectrum) of Cu(10%)Mn(5%) / ZrO2 shows the presence of silicon oxide SiO2.

[0476] The sodium Na1s spectrum (C spectrum) of Cu(10%)Mn(5%) / ZrO2 contains characteristic components typical of air pollution.

[0477] conclusion Cu(10%)Mn(5%) / ZrO2 (Spectrum C) XPS analysis of Cu(10%)Mn(5%) / ZrO2 shows that a large proportion of zirconium oxide ZrO2 is present at the surface. It also reveals a low proportion of manganese. Manganese is present in various ionic states, Mn 2+ , Mn 3+ , Mn 4+ In most cases, Mn 2+ This is thought to correspond to the presence of MnO oxide. 3+ The presence of ions is believed to correspond to the compound CuMn2O4 identified by XRD. 2+ This is evident in the ionic state, which corresponds to copper(II) oxide CuO and the compound CuMn2O4.

[0478] Cu(10%)Mn(5%) / γ-Al2O3 (Spectrum D) XPS analysis of Cu(10%)Mn(5%) / γ-Al2O3 shows the presence of a large proportion of aluminum oxide γ-Al2O3 at the surface. It also reveals a low proportion of manganese. Manganese is present in various ionic states, Mn 2+ , Mn 3+ , Mn 4+ Trace amounts of Mn 3+ The state corresponds to the compound CuMn2O4 identified by XRD. 2+ The ionic state corresponds to copper(II) oxide, CuO, and the compounds CuMn2O4 and CuAl2O4 identified by XRD.

[0479] Example 11 - Continuous Flow Hydrogenation Procedure

[0480] A 0.05–0.5 M oxamide solution in THF is pumped into the reactor at a rate of 0.3–3 mL / min. Next, the system pressure is set to 30–100 bar using a backpressure regulator, and the reactor is heated to 150–220 °C. The reactor is constructed of a stainless steel tube, and the catalyst (150–700 mg) used in the reaction is placed inside. Finally, hydrogen generated in situ or introduced externally through a valve is injected into the system at the desired flow rate of 20–100 mL / min. Finally, the catalyst is contacted with the hydrogen flow, and then the reagents are introduced. Once the system stabilizes, the product is collected in a vial at the reactor outlet and analyzed by GC-MS.

[0481] Example 12 - Procedure for decomposition of ethylene glycol by hydrogen reduction in the presence of CuCo / ZrO2 catalyst

[0482] A 450 mL Parr autoclave equipped with a magnetic stirrer was charged with a heterogeneous copper (4 mmol Cu) cobalt catalyst, ethylene glycol (10 mmol), potassium tert-butoxide (KOtBu) as a base, and tetrahydrofuran (THF) (75 mL) as a solvent. The reactor was sealed, and the reaction mixture was flushed with nitrogen (5 bar) three times and with hydrogen (5 bar) twice.

[0483] The autoclave was then pressurized under 60 bar of hydrogen and the reaction medium was then stirred at a temperature of 180-200° C. for 15 hours.

[0484] After the reaction was complete, the autoclave was allowed to cool to room temperature, then evacuated and flushed with nitrogen (5 bar) three times.

[0485] The resulting final mixture was diluted, an internal standard (mesitylene) was added, and the ethylene glycol yield was calculated using GC-MS.

[0486] The reaction balance for decomposition of ethylene glycol by hydrogenation in the presence of CuCo / ZrO2 catalyst is as follows: [ka]

[0487] Example 13 - Testing with Cu-Co / ZrO2 catalyst

[0488] Table 21 shows the conditions for the hydrogenolysis test of ethylene glycol in the presence of the CoCu / ZrO2 catalyst prepared according to Example 5. The conversion of ethylene glycol is calculated using GC-MS, with mesitylene as the internal standard.

[0489] [Table 21]

[0490] Example 14: Effect of introducing a second metal M into a copper catalyst supported on a zirconium dioxide support in the process for preparing ethylene glycol by hydrogenation of oxamide

[0491] Table 3 in Example 5 shows that the monometallic catalysts of copper, cobalt, and nickel on a zirconium dioxide support are inactive in the hydrogenation reaction of oxamide in the process for preparing ethylene glycol. It should be noted that iron and manganese are known to be reduced in a reducing atmosphere at high temperatures above 200°C, and the monometallic catalysts of iron and manganese do not have active metal sites for catalysis of the hydrogenation reaction, making them a priori inactive catalysts for the hydrogenation reaction of oxamide to ethylene glycol.

[0492] Table 22 below shows the results of the substrate (oxamide) conversion, ethylene glycol yield, and ethylene glycol production selectivity in the presence of a copper-supported catalyst with a constant copper content, i.e., 10% copper content relative to the total weight of the catalyst, under similar conditions (temperature, pressure, and temperature), in the absence of a second metal and in the presence of a second metal M (selected from Co, Fe, and Mn) with a content of 5% relative to the total weight of the catalyst.

[0493] [Table 22]

[0494] The following conclusions can be drawn from the tests in Tables 3 and 22: - Monometallic catalysts on zirconium dioxide supports are not active for the hydrogenation reaction of oxamide. - The presence of a second metal element on the support surface makes it possible to obtain a highly active copper catalyst. - The presence of a second metal element has a promoter effect on the catalytic activity of the copper catalyst in the hydrogenation of oxamide in terms of substrate conversion (50-70%) and selectivity for the reaction towards ethylene glycol (67-80%).

[0495] Example 15: Effect of introducing a second metal M into a copper-supported catalyst on an alumina support in the process for preparing ethylene glycol by hydrogenation of oxamide

[0496] Table 23 below shows the results of oxamide hydrogenation tests under similar conditions (temperature, pressure, temperature), showing the substrate (oxamide) conversion, ethylene glycol yield, and ethylene glycol production selectivity in the presence of a copper-supported catalyst with a constant copper content, i.e., 10% copper content relative to the total weight of the catalyst, and in the presence of a second metal M (selected from Co, Ni, and Mn) with a content of 2 to 5% relative to the total weight of the catalyst.

[0497] [Table 23]

[0498] The tests in Table 23 demonstrate the promoter effect of the presence of a second metal element on the catalytic activity of copper catalyst in the hydrogenation reaction of oxamide, with the following results: - Substrate conversion rate is 68-100%. - The reaction selectivity to ethylene glycol is 68-80%. - The production yield of ethylene glycol is 55-80%.

[0499] In the hydrogenation of oxamide, the selectivity to ethylene glycol with a bimetallic catalyst on an alumina support is significantly better than that of prior art hydrogenation reactions prepared with a copper monometallic catalyst on a mixed alumina and silicon support.

[0500] Example 16: Analysis of bimetallic catalysts by temperature-programmed reduction under reducing atmosphere

[0501] material and method Temperature-programmed reduction (PTR) or (TRP) analysis is used to characterize solid materials containing metal oxides (type of oxide, oxide mixture, dispersion on support). This technique, performed under reducing atmosphere, is known to those skilled in the art for the characterization of heterogeneous catalysts.

[0502] This consists in determining the amount of hydrogen consumed as a function of temperature, which allows determining the temperature at which the reduction from the oxidized state to the metallic state occurs, and possibly the nature of the metal oxides and the ratio between the metal oxides present.

[0503] Measurements by temperature-programmed hydrogen reduction (H2-TPR) were carried out using a Micromeritics Autochem II 2920 analyzer.

[0504] In a typical experiment, a 50 mg sample was pretreated at 200 °C (heating rate = 10 °C / min) for 30 min under a flow of He (30 mL / min). The sample was then allowed to cool to 30 °C while maintaining the He flow. Reduction analysis was performed from 30 to 900 °C (heating rate = 5 °C / min) under a flow of 5 vol% H in argon (30 mL / min). The final temperature (900 °C) was maintained for 30 min.

[0505] result FIG. 11 shows the bimetallic catalyst analysis by temperature programmed reduction under a dihydrogen reducing atmosphere for the following catalysts prepared according to Example 2: - Cu(10%)Co(5%) / γ-Al2O3 - Cu(10%)Mn(5%) / γ-Al2O3 - Cu(10%)Co(5%) / ZrO2 - Cu(10%)Mn(5%) / ZrO2

[0506] The analysis of the temperature curve is as follows: Cu(10%)Co(5%) / γ-Al2O3 (Fig. 11a): The low-temperature reduction peaks, with maxima at 204 and 215 °C, are thought to correspond to the sequential reduction of CuO to Cu2O and Cu2O to Cu, respectively. Furthermore, the high-temperature reduction peak centered at 285 °C is thought to be associated with the reduction of Co3O4 to CoO and its subsequent reduction to Co through close interaction with copper species.

[0507] Cu(10%)Mn(5%) / γ-Al2O3 (Fig. 11b): The main reduction peak was located at 233 °C, and by lowering the temperature to a similar level, the CuO on the alumina surface x and Mn x O y species (and / or corresponding oxide mixtures) Cu x Mn y O z ) to produce copper metal and MnO.

[0508] Cu(10%)Co(5%) / ZrO2 (Fig. 11c): The low-temperature reduction peaks, with maxima at 155 and 174 °C, are thought to correspond to the sequential reduction of CuO to Cu2O and Cu2O to Cu, respectively. Additionally, the high-temperature reduction peak centered at 221 °C is thought to be associated with the reduction of Co3O4 to CoO and the subsequent reduction to Co.

[0509] The Cu(10%)Mn(5%) / ZrO2-low temperature reduction peaks were maximal at 157°C and 169°C, which are considered to correspond to the successive reduction of CuO to Cu2O and Cu2O to Cu, respectively. The main reduction peak at 226°C corresponds to the Mn on the zirconia surface. x O y species (and / or the corresponding mixed oxides Cu x Mn y O z) to produce copper metal and MnO.

Claims

1. 1. Use of a bimetallic supported catalyst, the catalyst comprising copper and a metal M selected from manganese, cobalt, nickel and iron on a support, of the formula Cu-M / support, where M represents Mn, Co, Ni or Fe, respectively, in the production of ethylene glycol by hydrogenation (H ２ 2. Use of a compound selected from the group consisting of oxamide compounds and oxamate compounds in a process for preparing ethylene glycol from said compound by hydrogenation of said compound with 2,4-dimethyl-2,4-trimethyl ...

2. The use according to claim 1 , wherein the support is an oxide.

3. The support is zirconium dioxide (ZrO ２ ) or alumina (γ-Al ２ O ３ 3. The use according to claim 2, wherein

4. 1. A process for preparing ethylene glycol, comprising: A process for the preparation of ethylene glycol, comprising a step of hydrogenating an oxalate or oxamate compound with hydrogen to ethylene glycol in the presence of a bimetallic supported catalyst of formula Cu-M / support, comprising, on a support, copper and a metal M selected from manganese, cobalt, nickel and iron, wherein M represents Mn, Co, Ni or Fe, respectively.

5. The catalyst support is made of zirconium dioxide (ZrO ２ 5. The method for preparing ethylene glycol according to claim 4, wherein

6. The catalyst support is made of γ-alumina (γ-Al ２ O ３ 5. The method for preparing ethylene glycol according to claim 4, wherein

7. ● The hydrogenation process is ○ - the oxamide compound or oxamate compound; - dihydrogen and - said bimetallic supported catalyst of formula Cu-M / support, comprising, on a support, copper and a metal M chosen from manganese, cobalt, nickel and iron, where M represents Mn, Co, Ni or Fe; optionally a base, optionally a solvent, to obtain a pressurizable reaction medium, optionally, heating the reaction medium, A process for preparing ethylene glycol according to any one of claims 4 to 6, comprising obtaining ethylene glycol.

8. The method for preparing ethylene glycol according to any one of claims 4 to 7, wherein the oxamate compound is represented by Formula 1: 【Chemistry 1】 (In the formula, R ａ and R ｂ are independent of each other, hydrogen atoms, ・C １ ~C ２０ straight or branched chain alkyl groups, ・C ２ ~C ２０ a straight-chain or branched-chain alkenyl group; ・C １ ~C ２０ straight chain or branched chain heteroalkyl groups, ・C ３ ~C ２０ an aryl or heteroaryl group, ・C ５ ~C ２０ an alkylaryl or alkylheteroaryl group; ・C ３ ~C １０ represents a cycloalkyl group, R ａ group or R ｂ at least one of the groups is different from hydrogen; R ａ and R ｂ may be covalently bonded to form a ring.)

9. The method for preparing ethylene glycol according to any one of claims 4 to 7, wherein the oxamate compound is represented by formula 2: 【Chemistry 2】 (In the formula, R ａ and R ｂ are independent of each other, hydrogen atoms, ・C １ ~C ２０ straight or branched chain alkyl groups, ・C ２ ~C ２０ a straight-chain or branched-chain alkenyl group; ・C １ ~C ２０ straight chain or branched chain heteroalkyl groups, ・C ３ ~C ２０ an aryl or heteroaryl group, ・C ５ ~C ２０ an alkylaryl or alkylheteroaryl group; ・C ３ ~C １０ represents a cycloalkyl group, R ａ group or R ｂ at least one of the groups is different from hydrogen; R ａ and R ｂ may be covalently bonded to form a ring, R ｃ teeth, ・C １ ~C １０ straight or branched chain alkyl groups, ・C ３ ~C １０ cycloalkyl groups, ・C ３ ~C ２０ an aryl or heteroaryl group, ・C ５ ~C ２０ represents a group selected from an alkylaryl group or an alkylheteroaryl group.

10. Hydrogen is used under a pressure of 2 to 10 MPa, particularly 6 MPa; the reaction medium is heated to a temperature of from 100 to 250°C, in particular from 180 to 220°C, optionally the reaction medium is heated for a period of from 5 to 24 hours, in particular for 8 hours or 16 hours, During the heating step of the reaction medium, the bimetal supported catalyst is activated, and the activated catalyst comprises: metallic copper atoms Cu(0) with a degree of oxidation of 0, between 80 and 100%, in particular between 95 and 100%, preferably 100%, - a metal M atom having a degree of oxidation of 80% to 100% greater than 0, preferably said metal M being not in metallic state.

11. Formula Cu-M / ZrO ２ A bimetal supported catalyst comprising: copper and a metal M selected from Mn and Co on a zirconium dioxide support; The catalyst has a surface area of ​​1 to 50 m as analyzed by BET. ２ / g of catalyst.

12. 12. The catalyst of claim 11, wherein the zirconium dioxide support is free of manganese and / or chromium.

13. The catalyst has a surface area of ​​1 to 10 m as analyzed by BET. ２ / g, and in particular about 5m ２ 13. The catalyst according to claim 11 or 12, wherein the Cr content is 1.0 / g.

14. 13. The catalyst of claim 11 or 12, wherein the zirconium dioxide support comprises a crystalline phase crystallized in the monoclinic system as analyzed by X-ray diffraction.

15. 15. The catalyst of claim 14, wherein the crystalline phase comprises 50 to 90% by weight of the total weight of the catalyst.

16. Catalyst according to claim 14 or 15, wherein the crystalline phase is baddeleyite.

17. 17. The catalyst of any one of claims 11 to 16, wherein the catalyst comprises a crystalline phase analyzed by X-ray diffraction and consisting of crystallite sizes of 15 to 100 nm.

18. Formula Cu-M / γ-Al ２ O ３ A bimetal supported catalyst comprising: copper and a metal M selected from Mn and Co on a gamma-alumina support; The catalyst has a surface area of ​​100 to 200 m as analyzed by BET. ２ / g of catalyst.

19. The catalyst, analyzed by temperature-programmed reduction (TPR) performed under a dihydrogen reducing atmosphere at a temperature range of 30 to 900°C, has a reduction temperature of metallic copper with an oxidation degree of (0) in the range of 150 to 250°C; In particular, analyzed by TPR at a temperature at least 10° C. above the reduction temperature of copper metal; copper atoms are in the metallic state at 80 to 100%, preferably 100%; Catalyst according to any one of claims 11 to 18, wherein the metal M atoms are in the oxidation state between 80 and 100%, preferably 100%.

20. The catalyst is subjected to a hydrogen reduction atmosphere under a pressure of 2 to 10 MPa and a temperature of 150 to 250°C, particularly 180 to 220°C, 80 to 100%, in particular 95 to 100%, preferably 100% of said metallic copper atoms Cu(0), - metal M atoms with a degree of oxidation greater than 0, between 80% and 100%, preferably said metal M being not in the metallic state.

21. 1. A method for preparing a Cu-M catalyst / support, comprising: a copper salt and a metal M salt dissolved in an aqueous solution of additive-free and surfactant-free water with a volume of 5 to 10 mL, where M is a metal M salt selected from Mn, Co, Ni, and Fe, impregnated onto a powdered support, the ratio of solution to support mass being 0.6 to 1.0; Step A, in which a Cu-M / support catalyst is obtained in the form of a uniform mixture; Step B: drying the homogeneous material at a temperature ranging from 60 to 100°C for 10 to 24 hours to obtain a Cu-M / support catalyst in the form of a dry homogeneous mixture; an activation step C, which comprises calcining said dry homogeneous mixture in air at a temperature of 200-1000° C. for 1-15 hours to obtain said Cu-M / support catalyst.

22. The Cu-M / ZrO composition according to claim 11 ２ 22. The method of claim 21 for preparing a catalyst, comprising: impregnating a powdered zirconium dioxide support with a copper salt and a metal M salt dissolved in an aqueous solution of 5-10 mL of water containing no additives or surfactants, the ratio of solution to support mass being 0.6-1.0, and M being selected from Mn, Co, Ni and Fe; This resulted in a homogeneous mixture of Cu-M / ZrO ２ Step A for obtaining a catalyst, The carrier is Surface area: 1 to 250 m ２ / g, preferably 1 to 50 m ２ / g, preferably 1 to 10 m ２ / g, especially about 5m ２ / g, Step A, wherein the catalyst is analyzed by X-ray diffraction and contains a crystalline phase crystallized in the monoclinic system; The homogeneous mixture is preferably dried at a temperature in the range of 60 to 100°C for 10 to 24 hours to obtain Cu-M / ZrO in the state of a dried homogeneous mixture. ２ Step B for obtaining a catalyst; The dried homogeneous mixture is calcined in air, preferably at a temperature of 200 to 1000°C for 1 to 15 hours to obtain the Cu-M / ZrO ２ and an activation step C comprising obtaining a catalyst.

23. 23. A bimetallic supported catalyst of formula Cu-M / support, comprising, on a support, copper and a metal M selected from Mn, Co, Ni and Fe, obtainable by the process for preparing a catalyst according to claim 21 or 22.

24. The catalyst, analyzed by temperature-programmed reduction (TPR) performed under a dihydrogen reducing atmosphere at a temperature range of 30 to 900°C, has a reduction temperature of metallic copper with an oxidation degree of (0) in the range of 150 to 250°C; In particular, analyzed by RTP at a temperature at least 10° C. above the reduction temperature of copper metal; copper atoms are in the metallic state at 80 to 100%, preferably 100%; Catalyst according to claim 23, wherein the metal M atoms are in the oxidation state between 80 and 100%, preferably 100%.

25. The catalyst is subjected to a hydrogen reduction atmosphere under a pressure of 2 to 10 MPa and a temperature of 150 to 250°C, particularly 180 to 220°C, 80 to 100%, in particular 95 to 100%, preferably 100% of metallic copper atoms Cu(0), Catalyst according to claim 23 or 24, comprising a metal M atom with a degree of oxidation of between 80% and 100% greater than 0, the genus M not being in the metallic state.

26. A bimetallic active supported catalyst of the formula Cu-M / support, at the surface, on a support, copper and a metal M selected from Mn, Co, Ni and Fe, The copper atoms have an oxidation degree of 0, 80 to 100%, in particular 95 to 100%, preferably 100%, A catalyst in which the metal M atoms have an oxidation state with a degree of oxidation greater than 0 of 80 to 100%, in particular 95 to 100%, preferably 100%.

27. The method for preparing ethylene glycol according to any one of claims 4 to 10, wherein the catalyst is one according to any one of claims 11 to 18 and claims 23 to 26.

28. 1. Use of a catalyst of the formula Cu-M / support, which comprises, on a support, copper and a metal M selected from manganese, cobalt, nickel and iron, where M represents Mn, Co, Ni or Fe, respectively, for the hydrogenolysis of ethylene glycol.

29. The catalyst comprises copper and cobalt on a zirconium dioxide support, of the formula Cu—Co / ZrO ２ 29. Use of the catalyst according to claim 28 for the hydrogenolysis of ethylene glycol, wherein the catalyst is

30. 1. Use of a catalyst of formula Cu-M / support, which catalyst comprises, on a support, copper and a metal M selected from manganese, cobalt, nickel and iron, where M represents Mn, Co, Ni or Fe, respectively, for depolymerizing biomass by hydrogenolysis of ethylene glycol groups present in compounds comprising said biomass.

31. The catalyst comprises copper and cobalt on a zirconium dioxide support and has the formula Cu—Co / ZrO ２ 31. Use of a catalyst according to claim 30 for depolymerizing biomass by hydrogenolysis of the ethylene glycol groups present in compounds comprising said biomass.

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