CATALYST COMPRISING AN ACTIVE PHASE OF NICKEL IN THE FORM OF SMALL PARTICLES AND A NICKEL COPPER ALL

专利摘要:
Catalyst comprising nickel and copper, at a rate of 1 and 50% by weight of nickel element relative to the total weight of the catalyst, at a rate of 0.5 to 15% by weight of copper element relative to the total weight of the catalyst, and an alumina support, said catalyst being characterized in that: - the molar ratio between nickel and copper is between 0.5 and 5 mol / mol; - at least part of the nickel and copper is present under the form of a nickel-copper alloy; - the nickel content in the nickel-copper alloy is between 0.5 and 15% by weight of nickel element relative to the total weight of the catalyst, - the size of the nickel particles in the catalyst is less than 7 nm.
公开号:FR3099390A1
申请号:FR1908725
申请日:2019-07-31
公开日:2021-02-05
发明作者:Anne-Claire Dubreuil；Malika Boualleg
申请人:IFP Energies Nouvelles IFPEN；
IPC主号:

专利说明:

[0001] The present invention relates to a supported metal catalyst based on nickel and copper intended particularly for the hydrogenation of unsaturated hydrocarbons, and more particularly, for the selective hydrogenation of polyunsaturated compounds or for the hydrogenation of aromatics.
[0002] State of the art
[0003] Catalysts for the hydrogenation of aromatic compounds are generally based on metals from group VIII of the periodic table of elements, such as nickel. The metal is in the form of nanometric metallic particles deposited on a support which may be a refractory oxide. The group VIII metal content, the possible presence of a second metallic element, the size of the metal particles and the distribution of the active phase in the support as well as the porous nature and distribution of the support are parameters which can have a importance on catalyst performance.
[0004] The rate of the hydrogenation reaction is governed by several criteria, such as the diffusion of the reactants towards the surface of the catalyst (external diffusional limitations), the diffusion of the reactants into the pores of the support towards the active sites (internal diffusional limitations) and the intrinsic properties of the active phase such as the size of the metal particles and the distribution of the active phase within the support.
[0005] The promotion of nickel-based catalysts has frequently been proposed in order to improve the performance in hydrogenation of unsaturated hydrocarbons. By way of illustration, US patent 5,208,405 discloses a catalyst based on nickel and silver for the selective hydrogenation of C4-C10 diolefins. On the other hand, it is known to promote nickel, present mainly, with group IB metals, in particular gold (FR 2,949,077) or tin (FR 2,949,078). Document FR 3,011,844 discloses a catalyst for implementing a selective hydrogenation process comprising a support and an active metallic phase deposited on the support, the active metallic phase comprising copper and at least one nickel or cobalt metal. in a Cu:(Ni and/or Co) molar ratio greater than 1.
[0006] Furthermore, prior to the use of such catalysts and their implementation in a hydrogenation process, a step of reducing treatment in the presence of a reducing gas is carried out so as to obtain a catalyst comprising an active phase at least partially in metallic form. This treatment activates the catalyst and forms metal particles. This treatment can be carried out in-situ or ex-situ, i.e. after or before loading the catalyst into the hydrogenation reactor.
[0007] Finally, with a view to obtaining better catalytic performance, in particular better selectivity and/or activity, it is known in the state of the art to use additives of the organic compound type for the preparation of metal catalysts for selective hydrogenation or hydrogenation of aromatics.
[0008] Objects of the invention
[0009] Pursuing its research in the field of hydrogenating catalysts, the Applicant has now discovered that it is possible to prepare particularly active, and particularly selective catalysts, in the selective hydrogenation of polyunsaturated compounds or in the hydrogenation of aromatic compounds, by bringing into contact on a support porous, in a specific order, at least one nickel precursor, at least one copper precursor, and at least one specific organic compound, with a specific Cu:Ni ratio, and by carrying out after these contacting steps, a reduction stage in the catalytic reactor in the presence of a reducing gas, at a temperature below 200°C. Without wanting to be bound by any theory, it has been observed by the Applicant that during the preparation of the catalyst, the presence of copper greatly improves the reducibility of the nickel on the support, which makes it possible to carry out a stage of reduction of the metallic elements in presence of a reducing gas at lower temperatures and shorter reaction times than those commonly used in the prior art. The use of less severe operating conditions than in the prior art makes it possible to carry out the reduction step directly within the reactor in which it is desired to carry out the hydrogenation of the unsaturated compounds or the aromatic compounds.
[0010] In addition, it has been observed by the Applicant that during the preparation of the catalyst, carrying out a step of bringing the support into contact with at least one solution containing simultaneously a metal precursor based on copper and a metal precursor based on of nickel, followed by a stage of final drying and reduction in the presence of a reducing gas at low temperature (between 150°C and 250°C) makes it possible to obtain a nickel-copper alloy (in reduced form) which unexpectedly makes it possible to greatly improve the reducibility of the active phase of nickel on the support. Furthermore, the presence of copper in the catalyst makes it possible to maintain good activity and a longer life of the catalyst when the latter is brought into contact with a hydrocarbon feed comprising sulfur, in particular in the aromatic hydrocarbon cuts. Indeed, compared to nickel, the copper present in the catalyst more easily captures the sulfur compounds included in the charge, which limits the irreversible poisoning of the active sites.
[0011] It has also been observed that the catalysts according to the invention prepared in the presence of an organic compound (cited below) are much more active than the catalysts prepared in the absence of this type of organic compound.
[0012] The relative synergistic effect obtained in this preparation process makes it possible to obtain a catalyst comprising nickel of small particle size, which is particularly active, reducible at low temperature and particularly selective, in the selective hydrogenation of polyunsaturated compounds or in the hydrogenation of aromatic compounds .
[0013] A first object according to the invention relates to a catalyst comprising nickel and copper, in an amount of 1 and 50% by weight in element nickel relative to the total weight of the catalyst, in an amount of 0.5 to 15% by weight in element copper relative to the total weight of the catalyst, and an alumina support, said catalyst being characterized in that:
[0014] - the molar ratio between nickel and copper is between 0.5 and 5 mol/mol;
[0015] - at least part of the nickel and the copper is in the form of a nickel-copper alloy;
[0016] - the nickel content included in the nickel-copper alloy is between 0.5 and 15% by weight of nickel element relative to the total weight of the catalyst,
[0017] - the size of the nickel particles in the catalyst is less than 7 nm.
[0018] Advantageously, the size of the nickel particles in the catalyst is less than 5 nm.
[0019] Advantageously, the support is in the form of an extrudate with an average diameter of between 0.5 and 10 mm.
[0020] Advantageously, the support is in the form of a trilobed or quadrilobed extrudate.
[0021] Another object according to the invention relates to a method for preparing a catalyst according to the invention, comprising the following steps:
[0022] a) the alumina support is brought into contact with at least one solution containing at least one nickel precursor;
[0023] b) the alumina support is brought into contact with at least one solution containing at least one nickel precursor and at least one copper precursor;
[0024] c) the alumina support is brought into contact with at least one solution containing at least one organic compound comprising at least one carboxylic acid function, or at least one alcohol function, or at least one ester function, or at least one amide function , or at least one amine function,
[0025] Being heard that :
[0026] - steps a), b) and c) are carried out separately, in any order, or
[0027] - steps a) and c) are carried out simultaneously, step b) being carried out either before the combination of steps a) and c), or after;
[0028] - steps b) and c) are carried out simultaneously, step a) being carried out either before the combination of steps b) and c), or after;
[0029] d) at least one step of drying the catalyst precursor obtained at the end of steps a) to c) is carried out at a temperature below 250° C.;
[0030] e) a step of reducing the catalyst precursor obtained at the end of step d) is carried out by bringing said precursor into contact with a reducing gas at a temperature greater than or equal to 150° C. and less than 250° C.
[0031] Advantageously, the molar ratio between said organic compound introduced in step c) and the nickel element also introduced in step a) is between 0.01 and 5.0 mol/mol.
[0032] Advantageously, the organic compound of step c) is chosen from oxalic acid, malonic acid, glycolic acid, lactic acid, tartronic acid, citric acid, tartaric acid, pyruvic acid, levulinic acid, ethylene glycol, propane-1,3-diol, butane-1,4-diol, glycerol, xylitol, mannitol, sorbitol, glycol, glucose , dimethyl carbonate, diethyl carbonate, formamide, N-methylformamide, acetamide, N-methylacetamide, N,N-dimethylmethanamide, 2-pyrrolidone, γ-lactam, lactamide, urea , alanine, arginine, lysine, proline, serine, EDTA.
[0033] Advantageously, step e) is carried out at a temperature between 130 and 190°C.
[0034] Advantageously, step e) is carried out between 10 minutes and 110 minutes.
[0035] Advantageously, the copper content is between 0.5 and 12% by weight of copper element relative to the total weight of the catalyst.
[0036] Advantageously, the copper precursor is chosen from copper acetate, copper acetylacetonate, copper nitrate, copper sulphate, copper chloride, copper bromide, copper iodide or copper fluoride. copper. Preferably, the copper precursor is copper nitrate.
[0037] Another object according to the invention relates to a process for the selective hydrogenation of polyunsaturated compounds containing at least 2 carbon atoms per molecule contained in a charge of hydrocarbons having a final boiling point less than or equal to 300° C., which process being carried out at a temperature of between 0 and 300°C, at a pressure of between 0.1 and 10 MPa, at a hydrogen/(polyunsaturated compounds to be hydrogenated) molar ratio of between 0.1 and 10 and at an hourly volumetric speed between 0.1 and 200 h ^-1 when the process is carried out in the liquid phase, or at a hydrogen/(polyunsaturated compounds to be hydrogenated) molar ratio of between 0.5 and 1000 and at an hourly volume rate between 100 and 40000 h ^-1 when the process is carried out in the gas phase, in the presence of a catalyst according to the invention.
[0038] Another object according to the invention relates to a process for the hydrogenation of at least one aromatic or polyaromatic compound contained in a charge of hydrocarbons having a final boiling point less than or equal to 650° C., said process being carried out in phase gaseous or in the liquid phase, at a temperature between 30 and 350°C, at a pressure between 0.1 and 20 MPa, at a hydrogen/(aromatic compounds to be hydrogenated) molar ratio between 0.1 and 10 and at a hourly volume velocity VVH of between 0.05 and 50 h ⁻¹ , in the presence of a catalyst according to the invention.
[0039] Detailed description of the invention
[0040] 1. Definitions
[0041] In the following, the groups of chemical elements are given according to the CAS classification (CRC Handbook of Chemistry and Physics, publisher CRC press, editor-in-chief D.R. Lide, 81st edition, 2000-2001). For example, group VIII according to the CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IUPAC classification.
[0042] The degree of reduction (TR) of a metal M contained in the catalyst is defined as being the percentage of said metal M reduced after the step of reducing said catalyst. The reduction rate (TR) corresponds to the ratio between the quantity of reduced metal (M1) and the quantity of theoretically reducible metal present on the catalyst measured by Fluorescence X (M2), i.e. TR (%) = (M1/M2)x100 . In the context of the present invention, the rate of reduction of nickel (Ni) was measured by X-ray diffraction analysis (XRD or “X-ray diffraction” according to the English terminology). The description of the method for measuring the quantity of reducible metal on oxide catalysts is explained later in the description (cf. examples section).
[0043] By the specific surface of the catalyst or of the support used for the preparation of the catalyst according to the invention is meant the specific surface B.E.T. determined by nitrogen adsorption in accordance with standard ASTM D 3663-78 established from the BRUNAUER-EMMETT-TELLER method described in the periodical “The Journal of American Society”, 60, 309, (1938).
[0044] In this application, the term "comprise" is synonymous with (means the same as) "include" and "contain", and is inclusive or open-ended and does not exclude other non-recited material. It is understood that the term “include” includes the exclusive and closed term “consist”.
[0045] By “macropores”, we mean pores whose opening is greater than 50 nm.
[0046] By "mesopores", we mean pores whose opening is between 2 nm and 50 nm, limits included.
[0047] By “micropores”, we mean pores whose opening is less than 2 nm.
[0048] By total pore volume of the catalyst or of the support used for the preparation of the catalyst according to the invention is meant the volume measured by intrusion with a mercury porosimeter according to the ASTM D4284-83 standard at a maximum pressure of 4000 bar (400 MPa), using a surface tension of 484 dyne/cm and a contact angle of 140°. The wetting angle was taken as equal to 140° by following the recommendations of the work “Engineering techniques, treatise on analysis and characterization”, pages 1050-1055, written by Jean Charpin and Bernard Rasneur.
[0049] In order to obtain better precision, the value of the total pore volume corresponds to the value of the total pore volume measured by intrusion with a mercury porosimeter measured on the sample minus the value of the total pore volume measured by intrusion with a mercury porosimeter measured on the same sample for a pressure corresponding to 30 psi (about 0.2 MPa).
[0050] The volume of macropores and mesopores is measured by mercury intrusion porosimetry according to ASTM D4284-83 at a maximum pressure of 4000 bar (400 MPa), using a surface tension of 484 dyne/cm and a contact angle of 140°. The value from which the mercury fills all the intergranular voids is fixed at 0.2 MPa, and it is considered that beyond that the mercury penetrates into the pores of the sample.
[0051] The macroporous volume of the catalyst or of the support used for the preparation of the catalyst according to the invention is defined as being the cumulative volume of mercury introduced at a pressure of between 0.2 MPa and 30 MPa, corresponding to the volume contained in the pores of diameter apparent greater than 50 nm.
[0052] The mesoporous volume of the catalyst or of the support used for the preparation of the catalyst according to the invention is defined as being the cumulative volume of mercury introduced at a pressure of between 30 MPa and 400 MPa, corresponding to the volume contained in the pores of apparent diameter included between 2 and 50 nm.
[0053] The volume of the micropores is measured by nitrogen porosimetry. The quantitative analysis of the microporosity is carried out using the "t" method (method of Lippens-De Boer, 1965) which corresponds to a transformation of the initial adsorption isotherm as described in the work "Adsorption by powders and porous solids. Principles, methodology and applications” written by F. Rouquérol, J. Rouquérol and K. Sing, Academic Press, 1999.
[0054] The median mesoporous diameter is also defined as being the diameter such that all the pores, among all the pores constituting the mesoporous volume, of size less than this diameter constitute 50% of the total mesoporous volume determined by intrusion with a mercury porosimeter.
[0055] The median macroporous diameter is also defined as being the diameter such that all the pores, among all the pores constituting the macroporous volume, of size less than this diameter constitute 50% of the total macroporous volume determined by intrusion with a mercury porosimeter.
[0056] The term “size of the nickel particles” means the diameter of the crystallites of nickel in oxide form. The diameter of nickel crystallites in oxide form is determined by X-ray diffraction, from the width of the diffraction line located at the angle 2theta=43° (i.e. along the crystallographic direction [200 ]) using the Scherrer relation. This method, used in X-ray diffraction on powders or polycrystalline samples which links the width at mid-height of the diffraction peaks to the size of the particles, is described in detail in the reference: Appl. Crystal. (1978), 11, 102-113 "Scherrer after sixty years: A survey and some new results in the determination of crystallite size", J. I. Langford and A. J. C. Wilson.
[0057] The nickel and copper content is measured by X-ray fluorescence.
[0058] 2. Description
[0059] Catalyst
[0060] The invention relates to a catalyst comprising nickel and copper, in an amount of 1 and 50% by weight in nickel element relative to the total weight of the catalyst, in an amount of 0.5 to 15% by weight in copper element relative to the total weight of the catalyst, and an alumina support, said catalyst being characterized in that:
[0061] - the molar ratio between nickel and copper is between 0.5 and 5 mol/mol, preferably between 0.7 and 4.5 mol/mol, more preferably between 0.9 and 4 mol/mol;
[0062] - at least part of the nickel and the copper is in the form of a nickel-copper alloy, advantageously corresponding to the NixCuy formula with x between 0.1 and 0.9 and including between 0.1 and 0 .9;
[0063] - the nickel content included in the nickel-copper alloy is between 0.5 and 15% by weight of nickel element relative to the total weight of the catalyst, preferably between 1 and 12% by weight, and more preferably between 1 and 10% by weight;
[0064] - the size of the nickel particles, measured in oxide form, in the catalyst is less than 7 nm, preferably less than 5 nm, more preferably less than 4 nm, and even more preferably less than 3 nm.
[0065] The nickel content in said catalyst according to the invention is advantageously between 1 and 50% by weight relative to the total weight of the catalyst, more preferably between 2 and 40% by weight and even more preferably between 3 and 35% by weight and even more preferably 5 and 25% by weight relative to the total weight of the catalyst.
[0066] The copper content is between 0.5 and 15% by weight of copper element relative to the total weight of the catalyst, preferably between 0.5 and 12% by weight, preferably between 0.75 and 10% by weight , and even more preferably between 1 and 9% by weight.
[0067] The nickel content included in the copper-nickel alloy is advantageously between 0.5 and 15% by weight of nickel element relative to the total weight of the catalyst, preferably between 1 and 12% by weight, and more preferably between 1 and 10% by weight.
[0068] The molar ratio between nickel and copper is between 0.5 and 5 mol/mol, preferably between 0.7 and 4.5 mol/mol, more preferably between 0.9 and 4 mol/mol.
[0069] The active phase of the catalyst does not include any Group VIB metal. In particular, it does not include molybdenum or tungsten.
[0070] Said catalyst is generally presented in all the forms known to those skilled in the art, for example in the form of beads (generally having a diameter of between 1 and 8 mm), extrudates, tablets, hollow cylinders. Preferably, it consists of extrudates with a diameter generally between 0.5 and 10 mm, preferably between 0.8 and 3.2 mm and very preferably between 1.0 and 2.5 mm and of average length between 0.5 and 20 mm. The term "average diameter" of the extrudates means the average diameter of the circle circumscribed to the cross section of these extrudates. The catalyst can advantageously be presented in the form of cylindrical, multi-lobed, tri-lobed or quadri-lobed extrudates. Preferably, its shape will be trilobed or quadrilobed. The shape of the lobes can be adjusted according to all known methods of the prior art.
[0071] The specific surface of the catalyst is generally greater than or equal to 30 m ² /g, preferably greater than or equal to 50 m ² /g, more preferentially comprised between 60 m ² /g and 500 m ² /g, and even more preferentially comprised between 70 m ² /g and 400 m ² /g.
[0072] The total pore volume of the catalyst is generally between 0.1 and 1.5 cm ³ /g, preferably between 0.35 and 1.2 cm ³ /g, and even more preferably between 0.4 and 1, 0 cm ³ /g, and even more preferably between 0.45 and 0.9 cm ³ /g.
[0073] The catalyst advantageously has a macropore volume less than or equal to 0.6 mL/g, preferably less than or equal to 0.5 mL/g, more preferably less than or equal to 0.4 mL/g, and even more preferably less than or equal to equal to 0.3 mL/g.
[0074] The mesoporous volume of the catalyst is generally at least 0.10 mL/g, preferably at least 0.20 mL/g, preferably between 0.25 mL/g and 0.80 mL/g, more preferably between 0.30 and 0.65 mL/g.
[0075] The median mesoporous diameter is advantageously between 3 nm and 25 nm, and preferably between 6 and 20 nm, and particularly preferably between 8 and 18 nm.
[0076] The catalyst advantageously has a median macroporous diameter of between 50 and 1500 nm, preferably between 80 and 1000 nm, even more preferably between 250 and 800 nm.
[0077] Preferably, the catalyst has low microporosity, very preferably it has no microporosity.
[0078] Support
[0079] According to the invention, the support is an alumina, that is to say that the support comprises at least 95%, preferably at least 98%, and in a particularly preferred manner at least 99% by weight of alumina relative to the weight of the medium. Alumina generally has a crystallographic structure of the delta, gamma or theta alumina type, alone or in a mixture.
[0080] According to the invention, the alumina support may comprise impurities such as metal oxides of groups IIA, IIIB, IVB, IIB, IIIA, IVA according to the CAS classification, preferably silica, titanium dioxide, zirconium dioxide, zinc oxide, magnesium oxide and calcium oxide, or alternatively alkali metals, preferably lithium, sodium or potassium, and/or alkaline earth metals, preferably magnesium, calcium, strontium or barium or sulfur.
[0081] The specific surface of the support is generally greater than or equal to 30 m ² /g, preferably greater than or equal to 50 m ² /g, more preferentially comprised between 60 m ² /g and 500 m ² /g, and even more preferentially comprised between 70 m ² /g and 400 m ² /g. The BET specific surface is measured by nitrogen physisorption.
[0082] The total pore volume of the support is generally between 0.1 and 1.5 cm ³ /g, preferably between 0.35 and 1.2 cm ³ /g, and even more preferably between 0.4 and 1, 0 cm ³ /g, and even more preferably between 0.45 and 0.9 cm ³ /g.
[0083] Catalyst Preparation Process
[0084] The subject of the present invention is a process for preparing a catalyst according to the invention, which process comprises the following steps:
[0085] a) the alumina support is brought into contact with at least one solution containing at least one nickel precursor;
[0086] b) the alumina support is brought into contact with at least one solution containing at least one nickel precursor and at least one copper precursor;
[0087] c) the alumina support is brought into contact with at least one solution containing at least one organic compound comprising at least one carboxylic acid function, or at least one alcohol function, or at least one ester function, or at least one amide function , or at least one amine function,
[0088] Being heard that :
[0089] - steps a), b) and c) are carried out separately, in any order, or
[0090] - steps a) and c) are carried out simultaneously, step b) being carried out either before the combination of steps a) and c), or after;
[0091] - steps b) and c) are carried out simultaneously, step a) being carried out either before the combination of steps b) and c), or after;
[0092] d) at least one step of drying the catalyst precursor obtained at the end of steps a) to c) is carried out at a temperature below 250°C.
[0093] e) a step of reducing the catalyst precursor obtained at the end of step d) is carried out by bringing said precursor into contact with a reducing gas at a temperature greater than or equal to 150° C. and less than 250° C.
[0094] The steps of the catalyst preparation process are explained in detail below.
[0095] Step a) Bringing the support into contact with a nickel precursor
[0096] The deposition of nickel on said support, in accordance with the implementation of step a), can be carried out by impregnation, dry or in excess, or by deposition - precipitation, according to methods well known to those skilled in the art. job.
[0097] Said step a) is preferably carried out by impregnating the support, consisting for example of bringing said support into contact with at least one aqueous or organic solution (for example methanol or ethanol or phenol or acetone or toluene or dimethyl sulfoxide (DMSO)) or consisting of a mixture of water and at least one organic solvent, containing at least one nickel precursor at least partially in the dissolved state, or even by bringing said support into contact with at least one colloidal solution of at least one precursor of nickel, in oxidized form (nickel oxide, oxy(hydroxide) or hydroxide nanoparticles) or in reduced form (metal nanoparticles of nickel in the reduced). Preferably, the solution is aqueous. The pH of this solution may be modified by the possible addition of an acid or a base. According to another preferred variant, the aqueous solution may contain aqueous ammonia or NH ₄ ⁺ ammonium ions.
[0098] Preferably, said step a) is carried out by dry impregnation, which consists in bringing the catalyst support into contact with a solution, containing at least one nickel precursor, the volume of the solution of which is between 0.25 and 1.5 times the porous volume of the support to be impregnated.
[0099] When the nickel precursor is introduced in aqueous solution, a nickel precursor is advantageously used in the form of nitrate, carbonate, acetate, chloride, hydroxide, hydroxycarbonate, oxalate, sulphate, formate , complexes formed by a polyacid or an acid-alcohol and its salts, complexes formed with acetylacetonates, tetrammine or hexammine complexes, or any other inorganic derivative soluble in aqueous solution, which is brought into contact with said support.
[0100] Preferably, the nickel precursor used is advantageously nickel nitrate, nickel hydroxide, nickel carbonate, nickel chloride, or nickel hydroxycarbonate. Very preferably, the nickel precursor is nickel nitrate, nickel carbonate or nickel hydroxide.
[0101] The quantities of the nickel precursor(s) introduced into the solution are chosen such that the total nickel content is between 1 and 50% by weight, preferably between 2 and 40% by weight, preferably between 3 and 35 % weight of said element relative to the total weight of the catalyst, and even more preferably between 5 and 25% by weight. In the embodiment in which step a) is carried out by impregnation, dry or in excess, preferably dry, the impregnation of the nickel with the support can advantageously be carried out via at least two cycles of impregnation, in using identical or different nickel precursors in each cycle. In this case, each impregnation is advantageously followed by drying and possibly by heat treatment.
[0102] Step b) Bringing the support into contact with a copper precursor and a nickel precursor
[0103] The deposition of nickel and copper on the alumina support can be carried out by impregnation, dry or in excess, or by deposition-precipitation, according to methods well known to those skilled in the art.
[0104] Said step b) is preferably carried out by impregnation of the catalyst precursor consisting for example of bringing said support into contact with at least one aqueous or organic solution (for example methanol or ethanol or phenol or acetone or toluene or dimethyl sulfoxide (DMSO)) or consisting of a mixture of water and at least one organic solvent, comprising, preferably consisting of, at least one nickel precursor and at least one copper precursor at least partially in the dissolved state, or even by bringing said catalyst precursor into contact with at least one colloidal solution comprising, preferably consisting of, at least one nickel precursor and one copper precursor in oxidized form (nanoparticles oxide, oxy(hydroxide) or hydroxide of nickel and copper) or in reduced form (metallic nanoparticles of nickel and copper in the reduced state). Preferably, the solution is aqueous. The pH of this solution can be modified by the possible addition of an acid or a base.
[0105] Preferably, said step b) is carried out by dry impregnation, which consists in bringing the support of the catalyst precursor into contact with a solution, comprising, preferably consisting of, at least one precursor of nickel and at least one precursor of copper, the volume of the solution of which is between 0.25 and 1.5 times the porous volume of the support to be impregnated.
[0106] When the nickel precursor is introduced in aqueous solution, a nickel precursor is advantageously used in the form of nitrate, carbonate, acetate, chloride, hydroxide, hydroxycarbonate, oxalate, sulphate, formate , of complexes formed by a polyacid or an acid-alcohol and its salts, of complexes formed with acetylacetonates, of tetrammine or hexammine complexes, or of any other inorganic derivative which is soluble in aqueous solution, which is brought into contact with the said precursor of catalyst. Preferably, the nickel precursor used is advantageously nickel nitrate, nickel hydroxide, nickel carbonate, nickel chloride, or nickel hydroxycarbonate. Very preferably, the nickel precursor is nickel nitrate, nickel carbonate or nickel hydroxide.
[0107] When the copper precursor is introduced in aqueous solution, a copper precursor in mineral or organic form is advantageously used. In mineral form, the copper precursor can be chosen from copper acetate, copper acetylacetonate, copper nitrate, copper sulphate, copper chloride, copper bromide, copper iodide or copper fluoride. Very preferably, the copper precursor salt is copper nitrate.
[0108] According to the invention, the nickel precursor is supplied to stage b) at a desired concentration to obtain on the final catalyst (ie obtained at the end of stage e) of reduction or of stage f) of passivation if the latter is carried out) a content of between 0.5 and 10% by weight of nickel element relative to the total weight of the final catalyst, preferably between 0.5 and 8% by weight, more preferably between 1 and 7% by weight, even more preferably between 1 and 5% by weight.
[0109] The quantities of the copper precursor(s) introduced into the solution according to step b) are chosen such that the total copper content is between 0.5 and 15% by weight of copper element relative to the total weight of the catalyst. (ie obtained at the end of step e) reduction or step f) passivation if the latter is carried out), preferably between 0.5 and 12% by weight, preferably between 0 75 and 10% by weight, and even more preferably between 1 and 9% by weight.
[0110] Step c) Bringing the support into contact with an organic compound
[0111] Bringing said support into contact with at least one solution containing at least one organic compound comprising at least one carboxylic acid function, or at least one alcohol function, or at least one ester function, or at least one amide function, or at least one amine function in accordance with the implementation of said step c), can be carried out by any method well known to those skilled in the art. Indeed, it has also been observed that the catalysts according to the invention prepared in the presence of an organic compound (cited below) are more active than the catalysts prepared in the absence of this type of organic compound. This effect is linked to the decrease in the size of the nickel particles.
[0112] In particular, said step c) can be carried out by impregnation, dry or in excess according to methods well known to those skilled in the art. Preferably, said step c) is carried out by dry impregnation, which consists in bringing the catalyst support into contact with a volume of said solution of between 0.25 and 1.5 times the pore volume of the support to be impregnated.
[0113] Said solution containing at least one organic compound comprising at least one carboxylic acid function, or at least one alcohol function, or at least one ester function, or at least one amide function or at least one amine function, can be aqueous or organic (for example methanol or ethanol or phenol or acetone or toluene or dimethyl sulfoxide (DMSO)) or consisting of a mixture of water and at least one organic solvent. Said organic compound is previously at least partially dissolved in said solution at the desired concentration. Preferably, said solution is aqueous or contains ethanol. Even more preferably, said solution is aqueous. The pH of said solution may be modified by the possible addition of an acid or a base. In another possible embodiment, the solvent may be absent from the impregnation solution.
[0114] In the embodiment in which step c) is carried out by impregnation, dry or in excess, preferably dry, the impregnation of the support with at least one solution containing at least said organic compound can be advantageously carried out via at least at least two impregnation cycles, using identical or different organic compounds for each cycle. In this case, each impregnation is advantageously followed by drying and possibly by heat treatment.
[0115] Advantageously, the molar ratio between said organic compound introduced in step c) and the nickel element also introduced in step a) is between 0.01 and 5.0 mol/mol, preferably between 0.05 and 2.0 mol/mol, more preferably between 0.1 and 1.5 mol/mol and even more preferably between 0.3 and 1.2 mol/mol.
[0116] The organic compound according to step c) can comprise within the same molecule several organic carboxylic acid functions, alcohol esters, amides or amines, which are identical or different. The organic compound according to step c) may comprise a combination of several organic functions chosen from the organic functions of carboxylic acids, alcohol esters, amides or amines.
[0117] A) Organic compound comprising at least one carboxylic acid function
[0118] In one embodiment according to the invention, the organic compound comprises at least one carboxylic acid function.
[0119] Said organic compound comprising at least one carboxylic acid function can be an aliphatic, saturated or unsaturated organic compound, or an aromatic organic compound. Preferably, the aliphatic organic compound, saturated or unsaturated, comprises between 1 and 9 carbon atoms, preferably between 2 and 7 carbon atoms. Preferably, the aromatic organic compound comprises between 7 and 10 carbon atoms, preferably between 7 and 9 carbon atoms.
[0120] Said aliphatic organic compound, saturated or unsaturated, or said aromatic organic compound, comprising at least one carboxylic acid function can be chosen from monocarboxylic acids, dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids.
[0121] Advantageously, the organic compound comprising at least one carboxylic acid function is chosen from ethanedioic acid (oxalic acid), propanedioic acid (malonic acid), pentanedioic acid (glutaric acid), hydroxyacetic acid (glycolic acid) , 2-hydroxypropanoic acid (lactic acid), 2-hydroxypropanedioic acid (tartronic acid), 2-hydroxypropane-1,2,3-tricarboxylic acid (citric acid), 2,3-dihydroxybutanedioic acid (tartaric acid), 2-oxopropanoic acid (pyruvic acid), 4-oxopentanoic acid (levulinic acid).
[0122] B) Organic compound comprising at least one alcohol function
[0123] In another embodiment according to the invention, the organic compound comprises at least one alcohol function.
[0124] Preferably, said organic compound comprises between 2 and 20 carbon atoms, preferably between 2 and 12 carbon atoms, and even more preferably between 2 and 8 carbon atoms.
[0125] Advantageously, the organic compound is chosen from methanol, ethanol, phenol, ethylene glycol, propane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, glycerol, xylitol, mannitol, sorbitol, pyrocatechol, resorcinol, hydroquinol, diethylene glycol, triethylene glycol, polyethylene glycols having an average molar mass lower than 600 g/mol, glucose, mannose, fructose, sucrose, maltose, lactose, in any of their isomeric forms.
[0126] C) Organic compound comprising at least one ester function
[0127] In another embodiment according to the invention, the organic compound comprises at least one ester function. Preferably, said organic compound comprises between 2 and 20 carbon atoms, preferably between 3 and 14 carbon atoms, and even more preferably between 3 and 8 carbon atoms.
[0128] Said organic compound can be chosen from a linear or cyclic or unsaturated cyclic carboxylic acid ester, or a cyclic or linear carbonic acid ester or even a linear carbonic acid diester. In the case of a cyclic carboxylic acid ester, said compound is g-valerolactone.
[0129] In the case of an unsaturated cyclic ester (containing unsaturations in the cycle) of carboxylic acid, the compound can be furan or pyrone or any of their derivatives, such as 6-pentyl-α-pyrone .
[0130] In the case of a linear carboxylic acid ester, the compound may be a compound comprising a single ester function corresponding to the structural formula RCOOR', in which R and R' are alkyl groups, linear, branched, or cyclic, or alkyl groups containing unsaturations, or alkyl groups substituted by one or more aromatic rings, or aryl groups, each containing between 1 and 15 carbon atoms, and which may be identical or different. The group R can also be the hydrogen atom H. Said organic compound is preferably methyl laurate.
[0131] In another embodiment according to the invention, the organic compound may be a compound comprising at least two carboxylic acid ester functions. Preferably, said compound is dimethyl succinate.
[0132] In another embodiment according to the invention, the organic compound may be a compound comprising at least one carboxylic acid ester function and at least one second functional group chosen from alcohols, ethers, ketones, aldehydes.
[0133] Preferably, said compound is dimethyl malate.
[0134] Advantageously, said organic compound comprises at least one carboxylic acid ester function and at least one ketone or aldehyde function. In the case of a cyclic ester of carbonic acid, the compound is propylene carbonate. In the case of a linear carbonic acid ester, the compound is chosen from dimethyl carbonate, diethyl carbonate or diphenyl carbonate. In the case of a linear carbonic acid diester, the compound is chosen from dimethyl dicarbonate, diethyl dicarbonate, di-tert-butyl dicarbonate.
[0135] D) Organic compound comprising at least one amide function
[0136] In another embodiment according to the invention, the organic compound comprises at least one amide function, chosen from an acyclic amide function or a cyclic amide function, optionally comprising alkyl or aryl or alkyl substituents containing unsaturations. The amide functions can be chosen from primary, secondary or tertiary amides.
[0137] Advantageously, the organic compound comprising at least one amide function is chosen from formamide, N-methylformamide, N,N-dimethylformamide, N-ethylformamide , N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylmethanamide, N,N-diethylacetamide, N,N-dimethylpropionamide, propanamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, γ-lactam, caprolactam, acetylleucine, N-acetylaspartic acid, aminohippuric acid, N-acetylglutamic acid, 4-acetamidobenzoic acid, lactamide and glycolamide, urea, N-methylurea, N,N′-dimethylurea, 1,1-dimethylurea, tetramethylurea in any of their isomeric forms.
[0138] E) Organic compound comprising at least one amine function
[0139] In another embodiment according to the invention, the organic compound comprises at least one amine function. Said organic compound comprises between 1 and 20 carbon atoms, preferably between 1 and 14 carbon atoms, and even more preferably between 2 and 8 carbon atoms.
[0140] In one embodiment according to the invention, said organic compound comprising at least one amine function corresponding to the formula C _x N _y H _z in which 1 ≤ x ≤ 20, 1 ≤ y ≤ x, 2 ≤ z ≤ 2x+ 2. More particularly, the organic compound is chosen from ethylenediamine, diaminohexane, tetramethylenediamine, hexamethylenediamine, tetramethylethylenediamine, tetraethylethylenediamine, diethylenetriamine, triethylenetetramine.
[0141] In one embodiment according to the invention, said organic compound comprises at least one amine function and at least one carboxylic acid (amino acid) function. When the compound is an amino acid, it is preferably chosen from alanine, arginine, lysine, proline, serine, threonine, EDTA.
[0142] Among all the embodiments above, the organic compound is chosen from oxalic acid, malonic acid, glycolic acid, lactic acid, tartronic acid, citric acid, tartaric acid, pyruvic acid, levulinic acid, ethylene glycol, propane-1,3-diol, butane-1,4-diol, glycerol, xylitol, mannitol, sorbitol, diethylene glycol , glucose, gamma valerolactone, dimethyl carbonate, diethyl carbonate, formamide, N-methylformamide, acetamide, N-methylacetamide, N,N-dimethylmethanamide, 2-pyrrolidone, γ- lactam, lactam, urea, alanine, arginine, lysine, proline, serine, EDTA.
[0143] Implementation of steps a), b) and c)
[0144] According to the invention:
[0145] - steps a), b) and c) are carried out separately, in any order, or
[0146] - steps a) and c) are carried out simultaneously, step b) being carried out either before the combination of steps a) and c), or after;
[0147] - steps b) and c) are carried out simultaneously, step a) being carried out either before the combination of steps b) and c), or after.
[0148] In a preferred embodiment, step a) is carried out before simultaneously carrying out steps b) and c).
[0149] In another preferred embodiment, steps a) and c) are carried out simultaneously, then step b) is carried out.
[0150] Step d) Drying of the impregnated support
[0151] Step d) of drying the impregnated support is carried out at a temperature below 250° C., preferably between 15 and 180° C., more preferably between 30 and 160° C., even more preferably between 50 and 150° C., and even more preferably between 70 and 140° C., typically for a period of between 10 minutes and 24 hours. Longer durations are not excluded, but do not necessarily bring improvement.
[0152] The drying step can be carried out by any technique known to those skilled in the art. It is advantageously carried out under an inert atmosphere or under an atmosphere containing oxygen or under a mixture of inert gas and oxygen. It is advantageously carried out at atmospheric pressure or at reduced pressure. Preferably, this step is carried out at atmospheric pressure and in the presence of air or nitrogen.
[0153] Heat treatment of the dried catalyst (optional step)
[0154] The dried catalyst precursor may undergo an additional heat treatment step, before step e) of reduction, at a temperature of between 250 and 1000° C. and preferably between 250 and 750° C., typically for a period of between 15 minutes and 10 hours, under an inert atmosphere or under an atmosphere containing oxygen, in the presence of water or not. Longer treatment times are not excluded, but do not bring necessary improvement.
[0155] The term “heat treatment” is understood to mean the temperature treatment respectively without the presence or in the presence of water. In the latter case, contact with water vapor can take place at atmospheric pressure or at autogenous pressure. Several combined cycles without the presence or with the presence of water can be carried out. After this or these treatment(s), the catalyst precursor comprises nickel in oxide form, that is to say in NiO form.
[0156] In the event of the presence of water, the water content is preferably between 150 and 900 grams per kilogram of dry air, and even more preferably between 250 and 650 grams per kilogram of dry air.
[0157] Step e) Reduction with a reducing gas
[0158] Prior to the use of the catalyst in the catalytic reactor and the implementation of a hydrogenation process, a reducing treatment step e) is carried out in the presence of a reducing gas so as to obtain a catalyst comprising nickel in least partially in metallic form. This step is advantageously carried out in situ , that is to say after loading the catalyst into a reactor for the hydrogenation of aromatic or polyaromatic compounds. This treatment makes it possible to activate said catalyst and to form metallic particles, in particular nickel in the zero valent state. Performing the catalyst reduction treatment in situ makes it possible to dispense with an additional step of passivation of the catalyst by an oxygenated compound or by CO ₂ , which is necessarily the case when the catalyst is prepared by carrying out a reduction treatment. ex-situ, that is to say outside the reactor used for the hydrogenation of aromatic or polyaromatic compounds. Indeed, when the reducing treatment is carried out ex-situ, it is necessary to carry out a passivation step in order to preserve the metallic phase of the catalyst in the presence of air (during transport and loading operations of the catalyst in the reactor of hydrogenation), then to carry out a new step of reduction of the catalyst.
[0159] The reducing gas is preferably hydrogen. The hydrogen can be used pure or in a mixture (for example a hydrogen/nitrogen, hydrogen/argon, hydrogen/methane mixture). In the case where the hydrogen is used as a mixture, all the proportions are possible.
[0160] According to an essential aspect of the preparation process according to the invention, said reducing treatment is carried out at a temperature greater than or equal to 150° C. and less than 250° C., preferably between 160 and 230° C., and more preferably between 170 and 220°C. The duration of the reducing treatment is between 5 minutes and less than 5 hours, preferably between 10 minutes and 4 hours, and even more preferably between 10 minutes and 110 minutes.
[0161] The presence of the nickel-copper alloy at least partially in reduced form makes it possible to use less severe operating conditions for reducing the active phase of nickel than in the prior art and thus makes it possible to directly carry out the reduction step within the reactor in which it is desired to carry out the hydrogenation of aromatic or polyaromatic compounds.
[0162] Furthermore, the presence of copper in the catalyst makes it possible to maintain good activity of the catalyst and good life of the catalyst when the latter is brought into contact with a hydrocarbon feedstock comprising sulfur. Indeed, compared to nickel, the copper present in the catalyst more easily captures the sulfur compounds included in the charge, which limits the irreversible poisoning of the active sites. The rise in temperature up to the desired reduction temperature is generally slow, for example fixed between 0.1 and 10° C./min, preferably between 0.3 and 7° C./min.
[0163] The hydrogen flow, expressed in L/hour/gram of catalyst precursor is between 0.01 and 100 L/hour/gram of catalyst, preferably between 0.05 and 10 L/hour/gram of catalyst precursor , even more preferably between 0.1 and 5 L/hour/gram of catalyst precursor.
[0164] Step f) Passivation (optional)
[0165] The catalyst prepared according to the process according to the invention can undergo a step of passivation by a sulfur compound which makes it possible to improve the selectivity of the catalysts and to avoid thermal runaways during the start-up of new catalysts ("run away" according to the terminology Anglo-Saxon). Passivation generally consists in irreversibly poisoning with the sulfur compound the most virulent active sites of nickel which exist on the new catalyst and therefore in attenuating the activity of the catalyst in favor of its selectivity. The passivation step is carried out by implementing methods known to those skilled in the art.
[0166] The passivation step with a sulfur compound is generally carried out at a temperature of between 20 and 350° C., preferably between 40 and 200° C., for 10 to 240 minutes. The sulfur compound is for example chosen from the following compounds: thiophene, thiophane, alkylmonosulfides such as dimethylsulfide, diethylsulfide, dipropylsulfide and propylmethylsulfide or else an organic disulfide of formula HO-R ₁ -SSR ₂ -OH such as di-thio-di -ethanol of formula HO-C ₂ H ₄ -SSC ₂ H ₄ -OH (often called DEODS). The sulfur content is generally between 0.1 and 2% by weight of said element relative to the total weight of the catalyst.
[0167] In one embodiment according to the invention, the preparation of the catalyst is carried out ex-situ, that is to say before loading the catalyst into the reaction unit of the selective hydrogenation or aromatics hydrogenation process.
[0168] Selective hydrogenation process
[0169] The catalyst obtained according to the process according to the invention can be used in a process for the selective hydrogenation of polyunsaturated compounds containing at least 2 carbon atoms per molecule, such as diolefins and/or acetylenics and/or alkenylaromatics, also called styrenics, contained in a charge of hydrocarbons having a final boiling point less than or equal to 300°C. The process can be carried out at a temperature of between 0 and 300°C, at a pressure of between 0.1 and 10 MPa, at a hydrogen/(polyunsaturated compounds to be hydrogenated) molar ratio of between 0.1 and 10 and at a hourly volume rate between 0.1 and 200 h ^-1 when the process is carried out in the liquid phase, or at a hydrogen/(polyunsaturated compounds to be hydrogenated) molar ratio between 0.5 and 1000 and at an hourly volume rate between 100 and 40,000 h ⁻¹ when the process is carried out in the gas phase, in the presence of the catalyst obtained by the preparation process as described above in the description.
[0170] Monounsaturated organic compounds such as ethylene and propylene, for example, are the source of the manufacture of polymers, plastics and other value-added chemicals. These compounds are obtained from natural gas, naphtha or gas oil which have been treated by steam cracking or catalytic cracking processes. These processes are operated at high temperature and produce, in addition to the desired monounsaturated compounds, polyunsaturated organic compounds such as acetylene, propadiene and methylacetylene (or propyne), 1-2-butadiene and 1-3 -butadiene, vinylacetylene and ethylacetylene, and other polyunsaturated compounds whose boiling point corresponds to the C5+ cut (hydrocarbon compounds having at least 5 carbon atoms), in particular diolefinic or styrenic or indenic compounds. These polyunsaturated compounds are very reactive and lead to side reactions in the polymerization units. It is therefore necessary to eliminate them before recovering these cuts.
[0171] Selective hydrogenation is the main treatment developed to specifically remove unwanted polyunsaturated compounds from these hydrocarbon feedstocks. It allows the conversion of polyunsaturated compounds to the corresponding alkenes or aromatics while avoiding their total saturation and therefore the formation of the corresponding alkanes or naphthenes. In the case of steam cracked gasolines used as feed, selective hydrogenation also makes it possible to selectively hydrogenate alkenylaromatics into aromatics by avoiding the hydrogenation of aromatic rings.
[0172] The hydrocarbon feed treated in the selective hydrogenation process has a final boiling point less than or equal to 300°C and contains at least 2 carbon atoms per molecule and includes at least one polyunsaturated compound. The term “polyunsaturated compounds” means compounds comprising at least one acetylenic function and/or at least one diene function and/or at least one alkenylaromatic function.
[0173] More particularly, the feedstock is selected from the group consisting of a C2 steam cracking cut, a C2-C3 steam cracking cut, a C3 steam cracking cut, a C4 steam cracking cut, a C5 steam cracking cut and a steam cracking gasoline also called pyrolysis gasoline or C5+ cut.
[0174] The C2 cut from steam cracking, advantageously used for the implementation of the selective hydrogenation process, has for example the following composition: between 40 and 95% by weight of ethylene, of the order of 0.1 to 5% by weight of acetylene, the remainder being essentially ethane and methane. In certain C2 cuts from steam cracking, between 0.1 and 1% by weight of C3 compounds may also be present.
[0175] The C3 steam cracking cut, advantageously used for the implementation of the selective hydrogenation process, has for example the following average composition: of the order of 90% by weight of propylene, of the order of 1 to 8% by weight of propadiene and methylacetylene, the remainder being essentially propane. In some C3 cuts, between 0.1 and 2% by weight of C2 compounds and C4 compounds may also be present.
[0176] A C2-C3 cut can also be advantageously used for carrying out the selective hydrogenation process. It has for example the following composition: of the order of 0.1 to 5% by weight of acetylene, of the order of 0.1 to 3% by weight of propadiene and methylacetylene, of the order of 30% by weight of ethylene, of the order of 5% by weight of propylene, the remainder being essentially methane, ethane and propane. This filler may also contain between 0.1 and 2% by weight of C4 compounds.
[0177] The C4 steam cracking cut, advantageously used for the implementation of the selective hydrogenation process, has for example the following average mass composition: 1% weight of butane, 46.5% weight of butene, 51% weight of butadiene, 1 3% by weight of vinylacetylene and 0.2% by weight of butyne. In some C4 cuts, between 0.1 and 2% by weight of C3 compounds and C5 compounds may also be present.
[0178] The C5 cut from steam cracking, advantageously used for carrying out the selective hydrogenation process, has for example the following composition: 21% by weight of pentanes, 45% by weight of pentenes, 34% by weight of pentadienes.
[0179] The steam cracking gasoline or pyrolysis gasoline, advantageously used for the implementation of the selective hydrogenation process, corresponds to a hydrocarbon cut whose boiling point is generally between 0 and 300° C., preferably between 10 and 250°C. The polyunsaturated hydrocarbons to be hydrogenated present in said steam cracked gasoline are in particular diolefinic compounds (butadiene, isoprene, cyclopentadiene, etc.), styrenic compounds (styrene, alpha-methylstyrene, etc.) and indene compounds (indene, etc.). ). Steam cracked gasoline generally comprises the C5-C12 cut with traces of C3, C4, C13, C14, C15 (for example between 0.1 and 3% by weight for each of these cuts). For example, a charge formed from pyrolysis gasoline generally has the following composition: 5 to 30% by weight of saturated compounds (paraffins and naphthenes), 40 to 80% by weight of aromatic compounds, 5 to 20% by weight of mono-olefins, 5 to 40% by weight of diolefins, 1 to 20% by weight of alkenylaromatic compounds, all the compounds forming 100%. It also contains from 0 to 1000 ppm by weight of sulphur, preferably from 0 to 500 ppm by weight of sulphur.
[0180] Preferably, the charge of polyunsaturated hydrocarbons treated in accordance with the selective hydrogenation process is a C2 cut from steam cracking, or a C2-C3 cut from steam cracking, or a gasoline from steam cracking.
[0181] The selective hydrogenation process aims to eliminate said polyunsaturated hydrocarbons present in said charge to be hydrogenated without hydrogenating the monounsaturated hydrocarbons. For example, when said feed is a C2 cut, the selective hydrogenation process aims to selectively hydrogenate acetylene. When said feed is a C3 cut, the selective hydrogenation process aims to selectively hydrogenate propadiene and methylacetylene. In the case of a C4 cut, the aim is to eliminate the butadiene, vinylacetylene (VAC) and the butyne, in the case of a C5 cut, the aim is to eliminate the pentadienes. When said feedstock is a steam cracked gasoline, the selective hydrogenation process aims to selectively hydrogenate said polyunsaturated hydrocarbons present in said feedstock to be treated so that the diolefinic compounds are partially hydrogenated to mono-olefins and the styrenic and indenic compounds are partially hydrogenated to the corresponding aromatic compounds avoiding the hydrogenation of the aromatic rings.
[0182] The technological implementation of the selective hydrogenation process is for example carried out by injection, in ascending or descending current, of the charge of polyunsaturated hydrocarbons and hydrogen into at least one fixed-bed reactor. Said reactor can be of the isothermal type or of the adiabatic type. An adiabatic reactor is preferred. The charge of polyunsaturated hydrocarbons can advantageously be diluted by one or more re-injection(s) of the effluent, from said reactor where the selective hydrogenation reaction takes place, at various points of the reactor, located between the inlet and the outlet of the reactor in order to limit the temperature gradient in the reactor. The technological implementation of the selective hydrogenation process can also be advantageously carried out by the implantation of at least said supported catalyst in a reactive distillation column or in reactors-exchangers or in a slurry type reactor. The hydrogen flow can be introduced at the same time as the charge to be hydrogenated and/or at one or more different points of the reactor.
[0183] The selective hydrogenation of the C2, C2-C3, C3, C4, C5 and C5+ cuts from steam cracking can be carried out in the gaseous phase or in the liquid phase, preferably in the liquid phase for the C3, C4, C5 and C5+ cuts and in the carbonated for C2 and C2-C3 cuts. A reaction in the liquid phase makes it possible to lower the energy cost and to increase the cycle time of the catalyst.
[0184] In general, the selective hydrogenation of a hydrocarbon charge containing polyunsaturated compounds containing at least 2 carbon atoms per molecule and having a final boiling point less than or equal to 300°C is carried out at a temperature between 0 and 300°C, at a pressure between 0.1 and 10 MPa, at a hydrogen/(polyunsaturated compounds to be hydrogenated) molar ratio between 0.1 and 10 and at an hourly volumetric speed VVH (defined as the ratio of the volume flow rate of charge to the volume of the catalyst) of between 0.1 and 200 h ^-1 for a process carried out in the liquid phase, or at a molar hydrogen/(polyunsaturated compounds to be hydrogenated) ratio of between 0.5 and 1000 and at an hourly volumetric speed VVH of between 100 and 40,000 h ^-1 for a process carried out in the gaseous phase.
[0185] In one embodiment, when a selective hydrogenation process is carried out in which the feedstock is a steam cracked gasoline comprising polyunsaturated compounds, the molar ratio (hydrogen)/(polyunsaturated compounds to be hydrogenated) is generally between 0.5 and 10, preferably between 0.7 and 5.0 and even more preferably between 1.0 and 2.0, the temperature is between 0 and 200° C., preferably between 20 and 200 C and even more more preferably between 30 and 180° C., the hourly volume velocity (VVH) is generally between 0.5 and 100 h ^-1 , preferably between 1 and 50 h ^-1 and the pressure is generally between 0.3 and 8 .0 MPa, preferably between 1.0 and 7.0 MPa and even more preferably between 1.5 and 4.0 MPa.
[0186] More preferably, a selective hydrogenation process is carried out in which the feedstock is a steam cracked gasoline comprising polyunsaturated compounds, the hydrogen/(polyunsaturated compounds to be hydrogenated) molar ratio is between 0.7 and 5.0, the temperature is between 20 and 200° C., the hourly volume velocity (VVH) is generally between 1 and 50 h ^-1 and the pressure is between 1.0 and 7.0 MPa.
[0187] Even more preferably, a selective hydrogenation process is carried out in which the feedstock is a steam cracked gasoline comprising polyunsaturated compounds, the hydrogen/(polyunsaturated compounds to be hydrogenated) molar ratio is between 1.0 and 2.0, the temperature is between 30 and 180° C., the hourly volume velocity (VVH) is generally between 1 and 50 h ^-1 and the pressure is between 1.5 and 4.0 MPa.
[0188] The hydrogen flow is adjusted in order to have a sufficient quantity of it to theoretically hydrogenate all the polyunsaturated compounds and to maintain an excess of hydrogen at the reactor outlet.
[0189] In another embodiment, when a selective hydrogenation process is carried out in which the feed is a C2 cut from steam cracking and/or a C2-C3 cut from steam cracking comprising polyunsaturated compounds, the molar ratio (hydrogen)/( polyunsaturated compounds to be hydrogenated) is generally between 0.5 and 1000, preferably between 0.7 and 800, the temperature is between 0 and 300°C, preferably between 15 and 280°C, the hourly volume velocity (VVH ) is generally between 100 and 40,000 h ^-1 , preferably between 500 and 30,000 h ^-1 and the pressure is generally between 0.1 and 6.0 MPa, preferably between 0.2 and 5.0 MPa.
[0190] Aromatics hydrogenation process
[0191] The catalyst obtained according to the process according to the invention can be used in a process for the hydrogenation of at least one aromatic or polyaromatic compound contained in a charge of hydrocarbons having a final boiling point less than or equal to 650° C., generally between 20 and 650°C, and preferably between 20 and 450°C. Said hydrocarbon charge containing at least one aromatic or polyaromatic compound can be chosen from the following petroleum or petrochemical cuts: reformate from catalytic reforming, kerosene, light gas oil, heavy gas oil, cracking distillates, such as FCC recycle oil, coker diesel, hydrocracking distillates.
[0192] The content of aromatic or polyaromatic compounds contained in the hydrocarbon charge treated in the hydrogenation process is generally between 0.1 and 80% by weight, preferably between 1 and 50% by weight, and particularly preferably between 2 and 35% by weight, the percentage being based on the total weight of the hydrocarbon charge. The aromatic compounds present in said hydrocarbon charge are, for example, benzene or alkylaromatics such as toluene, ethylbenzene, o-xylene, m-xylene, or p-xylene, or alternatively aromatics having several aromatic (polyaromatic) rings such as naphthalene.
[0193] The sulfur or chlorine content of the charge is generally less than 5000 ppm by weight of sulfur or chlorine, preferably less than 100 ppm by weight, and in a particularly preferred manner less than 10 ppm by weight.
[0194] The technological implementation of the process for the hydrogenation of aromatic or polyaromatic compounds is for example carried out by injection, in ascending or descending current, of the hydrocarbon charge and hydrogen into at least one fixed-bed reactor. Said reactor can be of the isothermal type or of the adiabatic type. An adiabatic reactor is preferred. The hydrocarbon charge can advantageously be diluted by one or more re-injection(s) of the effluent, from said reactor where the hydrogenation reaction of the aromatics takes place, at various points of the reactor, located between the inlet and the outlet of the reactor in order to limit the temperature gradient in the reactor. The technological implementation of the aromatics hydrogenation process can also be advantageously carried out by the implantation of at least said supported catalyst in a reactive distillation column or in reactor-exchangers or in a slurry-type reactor. The hydrogen flow can be introduced at the same time as the charge to be hydrogenated and/or at one or more different points of the reactor.
[0195] The hydrogenation of the aromatic or polyaromatic compounds can be carried out in the gas phase or in the liquid phase, preferably in the liquid phase. In general, the hydrogenation of aromatic or polyaromatic compounds is carried out at a temperature between 30 and 350° C., preferably between 50 and 325° C., at a pressure between 0.1 and 20 MPa, from preferably between 0.5 and 10 MPa, at a hydrogen/(aromatic compounds to be hydrogenated) molar ratio between 0.1 and 10 and at an hourly volumetric speed VVH of between 0.05 and 50 h ^-1 , preferably between 0, 1 and 10 h ^-1 of a hydrocarbon charge containing aromatic or polyaromatic compounds and having a final boiling point less than or equal to 650°C, generally between 20 and 650°C, and preferably between 20 and 450 °C.
[0196] The hydrogen flow is adjusted in order to have a sufficient quantity of it to theoretically hydrogenate all the aromatic compounds and to maintain an excess of hydrogen at the reactor outlet.
[0197] The conversion of the aromatic or polyaromatic compounds is generally greater than 20% by mole, preferably greater than 40% by mole, more preferably greater than 80% by mole, and in a particularly preferred manner greater than 90% by mole of the aromatic compounds or polyaromatics contained in the hydrocarbon charge. The conversion is calculated by dividing the difference between the total moles of the aromatic or polyaromatic compounds in the hydrocarbon feed and in the product by the total moles of the aromatic or polyaromatic compounds in the hydrocarbon feed.
[0198] According to a particular variant of the process, a process is carried out for the hydrogenation of benzene from a hydrocarbon charge, such as the reformate from a catalytic reforming unit. The benzene content in said hydrocarbon charge is generally between 0.1 and 40% by weight, preferably between 0.5 and 35% by weight, and particularly preferably between 2 and 30% by weight, the percentage by weight being based on the total weight of the hydrocarbon charge.
[0199] The sulfur or chlorine content of the charge is generally less than 10 ppm by weight of sulfur or chlorine respectively, and preferably less than 2 ppm by weight.
[0200] The hydrogenation of the benzene contained in the hydrocarbon charge can be carried out in the gaseous phase or in the liquid phase, preferably in the liquid phase. When it is carried out in the liquid phase, a solvent may be present, such as cyclohexane, heptane, octane. In general, the hydrogenation of benzene is carried out at a temperature of between 30 and 250° C., preferably between 50 and 200° C., and more preferably between 80 and 180° C., at a pressure of between 0.1 and 10 MPa, preferably between 0.5 and 4 MPa, at a hydrogen/(benzene) molar ratio between 0.1 and 10 and at an hourly volumetric speed VVH of between 0.05 and 50 h ^-1 , preferably between 0.5 and 10 h ^-1 .
[0201] The conversion of benzene is generally greater than 50 mol%, preferably greater than 80 mol%, more preferably greater than 90 mol% and particularly preferably greater than 98 mol%.
[0202] The invention will now be illustrated via the examples below which are in no way limiting.
[0203] Examples
[0204] For all the catalysts mentioned in the examples mentioned below, the support is an alumina A having a specific surface area of 80 m²/g, a pore volume of 0.7 mL/g and a median pore diameter of 12 nm.
[0205] Example 1: Preparation of an aqueous solution of Ni precursors
[0206] The aqueous solution of Ni precursors (solution S1) used for the preparation of catalyst A is prepared by dissolving 43.5 g of nickel nitrate (NiNO ₃ , supplier Strem Chemicals®) in a volume of 13 mL of distilled water. The solution S1 is obtained, the Ni concentration of which is 350 g of Ni per liter of solution.
[0207] Example 2: Preparation of an aqueous solution of Ni precursors with additives
[0208] The aqueous solution of Ni precursors (solution S2) used for the preparation of catalysts B to G is prepared by dissolving 43.5 g of nickel nitrate (NiNO ₃ , supplier Strem Chemicals®) and malonic acid (CAS 141 -82-2; Fluka® supplier) in a volume of 13 mL of distilled water. The additive/Ni molar ratio being 0.5. The solution S2 is obtained, the Ni concentration of which is 350 g of Ni per liter of solution.
[0209] Example 3: Preparation of an aqueous solution of the precursors of the NiCu alloy (5% Ni)
[0210] The aqueous solution of Ni precursors (solution S3) used for the preparation of catalysts C, D, E, and G is prepared by dissolving 14.5 g of nickel nitrate (NiNO ₃ , supplier Strem Chemicals®) in a volume of 13 mL of distilled water. A solution is obtained whose Ni concentration is 116.6 g of Ni per liter of solution. The copper nitrate precursor is then added in order to have in particular a Ni/Cu molar ratio of 1 (catalysts C to F) and 2 (catalyst G) according to the examples. We obtain the solution S3. It makes it possible to introduce the precursors of the NiCu alloy with a mass content of Ni relative to the final catalyst of approximately 5% by weight.
[0211] This solution is suitable for obtaining an alloy containing 2% by weight of Ni with respect to the final catalyst (catalyst F).
[0212] Example 4: Catalyst A (non-compliant)
[0213] The solution S prepared in Example 1 is dry impregnated with 10 g of alumina A. The solid thus obtained is then dried in an oven overnight at 120° C., then calcined under a flow of dry air of 1 L /h/g of catalyst at 450° C. for 2 hours. The calcined catalyst thus prepared contains 15% by weight of the element nickel relative to the total weight of the catalyst supported on alumina.
[0214] The dry air used in this example and all examples below contains less than 5 grams of water per kilogram of air.
[0215] The catalyst precursor is then reduced under the conditions as described in Example 11 below.
[0216] Example 5: Catalyst B (non-compliant)
[0217] The solution S2 prepared in Example 2 is dry impregnated with 10 g of alumina A. The solid thus obtained is then dried in an oven overnight at 120° C., then calcined under an air flow of 1 L/ h/g of catalyst at 450° C. for 2 hours. The calcined catalyst thus prepared contains 15% by weight of the element nickel relative to the total weight of the catalyst supported on alumina.
[0218] The catalyst precursor is then reduced under the conditions as described in Example 11 below.
[0219] Example 6: Catalyst C (non-compliant)
[0220] Solution S2 and solution S3 prepared in Examples 2 and 3 are co-impregnated with 10 g of alumina A. The solid thus obtained is then dried in an oven overnight at 120°C. The solid thus obtained is then dried in an oven overnight at 120°C, then calcined under an air flow of 1 L/h/g of catalyst at 450°C for 2 hours.
[0221] The catalyst precursor is then reduced under the conditions as described in Example 11 below.
[0222] Example 7: Catalyst D (compliant)
[0223] Solution S2 is impregnated dry on alumina A to obtain 15% of Ni alone relative to the total weight of the final catalyst. The solid thus obtained is then dried in an oven overnight at 120°C, then calcined under an air flow of 1 L/h/g of catalyst at 450°C for 2 hours. Then the solution S3 (with a target molar ratio Ni/Cu=3) is dry impregnated onto the catalyst precursor. The Ni content aimed at in this stage is 5% by weight of Ni relative to the weight of the final catalyst. The solid thus obtained is then dried in an oven overnight at 120°C, then calcined under an air flow of 1 L/h/g of catalyst at 450°C for 2 hours.
[0224] The catalyst precursor is then reduced under the conditions as described in Example 11 below.
[0225] Example 8: Catalyst E (compliant)
[0226] Solution S3 (with a targeted ratio Ni/Cu=3) is dry impregnated on alumina A. The Ni content targeted in this step is 5% by weight of Ni relative to the weight of the final catalyst. The solid thus obtained is then dried in an oven overnight at 120°C, then calcined under an air flow of 1 L/h/g of catalyst at 450°C for 2 hours. The solution S2 is then impregnated dry onto the catalyst precursor to obtain 15% of Ni alone relative to the total weight of the final catalyst. The solid thus obtained is then dried in an oven overnight at 120°C, then calcined under an air flow of 1 L/h/g of catalyst at 450°C for 2 hours.
[0227] The catalyst precursor is then reduced under the conditions as described in Example 11 below.
[0228] Example 9: Catalyst F (compliant)
[0229] Solution S2 is impregnated dry on alumina A to obtain 15% of Ni alone relative to the total weight of the final catalyst. The solid thus obtained is then dried in an oven overnight at 120°C, then calcined under an air flow of 1 L/h/g of catalyst at 450°C for 2 hours. The S3 solution prepared and adapted in example 3 is dry impregnated onto the catalyst precursor. The Ni content aimed at in this stage is 2% by weight of Ni relative to the weight of the final catalyst. The Ni/Cu ratio targeted is 3. The solid thus obtained is then dried in an oven overnight at 120°C, then calcined under an air flow of 1 L/h/g of catalyst at 450°C for 2 time.
[0230] The catalyst precursor is then reduced under the conditions as described in Example 11 below.
[0231] Example 10: Catalyst G (compliant)
[0232] Solution S2 is impregnated dry on alumina A to obtain 15% of Ni alone relative to the total weight of the final catalyst. The solid thus obtained is then dried in an oven overnight at 120°C, then calcined under an air flow of 1 L/h/g of catalyst at 450°C for 2 hours. The S3 solution prepared in example 3 is dry impregnated onto the catalyst precursor. The Ni content aimed at in this stage is 2% by weight of Ni relative to the weight of the final catalyst. The target Ni/Cu ratio is 1. The solid thus obtained is then dried in an oven overnight at 120°C, then calcined under an air flow of 1 L/h/g of catalyst at 450°C for 2 time.
[0233] The catalyst precursor is then reduced under the conditions as described in Example 11 below.
[0234] Example 11: Characterization
[0235] All the catalysts contain the contents targeted during impregnation, i.e. 15% of nickel element (characterized by X-ray fluorescence) relative to the total weight of the catalyst, and the % of added copper (characterized by X-ray fluorescence) .
[0236] The amount of alloy obtained after the calcination then reduction step was determined by X-ray diffraction (XRD) analysis on catalyst samples in powder form.
[0237] The amount of nickel in metallic form obtained after the reduction step was determined by X-ray diffraction (XRD) analysis on catalyst samples in powder form. Between the reduction stage and throughout the duration of characterization by XRD, the catalysts are never released into the open air. The diffraction diagrams are obtained by X-ray crystallographic analysis using a diffractometer using the conventional powder method with Kα1 radiation from copper (λ=1.5406 Å).
[0238] The reduction rate was calculated by calculating the area of the Ni ⁰ line located around 52°2θ, on all the diffractograms of each sample of catalyst analyzed, then by subtracting the signal present from room temperature under the line at 52° and which is due to the alumina.
[0239] Table 1 below summarizes the reduction rates or even the metallic nickel content Ni° (expressed in % by weight relative to the total weight of active nickel, ie the nickel which does not make up the alloy) for all the catalysts A to E characterized by XRD after a reduction step at 170° C. for 90 minutes under a flow of hydrogen. These values were also compared with the reduction rate obtained for catalyst A (Ni alone) after a conventional reduction step (i.e. at a temperature of 400°C for 15 hours under a flow of hydrogen) .
[0240] At room temperature on all catalysts, after calcination, containing copper and nickel, we detect alumina in delta and theta form, and large lines of NiO and CuO.
[0241] We also detect after reduction a line corresponding to the alloy in the form of Ni _0.76 Cu _0.24.
[0242] In order to evaluate the rate of reducibility and therefore the formation of Ni ⁰ , we measure the area of the Ni ⁰ line located around 52°2θ, on all the diffractograms, by subtracting the signal present from room temperature under the line at 52° and which is due to the alumina. It is thus possible to determine the relative percentage of Ni ⁰ crystallized after the reduction.
[0243] Table 1 below summarizes the reducibility rates or the Ni° content for all the catalysts characterized by XRD after reduction at 170°C for 90 minutes under a hydrogen flow. These values were also compared with the reduction rate obtained for catalyst A (Ni alone) after a conventional reduction step (i.e. at a temperature of 400°C for 15 hours under a flow of hydrogen) .
[0244] Catalyst Final reduction Ni content for the ^1st imp. (% wt) Ni content for the ^2nd imp. (% wt) Ni/Cu molar ratio Particle size (m) Percentage of Ni° alone (DRX) after reduction (%) A (comparative) 400°C, 3 p.m. 15 - - 14 80 A (comparative) 170°C, 90 mins 15 - - 14 0* B (comparative) 170°C, 90 mins 15 - - 2 0* C (comparative) 170°C, 90 mins A single impregnation S2+S3 3 10 0** D (invention) 170°C, 90 mins 15 5 3 2 90 E (invention) 170°C, 90 mins 5 15 3 2 95 F (invention) 170°C, 90 mins 15 2 3 2 90 G (invention) 170°C, 90 mins 15 5 1 2 95
[0245] *Nickel as NiO
[0246] **Nickel as an alloy
[0247] For catalyst A (15% Ni alone/alumina), the nickel reducibility rate is 0% after exactly the same reduction treatment under hydrogen as for catalysts B to E. It is necessary to reduce to 400°C to have a reduction of nickel oxide to Ni° of the order of 80%.
[0248] Catalyst C prepared by co-impregnation of solutions S2 and S3 has, according to dRX, that NiCu alloy is of which there is no active phase alone Ni°.
[0249] The nickel post or pre-impregnation of the S3 solution with a Ni/Cu ratio of 3 (catalysts D, E, F) or 1 (catalyst G) with a Ni content of 2% (catalyst F) or 5% ( catalyst D, E, G) also allows a reduction of Nickel oxide to Ni° of the order of 90% in the end on the catalyst.
[0250] Example 12: Catalytic tests: performances in selective hydrogenation of a mixture containing styrene and isoprene (A _HYD1 )
[0251] Catalysts A to G described in the examples above are tested against the selective hydrogenation reaction of a mixture containing styrene and isoprene.
[0252] The composition of the charge to be selectively hydrogenated is as follows: 8% by weight styrene (Sigma Aldrich® supplier, purity 99%), 8% by weight isoprene (Sigma Aldrich® supplier, purity 99%), 84% by weight n-heptane (solvent ) (VWR® supplier, purity > 99% chromanorm HPLC). This composition corresponds to the initial composition of the reaction mixture. This mixture of model molecules is representative of a pyrolysis gasoline.
[0253] The selective hydrogenation reaction is carried out in a 500 mL stainless steel autoclave, equipped with mechanical stirring with magnetic drive and able to operate under a maximum pressure of 100 bar (10 MPa) and temperatures between 5°C and 200°C.
[0254] In an autoclave are added 214 mL of n-heptane (supplier VWR®, purity> 99% chromanorm HPLC) and a quantity of 3 mL of catalyst. The autoclave is closed and purged. Then the autoclave is pressurized under 35 bar (3.5 MPa) of hydrogen. The catalyst is first reduced in situ , at 170°C for 90 minutes under a hydrogen flow of 1 L/h/g (temperature rise ramp of 1°C/min) for catalysts A to G ( which here corresponds to step e) of the preparation process according to the invention according to one embodiment). Then the autoclave is brought to the test temperature equal to 30°C. At time t=0, approximately 30 g of a mixture containing styrene, isoprene, n-heptane, pentanethiol and thiophene are introduced into the autoclave. The reaction mixture then has the composition described above and stirring is started at 1600 rpm. The pressure is kept constant at 35 bar (3.5 MPa) in the autoclave using a reservoir bottle located upstream of the reactor.
[0255] Another test was carried out for catalyst A, but with a catalyst reduction temperature of 400° C. for 15 hours.
[0256] The progress of the reaction is monitored by taking samples from the reaction medium at regular time intervals: the styrene is hydrogenated to ethylbenzene, without hydrogenation of the aromatic ring, and the isoprene is hydrogenated to methyl-butenes. If the reaction is prolonged longer than necessary, the methyl-butenes are in turn hydrogenated to isopentane. Hydrogen consumption is also monitored over time by the decrease in pressure in a reservoir bottle located upstream of the reactor. The catalytic activity is expressed in moles of H ₂ consumed per minute and per gram of Ni.
[0257] The catalytic activities measured for catalysts A to G are reported in Table 2 below. They are related to the catalytic activity (A _HYD1 ) measured for catalyst A prepared under conventional reduction conditions (at a temperature of 400° C. for 15 hours under a flow of hydrogen).
[0258] Example 13: Catalytic tests: performance in hydrogenation of toluene (A _HYD2 )
[0259] Catalysts A to G described in the examples above are also tested with respect to the hydrogenation reaction of toluene.
[0260] The selective hydrogenation reaction is carried out in the same autoclave as that described in Example 10.
[0261] In an autoclave are added 214 mL of n-heptane (supplier VWR®, purity> 99% chromanorm HPLC) and a quantity of 3 mL of catalyst. The autoclave is closed and purged. Then the autoclave is pressurized under 35 bar (3.5 MPa) of hydrogen. The catalyst is first reduced in situ , at 170°C for 90 minutes under a hydrogen flow of 1 L/h/g (temperature rise ramp of 1°C/min) for catalysts A to G ( which here corresponds to step e) of the preparation process according to the invention according to one embodiment). After adding 216 mL of n-heptane (VWR® supplier, purity > 99% chromanorm HPLC), the autoclave is closed, purged, then pressurized under 35 bar (3.5 MPa) of hydrogen, and brought to the test temperature equal to 80°C. At time t=0, approximately 26 g of toluene (SDS® supplier, purity > 99.8%) are introduced into the autoclave (the initial composition of the reaction mixture is then toluene 6% w/w / n-heptane 94% w/w) and stirring is started at 1600 rpm. The pressure is kept constant at 35 bar (3.5 MPa) in the autoclave using a reservoir bottle located upstream of the reactor.
[0262] The progress of the reaction is monitored by taking samples of the reaction medium at regular time intervals: the toluene is completely hydrogenated to methylcyclohexane. Hydrogen consumption is also monitored over time by the decrease in pressure in a reservoir bottle located upstream of the reactor. The catalytic activity is expressed in moles of H2 consumed per minute and per gram of Ni.
[0263] The catalytic activities measured for catalysts A to G are reported in Table 2 below. They are related to the catalytic activity (AHYD2) measured for catalyst A prepared under conventional reduction conditions (at a temperature of 400°C for 15 hours under a flow of hydrogen in a continuous flow rector in situ).
[0264] Catalyst Final reduction Ni° particle size (m) Percentage of Ni° alone (DRX) after reduction (%) A _HYD1 (%) A _HYD2 (%) A (comparative) 400°C, 3 p.m. 14 80 100 100 A (comparative) 170°C, 90 mins 14 0* <1 <1 B (comparative) 170°C, 90 mins 2 0* <1 <1 C (comparative) 170°C, 90 mins - 0** 15 20 D (invention) 170°C, 90 mins 2 90 185 190 E (invention) 170°C, 90 mins 2 95 175 185 F (invention) 170°C, 90 mins 2 90 172 182 G (invention) 170°C, 90 mins 2 95 180 192
[0265] *Nickel as NiO
[0266] **Nickel as an alloy
[0267] Catalysts A and B reduced to 170°C for 90 minutes are not active due to their reduced Ni content of 0. On the other hand, if the temperature is increased to 400°C, catalyst A is active from because of its reduced Ni content of the order of 80%. However, the particle size of 14 nm gives it a relatively modest catalytic activity. Catalyst C does not show, according to the XRD, reduced Ni alone, the activity evaluated in examples 11 and 12 is due to the presence of the alloy which has a slightly hydrogenating character but much less than reduced Ni alone (an activity much lower than the benchmark (around 20%)).
[0268] This clearly shows the improved performance of catalysts D to G according to the invention, compared to the Ni catalyst alone on alumina reduced at 170° C. for 90 min, which is completely inactive. In addition, the small particles obtained due to the use of solution 2 allow a substantial gain in activity even compared to catalyst A reduced to 400°C.

权利要求:
Claims (13)
[0001]
Catalyst comprising nickel and copper, in an amount of 1 and 50% by weight in nickel element relative to the total weight of the catalyst, in an amount of 0.5 to 15% by weight in copper element relative to the total weight of the catalyst, and an alumina support, said catalyst being characterized in that: - the molar ratio between nickel and copper is between 0.5 and 5 mol/mol; - at least a part of the nickel and the copper is in the form of a nickel-copper alloy; - the nickel content included in the nickel-copper alloy is between 0.5 and 15% by weight of nickel element relative to the total weight of the catalyst, - the size of the nickel particles in the catalyst, measured in oxide form, is less than 7 nm.
[0002]
Catalyst according to Claim 1, characterized in that the size of the nickel particles in the catalyst is less than 5 nm.
[0003]
Catalyst according to one of Claims 1 or 2, characterized in that the support is in the form of an extrudate with an average diameter of between 0.5 and 10 mm.
[0004]
Catalyst according to Claim 3, characterized in that the support is in the form of a trilobed or quadrilobed extrudate.
[0005]
Process for the preparation of a catalyst according to any one of claims 1 to 4, comprising the following steps: a) the alumina support is brought into contact with at least one solution containing at least one nickel precursor; b) the alumina support is brought into contact with at least one solution containing at least one nickel precursor and at least one copper precursor; c) the alumina support is brought into contact with at least one solution containing at least one organic compound comprising at least one carboxylic acid function, or at least one alcohol function, or at least one ester function, or at least one amide function , or at least one amine function, Being heard that : - steps a), b) and c) are carried out separately, in any order, or - steps a) and c) are carried out simultaneously, step b) being carried out either before the combination of steps a) and c), or after; - steps b) and c) are carried out simultaneously, step a) being carried out either before the combination of steps b) and c), or after; d) at least one step of drying the catalyst precursor obtained at the end of steps a) to c) is carried out at a temperature below 250° C.; e) a step of reducing the catalyst precursor obtained at the end of step d) is carried out by bringing said precursor into contact with a reducing gas at a temperature greater than or equal to 150° C. and less than 250° C.
[0006]
Process according to Claim 5, in which the molar ratio between the said organic compound introduced in step c) and the nickel element also introduced in step a) is between 0.01 and 5.0 mol/mol.
[0007]
Process according to one of Claims 5 or 6, in which the organic compound of step c) is chosen from oxalic acid, malonic acid, glycolic acid, lactic acid, tartronic acid , citric acid, tartaric acid, pyruvic acid, levulinic acid, ethylene glycol, propane-1,3-diol, butane-1,4-diol, glycerol, xylitol, mannitol, sorbitol, diethylene glycol, glucose, gamma valerolactone, dimethyl carbonate, diethyl carbonate, formamide, N-methylformamide, acetamide, N-methylacetamide, N,N-dimethylmethanamide , 2-pyrrolidone, γ-lactam, lactamide, urea, alanine, arginine, lysine, proline, serine, EDTA.
[0008]
Process according to any one of Claims 5 to 7, in which step e) is carried out at a temperature of between 130 and 190°C.
[0009]
Process according to any one of Claims 5 to 8, in which step e) is carried out between 10 minutes and 110 minutes.
[0010]
Process according to any one of Claims 5 to 9, in which the copper precursor is chosen from copper acetate, copper acetylacetonate, copper nitrate, copper sulphate, copper chloride, bromide copper, copper iodide or copper fluoride.
[0011]
A method according to claim 10, wherein the copper precursor is copper nitrate.
[0012]
Process for the selective hydrogenation of polyunsaturated compounds containing at least 2 carbon atoms per molecule contained in a charge of hydrocarbons having a final boiling point less than or equal to 300°C, which process is carried out at a temperature between 0 and 300°C, at a pressure of between 0.1 and 10 MPa, at a hydrogen/(polyunsaturated compounds to be hydrogenated) molar ratio of between 0.1 and 10 and at an hourly volume rate of between 0.1 and 200 h ^{- 1} when the process is carried out in the liquid phase, or at a hydrogen/(polyunsaturated compounds to be hydrogenated) molar ratio of between 0.5 and 1,000 and at an hourly volume rate between 100 and 40,000 h ^-1 when the process is carried out in the gas, in the presence of a catalyst according to any one of claims 1 to 4.
[0013]
Process for the hydrogenation of at least one aromatic or polyaromatic compound contained in a charge of hydrocarbons having a final boiling point less than or equal to 650°C, said process being carried out in the gaseous phase or in the liquid phase, at a temperature between 30 and 350°C, at a pressure between 0.1 and 20 MPa, at a hydrogen/(aromatic compounds to be hydrogenated) molar ratio between 0.1 and 10 and at an hourly volumetric speed VVH between 0.05 and 50 h ^-1 , in the presence of a catalyst according to any one of Claims 1 to 4.

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FR3011844A1|2013-10-16|2015-04-17|IFP Energies Nouvelles|SELECTIVE HYDROGENATION PROCESS USING CATALYST CONTAINING COPPER AND AT LEAST ONE METAL SELECTED FROM NICKEL OR COBALT|

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FR3064500A1|2017-03-29|2018-10-05|IFP Energies Nouvelles|SELECTIVE HYROGENATION MULTILAYER CATALYST|

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FR3076746A1|2018-01-15|2019-07-19|IFP Energies Nouvelles|PROCESS FOR THE PREPARATION OF A PARTICULAR CATALYST OF SELECTIVE HYDROGENATION BY MIXING AND IMPREGNATION|

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WO2019201617A1|2018-04-18|2019-10-24|IFP Energies Nouvelles|Method for preparing a selective bimetallic hydrogenation catalyst made of nickel and copper|

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FR3112087A1|2020-07-03|2022-01-07|IFP Energies Nouvelles|PROCESS FOR PREPARING A CATALYST FOR HYDROGENATION OF AROMATIC COMPOUNDS OBTAINED FROM MELTED SALTS AND A NICKEL COPPER ALLOY|

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FR3112088A1|2020-07-03|2022-01-07|IFP Energies Nouvelles|PROCESS FOR THE PREPARATION OF A SELECTIVE HYDROGENATION CATALYST OBTAINED FROM MELTED SALTS AND A NICKEL COPPER ALLOY|

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2021-02-05| PLSC| Publication of the preliminary search report|Effective date: 20210205 |

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2021-07-26| PLFP| Fee payment|Year of fee payment: 3 |

优先权:

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申请号 | 申请日 | 专利标题

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FR1908725A|FR3099390B1|2019-07-31|2019-07-31|CATALYST INCLUDING AN ACTIVE PHASE OF NICKEL IN THE FORM OF SMALL PARTICLES AND A NICKEL COPPER ALLOY|

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FR1908725|2019-07-31|FR1908725A| FR3099390B1|2019-07-31|2019-07-31|CATALYST INCLUDING AN ACTIVE PHASE OF NICKEL IN THE FORM OF SMALL PARTICLES AND A NICKEL COPPER ALLOY|

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PCT/EP2020/070077| WO2021018599A1|2019-07-31|2020-07-16|Catalyst comprising an active nickel phase in the form of small particles and a nickel-copper alloy|

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CN202080054923.9A| CN114144257A|2019-07-31|2020-07-16|Catalyst comprising an active nickel phase in the form of small particles and a nickel-copper alloy|