SELECTIVE HYDROGENATION PROCESS USING A PREPARED NICKEL CATALYST USING AN ADDITIVE COMPRISING A CARB

专利摘要:
Process for the selective hydrogenation of polyunsaturated compounds containing at least 2 carbon atoms per molecule, contained in a hydrocarbon feed having a final boiling point less than or equal to 300 ° C in the presence of a catalyst comprising an alumina support and an active phase comprising nickel, said active phase comprising no Group VIB metal, said catalyst being prepared by a process comprising at least: i) a step of contacting said support with at least one solution containing at least one nickel precursor; ii) a step of bringing said support into contact with at least one solution containing at least one organic compound comprising at least one carboxylic acid function; iii) a step of drying said impregnated support at a temperature below 250 ° C; steps i) and ii) being performed separately, in any order.
公开号:FR3061194A1
申请号:FR1663091
申请日:2016-12-22
公开日:2018-06-29
发明作者:Anne-Claire Dubreuil；Agathe Martel
申请人:IFP Energies Nouvelles IFPEN；
IPC主号:

专利说明:

© Holder (s): IFP ENERGIES NOUVELLES Public establishment.
O Extension request (s):
® Agent (s): IFP ENERGIES NOUVELLES.
FR 3 061 194 - A1 (54) SELECTIVE HYDROGENATION PROCESS USING A NICKEL-BASED CATALYST PREPARED BY AN ADDITIVE COMPRISING A CARBOXYLIC ACID FUNCTION.
(© Process for the selective hydrogenation of polyunsaturated compounds containing at least 2 carbon atoms per molecule, contained in a hydrocarbon charge having a final boiling point less than or equal to 300 ° C in the presence of a catalyst comprising a support in alumina and an active phase comprising nickel, said active phase not comprising any group VIB metal, said catalyst being prepared by a process comprising at least:
i) a step of bringing said support into contact with at least one solution containing at least one nickel precursor;
ii) a step of bringing said support into contact with at least one solution containing at least one organic compound comprising at least one carboxylic acid function;
iii) a step of drying said impregnated support at a temperature below 250 ° C; steps i) and ii) being carried out separately, in any order.
Field of the invention
The subject of the invention is a process for the selective hydrogenation of polyunsaturated compounds in a hydrocarbon feed, in particular in C2-C5 steam cracking cuts and steam cracking gasolines, in the presence of a nickel-based catalyst supported on a alumina prepared by means of an organic additive comprising at least one function of the carboxylic acid type.
State of the art
Catalysts for the selective hydrogenation of polyunsaturated compounds are generally based on group VIII metals of the periodic table, such as nickel. The metal is in the form of nanometric metallic particles deposited on a support which can 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 nature and porous distribution of the support are parameters which can have a importance on the performance of catalysts.
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 diffusion limitations), the diffusion of the reactants in the porosity of the support towards the active sites (internal diffusion 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.
With regard to the size of the metal particles, it is generally accepted that the catalyst is more active the smaller the size of the metal particles. In addition, it is important to obtain a particle size distribution centered on the optimal value as well as a narrow distribution around this value.
In order to obtain better catalytic performances, in particular better selectivity and / or activity, it is known in the prior art to use additives of the organic compound type for the preparation of metallic catalysts. selective hydrogenation. For example, application FR2984761 discloses a process for the preparation of a selective hydrogenation catalyst comprising a support and an active phase comprising a group VIII metal, said catalyst being prepared by a process comprising a step of impregnating a solution containing a group VIII metal precursor and an organic additive, more particularly an organic compound having one to three carboxylic acid functions, a step of drying the impregnated support, and a step of calcining the dried support in order to obtain the catalyst.
Patent FR2963344 teaches the use of organic compounds comprising a cyclic oligosaccharide composed of at least 6 glucopyranose subunits linked in a- (1,4).
In this context, one of the objectives of the present invention is to provide a process for the selective hydrogenation of polyunsaturated compounds such as diolefins and / or acetylenics and / or alkenylaromatics in the presence of a supported catalyst with an active nickel phase, prepared by means of a particular organic additive making it possible to obtain hydrogenation performance in terms of activity at least as good, or even better, than the methods of the prior art than the methods known from the prior art.
The Applicant has discovered that a nickel-based catalyst supported on alumina prepared by means of an organic additive of the carboxylic acid type, and the impregnation of said additive is carried out in a stage distinct from the nickel impregnation stage. , has, when used in a selective hydrogenation process, improved catalytic performance, in terms of catalytic activity. This results in better conversion of the charge under identical operating conditions.
Objects of the invention
The present invention relates to 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, contained in a hydrocarbon charge having a point of final boiling less than or equal to 300 ° C, which process being carried out at a temperature between 0 and 300 ° C, at a pressure between 0.1 and 10 MPa, at a molar ratio hydrogen / (polyunsaturated compounds to be hydrogenated) between 0.1 and 10 and at an hourly volume speed of between 0.1 and 200 h ^-1 when the process is carried out in the liquid phase, or at a hydrogen / hydrogen (polyunsaturated compounds to be hydrogenated) ratio between 0.5 and 1000 and at an hourly volume speed between 100 and 40,000 h ^-1 when the process is carried out in the gas phase, in the presence of a catalyst comprising an alumina support and an active phase comprising nickel, said active phase not comprising any group VIB metal, said catalyst being prepared by a process comprising at least:
i) a step of bringing said support into contact with at least one solution containing at least one nickel precursor;
ii) a step of bringing said support into contact with at least one solution containing at least one organic compound comprising at least one carboxylic acid function;
iii) a step of drying said impregnated support at a temperature below 250 ° C;
steps i) and ii) being carried out separately, in any order.
According to an embodiment according to the invention, the method can also comprise at least one step iv) of calcining said catalyst obtained in step iii) at a temperature between 250 and 1000 ° C.
In an embodiment according to the invention, step i) of the method is carried out before step ii).
In another embodiment according to the invention, step ii) of the method is carried out before step i).
Advantageously, steps i) and / or ii) is (are) carried out by dry impregnation.
Preferably, the content of nickel element is between 1 and 35% by weight relative to the total weight of the catalyst.
Preferably, said organic compound comprises between 1 and 10 carbon atoms.
In an embodiment according to the invention, said organic compound is chosen from monocarboxylic acids, dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids.
In an embodiment according to the invention, said organic compound comprises at least one carboxylic acid function also comprises at least one second functional group chosen from ethers, hydroxyls, ketones, esters.
Preferably, when said organic compound comprises at least one carboxylic acid function and at least one ketone function, step ii) is carried out before step i).
Preferably, when said organic compound comprises at least one carboxylic acid function and at least one hydroxyl function, step i) is carried out before step ii).
In an embodiment according to the invention, said organic compound comprises at least three different functional groups chosen from at least one carboxylic acid function, at least one hydroxyl function and at least one ether function or ketone function.
Preferably, the molar ratio between said organic compound and nickel is between 0.01 and 5.
In an embodiment according to the invention, the method according to the invention is carried out in the presence of a charge chosen from a C2 steam cracking section or a C2-C3 steam cracking section, and in which the molar ratio (hydrogen) is carried out / (polyunsaturated compounds to be hydrogenated) is between 0.5 and 1000, the temperature is between 0 and 300 ° C, the hourly space velocity (VVH) is between 100 and 40,000 h-1, and the pressure is between 0.1 and 6.0 MPa.
In an embodiment according to the invention, the method according to the invention is carried out in the presence of a filler chosen from steam cracking essences and in which method the molar ratio (hydrogen) / (polyunsaturated compounds to be hydrogenated) is between 0.5 and 10, the temperature is between 0 and 200 ° C the hourly space velocity (VVH) is between 0.5 and 100 h-1, and the pressure is between 0.3 and 8.0 MPa.
detailed description
Definitions
In the following, groups of chemical elements are given according to CAS Classification (CRC Handbook of Chemistry and Physics, CRC press publisher, editor DR Lide, 81 ^th Edition, 2000-2001). For example, group VIII according to the CAS classification corresponds to the metals in columns 8, 9 and 10 according to the new IUPAC classification.
The textural and structural properties of the support and of the catalyst described below are determined by the characterization methods known to those skilled in the art. The total pore volume and the pore distribution are determined in the present invention by nitrogen porosimetry as described in the work "Adsorption by powders and porous solids. Principles, methodology and applications ”written by F. Rouquérol, J. Rouquérol and K. Sing, Academie Press, 1999.
By specific surface is meant the BET specific surface (S _B and in m ² / g) 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 ”, 1938, 60, 309.
The size of nickel nanoparticles is understood to mean the average diameter of the nickel crystallites in oxide form. The average diameter of the nickel crystallites in oxide form is determined by X-ray diffraction, from the width of the diffraction line located at the angle 2theta = 43 ° (that is to say according to the crystallographic direction [ 200]) using Scherrer's relation. This method, used in X-ray diffraction on powders or polycrystalline samples which relates the width at half-height of the diffraction peaks to the size of the particles, is described in detail in the reference: Appl. Cryst. (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.
Description of the process
The present invention relates to 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, which process being 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) of between 0.1 and 10 and at an hourly volume speed of between 0.1 and 200 h ^-1 when the process is carried out in the liquid phase, or at a hydrogen / hydrogen molar ratio (polyunsaturated compounds to be hydrogenated) between 0.5 and 1000 and at an hourly volume speed between 100 and 40,000 h ^-1 when the process is carried out in the gas phase, in the presence of a catalyst comprising an alumina support e an active phase comprising nickel, said active phase not comprising any group VIB metal, said catalyst being prepared by a process comprising at least:
i) a step of bringing said support into contact with at least one solution containing at least one nickel precursor;
ii) a step of bringing said support into contact with at least one solution containing at least one organic compound comprising at least one carboxylic acid function;
iii) a step of drying said impregnated support at a temperature below 250 ° C, so as to obtain a dried catalyst;
steps i) and ii) being carried out separately, in any order.
Monounsaturated organic compounds such as ethylene and propylene, are the source of the manufacture of polymers, plastics and other value-added chemicals. These compounds are obtained from natural gas, naphtha or diesel 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 1-3butadiene , 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 indene compounds. These polyunsaturated compounds are very reactive and lead to parasitic reactions in the polymerization units. It is therefore necessary to eliminate them before adding value to these cuts.
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 cracking essences used as a filler, selective hydrogenation also makes it possible to selectively hydrogenate alkenylaromatics to aromatics, avoiding the hydrogenation of aromatic rings.
The hydrocarbon feedstock treated in the selective hydrogenation process has a final boiling point less than or equal to 300 ° C and cortient at least 2 carbon atoms per molecule and comprises 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.
More particularly, the charge 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 gas cracking essence also called pyrolysis essence or C5 + cut.
The C2 steam cracking section, advantageously used for the implementation of the selective hydrogenation process according to the invention, 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 some C2 steam cracking cuts, between 0.1 and 1% by weight of C3 compounds may also be present.
The steam cracking cut C3, advantageously used for the implementation of the selective hydrogenation process according to the invention, 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 rest being essentially propane. In certain C3 sections, between 0.1 and 2% by weight of C2 compounds and C4 compounds may also be present.
A C2 - C3 cut can also be advantageously used for the implementation of the selective hydrogenation process according to the invention. 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 of methylacetylene, of the order of 30% by weight ethylene, of the order of 5% by weight of propylene, the remainder being essentially methane, ethane and propane. This charge can also contain between 0.1 and 2% by weight of C4 compounds.
The C4 steam cracking cut, advantageously used for the implementation of the selective hydrogenation process according to the invention, has for example the following average mass composition: 1% by weight of butane, 46.5% by weight of butene, 51% by weight butadiene,
1.3% by weight of vinyl acetylene and 0.2% by weight of butyne. In some C4 sections, between 0.1 and 2% by weight of C3 compounds and C5 compounds may also be present.
The C5 steam cracking section, advantageously used for the implementation of the selective hydrogenation process according to the invention, has for example the following composition: 21% by weight of pentanes, 45% by weight of pentenes, 34% by weight of pentadienes.
The steam cracking gasoline or pyrolysis gasoline, advantageously used for the implementation of the selective hydrogenation process according to the invention, corresponds to a hydrocarbon fraction whose boiling temperature is generally between 0 and 300 ° C, preferably between 10 and 250 ° C. The polyunsaturated hydrocarbons to be hydrogenated present in said steam cracking gasoline are in particular diolefinic compounds (butadiene, isoprene, cyclopentadiene, etc.), styrene compounds (styrene, alphamethylstyrene, etc.) and indene compounds (indene, etc.). The essence of steam cracking 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 of the compounds forming 100%. It also contains from 0 to 1000 ppm by weight of sulfur, preferably from 0 to 500 ppm by weight of sulfur.
Preferably, the charge of polyunsaturated hydrocarbons treated in accordance with the selective hydrogenation process according to the invention is a C2 steam cracking cut, or a C2-C3 steam cracking cut, or a steam cracked gasoline.
The selective hydrogenation process according to the invention aims to eliminate said polyunsaturated hydrocarbons present in said charge to be hydrogenated without hydrogenating monounsaturated hydrocarbons. For example, when said charge is a C2 cut, the selective hydrogenation process aims to selectively hydrogenate acetylene. When said charge 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 butadiene, vinyl acetylene (VAC) and butyne, in the case of a C5 cut, the aim is to eliminate the pentadienes. When said charge is a steam cracking essence, the selective hydrogenation process aims to selectively hydrogenate said polyunsaturated hydrocarbons present in said charge to be treated so that the diolefinic compounds are partially hydrogenated to mono-olefins and that the styrenic and indene compounds are partially hydrogenated to the corresponding aromatic compounds, avoiding the hydrogenation of the aromatic rings.
The technological implementation of the selective hydrogenation process is for example carried out by injection, in upward or downward flow, of the charge of polyunsaturated hydrocarbons and hydrogen in 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 reinjections) of the effluent, coming from said reactor where the selective hydrogenation reaction takes place, at various points of the reactor, situated 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 according to the invention 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 feed to be hydrogenated and / or at one or more different points of the reactor.
The selective hydrogenation of cuts C2, C2-C3, C3, C4, C5 and C5 + of steam cracking can be carried out in the gas phase or in the liquid phase, preferably in the liquid phase for the cuts C3, C4, C5 and C5 + and in phase gas for cuts C2 and C2-C3. A liquid phase reaction lowers the energy cost and increases the catalyst cycle time.
In general, the selective hydrogenation of a hydrocarbon feed 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 / molar ratio (polyunsaturated compounds to be hydrogenated) between 0.1 and 10 and at an hourly volume velocity VVH (defined as the ratio of the charge flow rate 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 hydrogen / hydrogen (polyunsaturated compounds to be hydrogenated) ratio between 0.5 and 1000 and at an hourly volume speed VVH of between 100 and 40,000 h ^-1 for a process carried out in the gas phase.
In an embodiment according to the invention, when a selective hydrogenation process is carried out in which the filler is a steam cracking essence comprising polyunsaturated compounds, the molar ratio (hydrogen) / (polyunsaturated compounds to be hydrogenated) is generally understood 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 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.
More preferably, a selective hydrogenation process is carried out in which the charge is a steam cracking essence comprising polyunsaturated compounds, the hydrogen / hydrogen molar ratio (polyunsaturated compounds to be hydrogenated) is between 0.7 and 5.0, the temperature is between 20 and 200 ° C, the hourly volume speed (VVH) is generally between 1 and 50 h ^-1 and the pressure is between 1.0 and 7.0 MPa.
Even more preferably, a selective hydrogenation process is carried out in which the charge is a steam cracking essence comprising polyunsaturated compounds, the hydrogen / hydrogen molar ratio (polyunsaturated compounds to be hydrogenated) is between 1.0 and 2.0, the temperature is between 30 and 180 ° C, the hourly volume speed (VVH) is generally between 1 and 50 h ^-1 and the pressure is between 1.5 and 4.0 MPa.
The hydrogen flow rate is adjusted in order to have enough of it to theoretically hydrogenate all of the polyunsaturated compounds and to maintain an excess of hydrogen at the outlet of the reactor.
In another embodiment according to the invention, when a selective hydrogenation process is carried out in which the filler is a C2 steam cracking cut and / or a C2-C3 steam cracking cut 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 speed hourly volume (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.
Description of the catalyst
The catalyst used for implementing the selective hydrogenation process according to the invention comprises an active phase deposited on a support comprising alumina, said active phase comprising nickel. Said active phase is free of metals belonging to group VIB (Cr, Mo, W) of the periodic table. More particularly, the active phase does not include molybdenum or tungsten. Even more preferably, the active phase consists of nickel. According to the invention, the content of nickel element in the catalyst is between 1 and 35% by weight of the mass of catalyst, preferably between 5 and 30% by weight, more preferably between 8 and 25% by weight, and again more preferably between 12 and 23% by weight. The Ni content is measured by X-ray fluorescence.
Nickel is in the form of nanoparticles deposited on said support. The size of the nickel nanoparticles in the catalyst, measured in their oxide form, is less than or equal to 18 nm, preferably less than or equal to 15 nm, more preferably between 0.5 and 12 nm, and even more preferably between 1.5 and 8.0 nm.
The active phase of said catalyst also advantageously comprises at least one additional metal chosen from metals from group VIII, metals from group IB and / or tin. Preferably, the additional metal from group VIII is chosen from palladium, platinum, ruthenium, rhodium and iridium. Preferably, the additional metal from group IB is chosen from copper, gold and silver. Said (s) additional metal (s) is (are) preferably present (s) with a content representing from 0.01 to 20% by weight of the mass of the catalyst, preferably from 0.05 to 10% by weight of the mass of the catalyst and even more preferably from 0.05 to 5% by weight of the mass of said catalyst. Tin is preferably present at a content representing from 0.02 to 15% by weight of the mass of the catalyst, so that the Sn / Ni molar ratio is between 0.01 and 0.2, preferably between 0.025 and 0.055, and even more preferably between 0.03 to 0.05.
Said catalyst according to the invention is generally presented in all the forms known to those skilled in the art, for example in the form of balls, extrudates, tablets, pellets, hollow cylinders or irregular and non-spherical agglomerates, the specific shape can result from a crushing stage.
In a particular embodiment according to the invention, the catalyst 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. This can advantageously be presented in the form of cylindrical, multilobed, trilobed or quadrilobed extrudates. Preferably its shape will be trilobed or quadrilobed. The shape of the lobes can be adjusted according to all the methods known from the prior art.
In another particular embodiment according to the invention, the catalyst is in the form of beads with a diameter between 1 and 8 mm, preferably between 2 and 7 mm.
The support on which said active phase is deposited comprises alumina (AI ₂ O ₃ ).
In a first variant embodiment, the alumina present in said support is a transition alumina such as a gamma, delta, theta, chi, rho, eta, or kappa alumina, alone or as a mixture. More preferably, the alumina is a gamma, delta or theta transition alumina, alone or as a mixture.
In a second variant embodiment, the alumina present in said support is an alpha alumina.
The support can comprise another oxide different from alumina, such as silica (SiO ₂ ), titanium dioxide (TiO ₂ ), cerine (CeO ₂ ) and zirconia (ZrO ₂ ). The support can be a silicon alumina. Very preferably, said support consists solely of alumina.
The pore volume of the support is generally between 0.1 cm ³ / g and 1.5 cm ³ / g, preferably between 0.5 cm ³ / g and 1.0 cm ³ / g. The specific surface of the support is generally greater than or equal to 5 m ² / g, preferably greater than or equal to 30 m ² / g, more preferably between 40 m ² / g and 250 m ² / g, and even more preferably included between 50 m ² / g and 200 m ² / g.
Description of the catalyst preparation process
In general, the catalyst used in the context of the selective hydrogenation process is prepared by a process comprising at least the following steps:
i) a step of bringing said support into contact with at least one solution containing at least one nickel precursor;
ii) a step of bringing said support into contact with at least one solution containing at least one organic compound comprising at least one carboxylic acid function;
iii) a step of drying said impregnated support at a temperature below 250 ° C, so as to obtain a dried catalyst;
steps i) and ii) being carried out separately, in any order.
Step i) Bringing the nickel precursor into contact with the support
The deposition of nickel on said support, in accordance with the implementation of said step i), can be carried out by any method well known to those skilled in the art. In particular, said step i) can be carried out by impregnation, dry or in excess, or even by precipitation deposition, according to methods well known to those skilled in the art.
Said step i) 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 else 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 alternatively by bringing said support into contact with at least one colloidal solution of at least one precursor of nickel, in oxidized form (nanoparticles of oxide, of oxy (hydroxide) or of hydroxide of nickel) or in reduced form (metallic nanoparticles of nickel in the state reduced). Preferably, the solution is aqueous. The pH of this solution can be modified by the optional addition of an acid or a base. According to another preferred variant, the aqueous solution may contain ammonia or ammonium NH ₄ ⁺ ions.
Preferably, said step i) 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 pore volume of the support to be impregnated.
When the nickel precursor is introduced in aqueous solution, a nickel precursor is advantageously used in the form of nitrate, carbonate, chloride, sulfate, hydroxide, hydroxycarbonate, formate, acetate, oxalate , complexes formed with acetylacetonates, or tetrammine or hexammine complexes, or any other inorganic derivative soluble in aqueous solution, which is brought into contact with said support. Advantageously used as nickel precursor, nickel nitrate, nickel carbonate, nickel chloride, nickel hydroxide, nickel hydroxycarbonate. Very preferably, the nickel precursor is nickel nitrate, nickel carbonate or nickel hydroxide.
The quantities of nickel precursor (s) introduced into the solution are chosen such that the total content of nickel element is between 1 and 35% by weight of the mass of catalyst, preferably between 5 and 30% by weight, more preferably between 8 and 25% by weight, and even more preferably between 12 and 23% by weight.
In the embodiment in which step i) 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 impregnation cycles, in using identical or different nickel precursors in each cycle. In this case, each impregnation is advantageously followed by drying and possibly a heat treatment.
Any other additional element may be introduced either at the time of the step of bringing nickel into contact with the support or in another separate step of bringing said additional element into contact with the support. When it is desired to introduce an additional metal chosen from the metals from group VIII, the metals from group IB and / or tin, a salt chosen from nitrate, sulphate, chloride or any other precursor is advantageously used as precursor. conventional. When any other additional element is introduced into a separate step of bringing said additional element into contact with the support, said step may be followed by drying and possibly by heat treatment.
Step ii) bringing the organic compound into contact with the support
Contacting said support with at least one solution containing at least one organic compound comprising at least one carboxylic acid function, in accordance with the implementation of said step ii), can be carried out by any method well known to those skilled in the art. job. In particular, said step ii) can be carried out by impregnation, dry or in excess according to methods well known to those skilled in the art. Preferably, said step ii) is carried out by dry impregnation, which consists in bringing the support of the catalyst 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.
Said solution containing at least one organic compound comprising at least one carboxylic acid function can be aqueous or organic (for example methanol or ethanol or phenol or acetone or toluene or dimethyl sulfoxide (DMSO)) or alternatively 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 optional addition of an acid or a base. In another possible embodiment, the solvent can be absent from the impregnation solution.
In the embodiment in which step ii) is carried out by impregnation, dry or in excess, preferably dry, the impregnation of the support can be carried out using one or more solutions, at least one of said solutions comprises at least one organic compound comprising at least one carboxylic acid function.
In the embodiment in which step ii) is carried out by impregnation, dry or in excess, preferably dry, the impregnation of the support can advantageously be carried out via at least two impregnation cycles, using compounds organic, or mixtures of organic compounds, at least one of which comprises at least one carboxylic acid function, identical or different in each cycle. In this case, each impregnation is advantageously followed by drying and possibly a heat treatment.
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, said organic compound comprises between 1 and 10 carbon atoms.
Preferably, when said organic compound is an aliphatic, saturated or unsaturated organic compound, said compound comprises between 1 and 9 carbon atoms, preferably between 2 and 7 carbon atoms.
Preferably, when said organic compound is an aromatic organic compound, said compound comprises between 7 and 10 carbon atoms, preferably between 7 and 9 carbon atoms.
The molar ratio of said organic compound comprising at least one carboxylic acid function introduced during step ii) relative to the nickel element introduced in step i) is between 0.01 and 5.0 mol / mol, from 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.
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.
In a particular embodiment of the invention, said organic compound is a saturated aliphatic monocarboxylic acid, the aliphatic chain being linear or branched or cyclic. When the organic compound is a saturated linear monocarboxylic acid, it is preferably chosen from formic acid, acetic acid, propionic acid, butanoic acid, valeric acid, hexanoic acid, acid heptanoic, octanoic acid, nonanoic acid. Preferably, said organic compound is chosen from formic acid, acetic acid, propionic acid. More preferably, said organic compound is formic acid. When the organic compound is a saturated branched monocarboxylic acid, it is preferably chosen from isobutyric acid, pivalic acid, methyl-4-octanoic acid, methyl-3-valeric acid, methyl- 4valeric, methyl-2-valeric acid, isovaleric acid, ethyl-2-hexanoic acid, methyl-2-butyric acid, ethyl-2-butyric acid, propyl-2- valerianic, valproic acid, in any of their isomeric forms. When the organic compound is a saturated cyclic monocarboxylic acid, it is preferably chosen from cyclopentane carboxylic acid, cyclohexane carboxylic acid.
In a particular embodiment of the invention, said organic compound is an unsaturated aliphatic monocarboxylic acid, the aliphatic chain being linear or branched or cyclic, preferably chosen from methacrylic acid, acrylic acid, vinylacetic acid, crotonic acid, isocrotonic acid, pentene-2-oic acid, pentene-3-oic acid, pentene-4-oic acid, tiglic acid, angelic acid, acid sorbic, acetylene carboxylic acid, in any of their isomeric forms.
In a particular embodiment of the invention, said organic compound is an aromatic monocarboxylic acid, preferably chosen from benzoic acid, methylbenzoic acid, dimethyl benzoic acid, trimethyl benzoic acid, ethyl benzoic acid, o-tolylacetic acid, phenylacetic acid, phenyl-2-propionic acid, phenyl-3propionic acid, vinyl-4-benzoic acid, phenylacetylenecarbonic acid, acid cinnamic, in any of their isomeric forms.
In a particular embodiment of the invention, said organic compound is a saturated or unsaturated aliphatic dicarboxylic acid, the aliphatic chain being linear or branched or cyclic.
When the organic compound is a saturated linear dicarboxylic acid, it is preferably chosen from ethanedioic acid (oxalic acid), propanedioic acid (malonic acid), butanedioic acid (succinic acid), pentanedioic acid (acid glutaric), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), octanedioic acid (suberic acid), nonanedioic acid (azelaic acid). When the organic compound is a saturated branched dicarboxylic acid, it is preferably chosen from methyl-2-glutaric acid, methyl-3-glutaric acid, dimethyl-3,3-glutaric acid, dimethyl acid -2,2-glutaric, butane-1,2-dicarboxylic acid, in any of their isomeric forms.
Preferably, said organic compound is chosen from ethanedioic acid (oxalic acid), propanedioic acid (malonic acid), butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), under any one of their isomeric forms.
When the organic compound is a cyclic saturated dicarboxylic acid, it is preferably chosen from cyclohexanedicarboxylic acid, pinic acid, in any of their isomeric forms.
Even more preferably, said organic compound is chosen from 1,2cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, in any of their isomeric forms.
When the organic compound is an unsaturated, linear or branched or cyclic dicarboxylic acid, it is preferably chosen from (Z) -butenedioic acid (maleic acid), (E) -butenedioic acid (fumaric acid), pent-2-enedioic acid (glutaconic acid), (2E-4E) -hexa-2,4-dienioic acid (muconic acid), mesaconic acid, citraconic acid, acetylenedicarboxylic acid, acid methylene-2-succinic (itaconic acid), hexadiene-2,4-dioic acid, in any of their isomeric forms.
Preferably, said organic compound is chosen from (Z) -butenedioic acid (maleic acid), (E) -butenedioic acid (fumaric acid), pent-2-enedioic acid (glutaconic acid), mesaconic acid, citraconic acid, methylene-2-succinic acid (itaconic acid), in any of their isomeric forms. Even more preferably, said organic compound is chosen from (Z) -butenedioic acid (maleic acid), (E) -butenedioic acid (fumaric acid), pent-2-enedioic acid (glutaconic acid) .
In a particular embodiment of the invention, said organic compound is an aromatic dicarboxylic acid, preferably chosen from benzene-1,2-dicarboxylic acid (phthalic acid), benzene-1,3-dicarboxylic acid ( isophthalic acid), benzene1,4-dicarboxylic acid (terephthalic acid), phenylsuccinic acid, in any of their isomeric forms. Preferably, said organic compound is benzene-1,2dicarboxylic acid (phthalic acid).
In a particular embodiment of the invention, said organic compound is an aliphatic, saturated or unsaturated, or aromatic tricarboxylic acid, preferably chosen from propanetricarboxylic acid-1,2,3 (tricarballylic acid), butanetricarboxylic acid -
1,2,4, propene-tricarboxylic acid-1,2,3 (aconitic acid), benzenetricarboxylic acid-1,3,5 (trimesic acid), benzenetricarboxylic acid-1,2,4, under any of their isomeric forms. Preferably, said organic compound is chosen from propanetricarboxylic acid-1,2,3 (tricarballylic acid), butanetricarboxylic acid-1,2,4, propene-tricarboxylic acid-1,2,3 (aconitic acid ), benzenetricarboxylic acid-1,2,4, in any of their isomeric forms.
In a particular embodiment of the invention, said organic compound is an aliphatic, saturated or unsaturated, or aromatic tetracarboxylic acid, preferably chosen from methanetetracarboxylic acid, butanetetracarboxylic acid-1,2,3,4,1 ethylenetetracarboxylic acid, benzenetetracarboxylic acid-1,2,4,5, in any of their isomeric forms. Preferably, said organic compound is chosen from butanetetracarboxylic acid-1,2,3,4, benzenetetracarboxylic acid-1,2,4,5, in any one of their isomeric forms.
In another embodiment according to the invention, said organic compound can comprise at least one second functional group chosen from ethers, hydroxyls, ketones, esters. Advantageously, said organic compound comprises at least one carboxylic acid function and at least one hydroxyl function, or at least one carboxylic acid function and at least one ether function, or at least one carboxylic acid function and at least one ketone function. Advantageously, said organic compound can comprise at least three different functional groups chosen from at least one carboxylic acid function, at least one hydroxyl function and at least one functional group different from the carboxylic and hydroxyl acid functions, such as an ether function or a ketone function.
Among the organic compounds comprising at least one carboxylic acid function and at least one hydroxyl function, mention may be made of the hydroxy acids of monocarboxylic acids, the hydroxy acids of dicarboxylic acids or of polycarboxylic acids, the dihydroxy acids of monocarboxylic acids or of polycarboxylic acids, the trihydroxy acids of monocarboxylic acids or polycarboxylic acids, and more generally polyhydroxy acids of monocarboxylic acids or polycarboxylic acids, the carbon chain of said acids may be saturated aliphatic (linear, branched or cyclic), or unsaturated aliphatic (linear, branched or cyclic) or may contain at least one aromatic cycle. Preferably, said organic compound is chosen from hydroxy acids or dihydroxy acids, monocarboxylic acids or dicarboxylic acids or tricarboxylic acids.
When the organic compound is a hydroxyacid of a monocarboxylic acid, it is preferably chosen from hydroxyacetic acid (glycolic acid), 2hydroxypropanoic acid (lactic acid), hydroxy-2-isobutyric acid or the other ahydroxy acids, 3-hydroxypropanoic acid, hydroxy-3-butyric acid, 3hydroxypentanoic acid, hydroxy-3-isobutyric acid, 3-hydroxy-3-methylbutanoic acid, or other β-hydroxy acids, the hydroxy-4-butyric acid or other γ-hydroxy acids, mandelic acid, 3-phenyllactic acid, tropic acid, hydroxybenzoic acid, salicylic acid, (hydroxy-2-phenyl) acid -acetic, (hydroxy-3-phenyl) -acetic acid, (hydroxy-4-phenyl) -acetic acid, coumaric acid, in any of their isomeric forms. Preferably, said organic compound is chosen from hydroxyacetic acid (glycolic acid), 2-hydroxypropanoic acid (lactic acid), 3hydroxypropanoic acid, hydroxy-3-butyric acid, hydroxy-3- acid isobutyric, mandelic acid, 3-phenyllactic acid, tropic acid, salicylic acid, in any of their isomeric forms. Even more preferably, said organic compound is chosen from hydroxyacetic acid (glycolic acid), 2hydroxypropanoic acid (lactic acid), 3-hydroxypropanoic acid, hydroxy-3butyric acid, hydroxy-3 acid -isobutyric.
When the organic compound is a hydroxy acid of a polycarboxylic acid, it is preferably chosen from 2-hydroxypropanedioic acid (tartronic acid), 2hydroxybutanedioic acid (malic acid), acetolactic acid or the other a-hydroxy acids or β-hydroxy acids or γ-hydroxy acids of dicarboxylic acids, hydroxy-53061194 isophthalic acid, 2-hydroxypropane-l, 2,3-tricarboxylic acid (citric acid), isocitric acid, homocitric acid, homoisocitric acid or the other α-hydroxy acids or β hydroxy acids or γ-hydroxy acids of tricarboxylic acids, in any of their isomeric forms. Preferably, said organic compound is chosen from 2hydroxypropanedioic acid (tartronic acid), 2-hydroxybutanedioic acid (malic acid), acetolactic acid, 2-hydroxypropane-1,2,3-tricarboxylic acid (acid citric), isocitric acid, homocitric acid, homoisocitric acid, in any of their isomeric forms. Even more preferably, said organic compound is chosen from 2-hydroxypropanedioic acid (tartronic acid), 2-hydroxybutanedioic acid (malic acid), acetolactic acid, 2-hydroxypropane-1,2 acid, 3-tricarboxylic (citric acid).
When the organic compound is a dihydroxy acid of a monocarboxylic acid, it is preferably chosen from glyceric acid, 2,3-dihydroxy-3-methylpentanoic acid, pantoic acid or the other α, α-dihydroxy acids or α, β-dihydroxyacids or α, γ-dihydroxyacids, 3,5-dihydroxy-3-methylpentanoic acid (mevalonic acid), or the other β, βdihydroxyacids or β, γ-dihydroxyacids or γ, γ-dihydroxyacids, l ' bis- (hydroxymethyl) acid -
2.2- propionic acid, 2,3-dihydroxybenzoic acid, α-resorcylic acid, βresorcylic acid, γ-resorcylic acid, gentisic acid, protocatechic acid, orsellinic acid, acid homogentisic, caffeic acid, in any of their isomeric forms. Preferably, said organic compound is chosen from glyceric acid, acid
2.3- dihydroxy-3-methylpentanoic acid, pantoic acid, 2,3-dihydroxybenzoic acid, β-resorcylic acid, γ-resorcylic acid, gentisic acid, orsellinic acid, under one any of their isomeric forms. Even more preferably, said organic compound is chosen from glyceric acid, 2,3-dihydroxy-3-methylpentanoic acid, pantoic acid.
When the organic compound is a dihydroxy acid of a polycarboxylic acid, it is preferably chosen from dihydroxymalonic acid, 2,3-dihydroxybutanedioic acid (tartaric acid) or the other α, α-dihydroxy acids or α, β-dihydroxy acids or α, γdihydroxyacids or β, β-dihydroxyacids or β, γ-dihydroxyacids or γ, γ-dihydroxyacids of dicarboxylic acids, hydroxycitric acid, in any of their isomeric forms. Preferably, said organic compound is chosen from dihydroxymalonic acid, 2,3-dihydroxybutanedioic acid (tartaric acid), hydroxycitric acid, in any of their isomeric forms. Even more preferably, said organic compound is chosen from dihydroxymalonic acid, 2,3dihydroxybutanedioic acid (tartaric acid).
When the organic compound is a polyhydroxy acid of a monocarboxylic acid or of a polycarboxylic acid, it is preferably chosen from shikimic acid, trihydroxybenzoic acid, gallic acid, phloroglucinic acid, pyrogallolcarboxylic acid, quinic acid, gluconic acid, mucic acid, saccharic acid, in any of their isomeric forms. Preferably, said organic compound is chosen from trihydroxybenzoic acid, quinic acid, gluconic acid, mucic acid, saccharic acid, in any of their isomeric forms. Even more preferably, said organic compound is chosen from quinic acid, gluconic acid, mucic acid, saccharic acid.
Among the organic compounds comprising at least one carboxylic acid function and at least one ether function, mention may be made of 2-methoxyacetic acid, 2,2'-oxidiacetic acid (diglycolic acid), 4-methoxybenzoic acid, isopropoxy-4-benzoic acid, methoxy-3-phenylacetic acid, methoxy-3-cinnamic acid, methoxy-4-cinnamic acid, 3,4-dimethoxycinnamic acid, veratric acid, l tetrahydrofuran-carboxylic-2 acid, furan-carboxylic acid-3, 2,5-dihydro-3,4-furan dicarboxylic acid, according to any one of their isomeric forms. Preferably, said organic compound is 2,2’-oxidiacetic acid (diglycolic acid).
Among the organic compounds comprising at least one carboxylic acid function and at least one ketone function, mention may be made of glyoxylic acid, 2-oxopropanoic acid (pyruvic acid), 2-oxobutanoic acid, 3-oxopentanoic acid , 3-methyl-2oxobutanoic acid, 4-methyl-2-oxopentanoic acid, phenylglyoxylic acid, phenylpyruvic acid, mesoxalic acid, 2-oxoglutaric acid, 2-oxohexanedioic acid, oxalosuccinic acid or the other α-keto acids of monocarboxylic acids or polycarboxylic acids, acetylacetic acid, acetonedicarboxylic acid, or the other β-keto acids of monocarboxylic acids or polycarboxylic acids, 4oxopentanoic acid (levulinic acid) or the other γ-keto acids of monocarboxylic acids or polycarboxylic acids, acetyl-4-benzoic acid, dioxosuccinic acid, 4-maleylacetoacetic acid or other polyketoac ides of monocarboxylic acids or polycarboxylic acids, according to any of their isomeric forms. Preferably, said organic compound is chosen from glyoxylic acid, 2-oxopropanoic acid (pyruvic acid), 2-oxobutanoic acid, 3 methyl-2-oxobutanoic acid, phenylglyoxylic acid, acid phenylpyruvic, mesoxalic acid, 2-oxoglutaric acid, 2-oxohexanedioic acid, oxalosuccinic acid, acetylacetic acid, acetonedicarboxylic acid, 4-oxopentanoic acid (levulinic acid), acid dioxosuccinic, according to any one of their isomeric forms. Even more preferably, said organic compound is chosen from glyoxylic acid, 2-oxopropanoic acid (pyruvic acid), 2-oxobutanoic acid, 3-methyl-2oxobutanoic acid, mesoxalic acid, l 2-oxoglutaric acid, acetylacetic acid, acetonedicarboxylic acid, 4-oxopentanoic acid (levulinic acid), dioxosuccinic acid.
Among the organic compounds comprising at least one carboxylic acid function and at least one ester function, mention may be made of acetylsalicylic acid.
Among the organic compounds comprising at least one carboxylic acid function, at least one hydroxyl function and at least one ether function, mention may be made of 4-hydroxy3-methoxybenzoic acid (vanillic acid), syringic acid, glucuronic acid, galacturonic acid, ferulic acid, sinapic acid, according to any one of their isomeric forms. Preferably, said organic compound is chosen from 4-hydroxy-3-methoxybenzoic acid (vanillic acid), glucuronic acid, galacturonic acid, according to any of their isomeric forms.
Among the organic compounds comprising at least one carboxylic acid function, at least one hydroxyl function and at least one ketone function, mention may be made of hydroxypyruvic acid, acetolactic acid, iduronic acid, ulosonic acid, acid meconic, 4-hydroxyphenylpyruvic acid, according to any one of their isomeric forms. Preferably, said organic compound is chosen from hydroxypyruvic acid, acetolactic acid, iduronic acid, meconic acid, according to any of their isomeric forms.
Among all the preceding embodiments, said organic compound comprising at least one carboxylic acid function is preferably chosen from formic acid, acetic acid, propionic acid, ethanedioic acid (oxalic acid), acid propanedioic (malonic acid), butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), 1,2-cyclohexanedicarboxylic acid, 1,3cyclohexanedicarboxylic acid, (Z) -butenedioic acid (acid maleic), (E) butenedioic acid (fumaric acid), pent-2-enedioic acid (glutaconic acid), mesaconic acid, citraconic acid, methylene-2-succinic acid (itaconic acid) , benzene-1,2-dicarboxylic acid (phthalic acid), propanetricarboxylic acid-1,2,3 (tricarballylic acid), butanetricarboxylic acid-1,2,4, propene-tricarboxylic acid-1 , 2,3 (aconitic acid), benzenetricarboxylic acid-1,2,4, butanetetracarboxylic acid-
1,2,3,4, benzenetetracarboxylic acid-1,2,4,5, hydroxyacetic acid (glycolic acid), 2-hydroxypropanoic acid (lactic acid), 3-hydroxypropanoic acid, hydroxy-3-butyric acid, hydroxy-3-isobutyric acid, mandelic acid, 3phenyllactic acid, tropic acid, salicylic acid, 2-hydroxypropanedioic acid (tartronic acid), acid 2-hydroxybutanedioic (malic acid), acetolactic acid, 2hydroxypropane-1,2,3-tricarboxylic acid (citric acid), isocitric acid, homocitric acid, homoisocitric acid, glyceric acid, 2,3-dihydroxy-3-methylpentanoic acid, pantoic acid, 2,3-dihydroxybenzoic acid, β-resorcylic acid, γ-resorcylic acid, gentisic acid, orsellinic acid , dihydroxymalonic acid, 2,3dihydroxybutanedioic acid (tartaric acid), hydroxycitric acid, trihydroxybenzoic acid, acid quinic, gluconic acid, mucic acid, saccharic acid, 2,2'-oxidiacetic acid (diglycolic acid), glyoxylic acid, 2oxopropanoic acid (pyruvic acid), 2- oxobutanoic acid, 3-methyl-2oxobutanoic acid, phenylglyoxylic acid, phenylpyruvic acid, mesoxalic acid, 2-oxoglutaric acid, 2-oxohexanedioic acid, oxalosuccinic acid, acetylacetic acid, acetonedicarboxylic acid, 4-oxopentanoic acid (levulinic acid), dioxosuccinic acid, acetylsalicylic acid, 4-hydroxy-3-methoxybenzoic acid (vanillic acid), glucuronic acid, galacturonic acid , hydroxypyruvic acid, acetolactic acid, iduronic acid, meconic acid, according to any one of their isomeric forms.
Among all the preceding embodiments, said organic compound comprising at least one carboxylic acid function is more preferably chosen from formic acid, ethanedioic acid (oxalic acid), propanedioic acid (malonic acid), butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), (Z) -butenedioic acid (maleic acid), (E) -butenedioic acid (fumaric acid), pent-2-enenedioic acid (acid glutaconic), benzene-1,2-dicarboxylic acid (phthalic acid), propanetricarboxylic acid-1,2,3 (tricarballylic acid), butanetricarboxylic acid-1,2,4, propene-tricarboxylic acid -1,2,3 (aconitic acid), benzenetricarboxylic acid-1,2,4, butanetetracarboxylic acid-1,2,3,4, benzenetetracarboxylic acid-1,2,4,5, hydroxyacetic acid (glycolic acid), 2hydroxypropanoic acid (lactic acid), 3-hydroxypropanoic acid e, hydroxy-33061194 butyric acid, hydroxy-3-isobutyric acid, 2-hydroxypropanedioic acid (tartronic acid), 2-hydroxybutanedioic acid (malic acid), acetolactic acid, 2hydroxypropane acid -1,2,3-tricarboxylic (citric acid), glyceric acid, 2,3dihydroxy-3-methylpentanoic acid, pantoic acid, dihydroxymalonic acid, 2,3dihydroxybutanedioic acid (tartaric acid), quinic acid, gluconic acid, mucic acid, saccharic acid, 2,2'-oxidiacetic acid (diglycolic acid), glyoxylic acid, 2-oxopropanoic acid (pyruvic acid), 2-oxobutanoic acid, 3methyl-2-oxobutanoic acid, mesoxalic acid, 2-oxoglutaric acid, acetylacetic acid, acetonedicarboxylic acid, 4-oxopentanoic acid (levulinic acid), l dioxosuccinic acid, acetylsalicylic acid, 4-hydroxy-3-methoxybenzoic acid (vanillic acid ), glucuronic acid, galacturonic acid, hydroxypyruvic acid, acetolactic acid, iduronic acid, meconic acid, according to any of their isomeric forms.
Even more preferably, the organic compound comprising at least one carboxylic acid function is chosen from formic acid, ethanedioic acid (oxalic acid), propanedioic acid (malonic acid), pentanedioic acid (glutaric acid), l hydroxyacetic acid (glycolic acid), 2-hydroxypropanoic acid (lactic acid), 2hydroxypropanedioic acid (tartronic acid), 2-hydroxybutanedioic acid (malic acid), 2-hydroxypropane-1,2 acid, 3-tricarboxylic (citric acid), 2,3dihydroxybutanedioic acid (tartaric acid), 2,2'-oxidiacetic acid (diglycolic acid), 2-oxopropanoic acid (pyruvic acid), 4-oxopentanoic acid (levulinic acid).
All the embodiments relating to the nature of said organic compound can be combined with one another so that step ii) can be carried out by bringing said support into contact with at least one solution containing at least one organic compound comprising at least one acid function carboxylic, in particular an organic compound comprising at least one carboxylic acid function as mentioned above.
Implementation of steps i) and ii)
The process for the preparation of the nickel catalyst comprises several modes of implementation. They are distinguished in particular by the order of introduction of the organic compound and the nickel precursor, the contacting of the organic compound with the support can be carried out either after the contact of the nickel precursor with the support, or before the bringing the nickel precursor into contact with the support.
A first mode of implementation consists in carrying out said step i) prior to said step ii).
A second mode of implementation consists in carrying out said step ii) before said step i).
Each step i) and ii) of bringing the support into contact with the nickel precursor (step i), and of bringing the support into contact with at least one solution containing at least one organic compound comprising at least one carboxylic acid function (step ii), is carried out at least once and can advantageously be carried out several times, optionally in the presence of a nickel precursor and / or of an identical or different organic compound (s) at each step i) and / or ii) respectively, all the possible combinations of implementation of steps i) and ii) are included within the scope of the invention.
According to a preferred embodiment, when said organic compound comprises at least one carboxylic acid function and at least one ketone function, step ii) is advantageously carried out before step i).
According to a preferred embodiment, when said organic compound comprises at least one carboxylic acid function and at least one hydroxyl function, step i) is advantageously carried out before step ii).
Each contacting step can preferably be followed by an intermediate drying step. The intermediate drying step is carried out at a temperature below 250 ° C, preferably between 15 and 240 ° C, more preferably between 30 and 220 ° C, even more preferably between 50 and 200 ° C, and even more preferably between 70 and 180 ° C. Advantageously, when an intermediate drying step is carried out, an intermediate calcination step can be carried out. The intermediate calcination step is carried out at a temperature between 250 ° C and 1000 ° C, preferably between 250 and 750 ° C.
Advantageously, after each contacting step, whether it is a contacting step of the nickel precursor or a contacting step of the organic compound, the impregnated support can be left to mature, possibly before an intermediate drying step. The maturation allows the solution to distribute itself evenly within the support. When a maturation step is carried out, said step is advantageously carried out at atmospheric pressure or at reduced pressure, under an inert atmosphere or under an atmosphere containing oxygen or under an atmosphere containing water, and at a temperature comprised between 10 ° C and 50 ° C, and preferably at room temperature. Generally a maturation period of less than forty-eight hours and preferably between five minutes and five hours is sufficient. Longer durations are not excluded, but do not necessarily bring improvement.
Step iii) - drying
In accordance with the drying step iii) of the implementation of the preparation of the catalyst, prepared according to at least one embodiment described above, the drying step is carried out at a temperature below 250 ° C. , preferably between 15 and 240 ° C, more preferably between 30 and 220 ° C, even more preferably between 50 and 200 ° C, and even more preferably between 70 and 180 ° C, for a period typically between 10 minutes and 24 hours. Longer durations are not excluded, but do not necessarily bring improvement.
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.
Step iv) - calcination (optional)
Optionally, at the end of step iii) of drying, a step iv) of calcination is carried out at a temperature between 250 ° C and 1000 ° C, preferably between 250 ° C and 750 ° C, under a inert atmosphere or under an oxygen-containing atmosphere. The duration of this heat treatment is generally between 15 minutes and 10 hours. Longer durations are not excluded, but do not necessarily bring improvement. After this treatment, the nickel in the active phase is thus in oxide form and the catalyst no longer contains or has very little organic compound introduced during its synthesis.
Step v) - reducing treatment (optional)
Prior to the use of the catalyst in the catalytic reactor and the implementation of a hydrogenation process, at least one step of reducing treatment is advantageously carried out v) in the presence of a reducing gas after steps iii) or iv ) so as to obtain a catalyst comprising nickel at least partially in metallic form.
This treatment makes it possible to activate said catalyst and to form metallic particles, in particular nickel in the zero-value state. Said reducing treatment can be carried out in situ or ex situ, that is to say after or before the loading of the catalyst into the hydrogenation reactor. Said step v) of reducing treatment can be implemented on the catalyst having been subjected or not to step vi) of passivation, described below.
The reducing gas is preferably hydrogen. The hydrogen can be used pure or as a mixture (for example a hydrogen / nitrogen mixture, or hydrogen / argon, or hydrogen / methane). In the case where hydrogen is used as a mixture, all the proportions are possible.
Said reducing treatment is carried out at a temperature between 120 and 500 ° C., preferably between 150 and 450 ° C. When the catalysis does not undergo passivation, or undergoes a reduction treatment before passivation, the reduction treatment is carried out at a temperature between 180 and 500 ° C, preferably between 200 and 450 ° C, and even more preferably between 350 and 450 ° C. When the catalyst has previously been passivated, the reducing treatment is generally carried out at a temperature between 120 and 350 ° C, preferably between 150 and 350 C.
The duration of the reducing treatment is generally between 2 and 40 hours, preferably between 3 and 30 hours. The temperature rise 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.
The hydrogen flow rate, expressed in L / hour / gram of catalyst is between 0.01 and 100 L / hour / gram of catalyst, preferably between 0.05 and 10 L / hour / gram of catalyst, again more preferred between 0.1 and 5 L / hour / gram of catalyst.
Step vi) - passivation (optional)
Prior to its implementation in the catalytic reactor, the catalyst according to the invention can optionally undergo a passivation step (step vi) with a sulfur-containing or oxygenated compound or with CO ₂ before or after the reducing treatment step v) . This passivation step can be carried out ex-situ or in-situ. The passivation step is carried out by the implementation of methods known to those skilled in the art.
The sulfur passivation stage makes it possible to improve the selectivity of the catalysts and to avoid thermal runaway during the start-up of new catalysts (“run away” according to English terminology). The passivation generally consists in irreversibly poisoning the sulfur compound with 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 the implementation of methods known to those skilled in the art and in particular, by way of example by the implementation of one of the methods described in patent documents EP0466567, US5153163, FR2676184, W02004 / 098774, EP0707890. The sulfur compound is for example chosen from the following compounds: thiophene, thiophane, alkylmonosulfides such as dimethylsulfide, diethylsulfide, dipropylsulfide and propylmethylsulfide or an organic disulfide of formula HO-R ₁ -SSR ₂ -OH such as di-thio-di -ethanol of formula HO-C2H4-SS-C2H4-OH (often called DEODS). The sulfur content is generally between 0.1 and 2% by weight of said element relative to the mass of the catalyst.
The passivation step with an oxygenated compound or with CO ₂ is generally carried out after a reduction treatment beforehand at high temperature, generally between 350 and 500 ° C., and makes it possible to preserve the metallic phase of the catalyst in the presence of air. . A second reducing treatment at a lower temperature, generally between 120 and 350 ° C., is then generally carried out. The oxygenated compound is generally air or any other flow containing oxygen.
The catalyst prepared according to at least any of the embodiments described above, whether or not in combination with said step iv) and / or said step v) and / or said step vi), is present, before the implementation of the selective hydrogenation process according to the invention, either entirely or at least partially rid of said organic compound comprising at least one carboxylic acid function. The introduction of the organic compound during its preparation has made it possible to increase the dispersion of the active phase, thus leading to a more active and / or more selective catalyst.
The invention is illustrated by the following examples.
Examples
All the catalysts prepared in Examples 1 to 10 are prepared with an isotomer of nickel element. The support used for the preparation of each of these catalysts is a delta alumina having a pore volume of 0.67 ml / g and a BET surface area equal to 70 m ² / g.
Example 1 Preparation of the aqueous solutions of Ni precursors
A first aqueous solution of Ni precursors (solution S1) used for the preparation of catalysts A, B, D, E, F, I is prepared at 25 ° C. by dissolving 276 g of nickel nitrate Ni (NO ₃ ) ₂ . 6H ₂ O (supplier Strem Chemicals®) in a volume of 100 mL of demineralized water. The solution S1 is obtained, the NiO concentration of which is 19.0% by weight (relative to the mass of the solution).
A second aqueous solution of Ni precursors (solution S2) used for the preparation of catalysts C, G and H is prepared at 25 ° C by dissolving 151 g of nickel nitrate Ni (NO ₃ ) ₂ .6H ₂ O (supplier Strem Chemicals®) in a volume of 50 mL of demineralized water. Solution S2 is obtained, the NiO concentration of which is 19.3% by weight (relative to the mass of the solution).
Example 2 (comparative): Preparation of a catalyst A by impregnation of nickel nitrate without additive
The solution S1 prepared in Example 1 is dry impregnated on 10 g of said alumina support. 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 A thus prepared contains 13.8% by weight of the nickel element supported on alumina and it has nickel oxide crystallites whose average diameter (determined by X-ray diffraction from the width of the line of diffraction located at the angle 2theta = 43 °) is 19.1 nm.
Example 3 (invention): Preparation of a catalyst B by successive impregnation of nickel nitrate then propanedioic acid (malonic acid)
Catalyst B is prepared by impregnating Ni nitrate on said alumina support and then by impregnating malonic acid using a molar ratio {malonic acid / nickel} equal to 0.6.
To do this, the solution S1 prepared in Example 1 is impregnated dry on said alumina support. The solid B1 thus obtained is then dried in an oven overnight at 120 ° C. Then, an aqueous solution B ’is prepared by dissolving 4.81 g of malonic acid (CAS 141-82-2, supplier Alfa Aesar, purity 99%) in 20 mL of demineralized water. This solution B 'is then impregnated to dryness on 10 g of the solid B1 previously prepared. 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 B thus prepared contains 13.8% by weight of the nickel element supported on alumina and it exhibits nickel oxide crystallites with an average diameter of 3.8 nm.
Example 4 (invention): Preparation of a catalyst C by successive impregnation of propanedioic acid (malonic acid) then nickel nitrate
Catalyst C is prepared by impregnating malonic acid on said alumina support and then by impregnating Ni nitrate using a molar ratio {malonic acid / nickel} equal to 0.6.
To do this, an aqueous solution C ’is prepared by dissolving 4.81 g of malonic acid (CAS 141-82-2, supplier Alfa Aesar, purity 99%) in 20 mL of demineralized water. This solution C ’is then impregnated dry on said alumina support. The solid C1 thus obtained is then dried in an oven overnight at 120 ° C. Then, the solution S2 prepared in Example 1 is impregnated to dryness on 10 g of the solid C1 previously prepared. 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 C thus prepared contains 13.8% by weight of the nickel element supported on alumina and it has nickel oxide crystallites with an average diameter of 4.5 nm.
Example 5 (invention): Preparation of a catalyst D by successive impregnation of nickel nitrate then 2-hvdroxypropanoic acid (lactic acid)
Catalyst D is prepared by impregnating Ni nitrate on said alumina support and then by impregnating lactic acid using a molar ratio {lactic acid / nickel} equal to 0.6.
To do this, the solution S1 prepared in Example 1 is impregnated dry on said alumina support. The solid D1 thus obtained is then dried in an oven overnight at 120 ° C. Then, an aqueous solution D ’is prepared by dissolving 4.19 g of lactic acid (CAS 15-21-5, supplier Fluka) in 20 ml of demineralized water. This solution D ′ is then impregnated to dryness on 10 g of the solid D1 previously prepared. 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 D thus prepared contains 13.8% by weight of the nickel element supported on alumina and it exhibits nickel oxide crystallites with an average diameter of 5.1 nm.
Example 6 (invention): Preparation of a catalyst E by successive impregnation of nickel nitrate then 2-hvdroxypropanoïaue acid (lactic acid), with an additive molar ratio of nickel of 0.3
Catalyst E is prepared by impregnating Ni nitrate on said alumina support and then by impregnating lactic acid using a molar ratio {lactic acid / nickel} equal to 0.3.
To do this, the solution S1 prepared in Example 1 is impregnated dry on said alumina support. The solid E1 thus obtained is then dried in an oven overnight at 120 ° C. Then, an aqueous solution E ’is prepared by dissolving 2.1 g of lactic acid (CAS 15-21-5, supplier Fluka) in 20 ml of demineralized water. This solution E ′ is then impregnated to dryness on 10 g of the solid E1 previously prepared. 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 E thus prepared contains 13.8% by weight of the nickel element supported on alumina and it has nickel oxide crystallites with an average diameter of 6.0 nm.
Example 7 (invention): Preparation of a catalyst F by successive impregnation of nickel nitrate then of 2-hydroxypropanoic acid (lactic acid), with an additive to nickel molar ratio of 1.2
Catalyst F is prepared by impregnating Ni nitrate on said alumina support and then by impregnating lactic acid using a molar ratio {lactic acid / nickel} equal to 1.2.
To do this, the solution S1 prepared in Example 1 is impregnated dry on said alumina support. The solid F1 thus obtained is then dried in an oven overnight at 120 ° C. Then, an aqueous solution F ’is prepared by dissolving 8.39 g of lactic acid (CAS 15-21-5, supplier Fluka) in 20 ml of demineralized water. This solution F 'is then impregnated to dryness on 10 g of the solid F1 previously prepared. 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 F thus prepared contains 13.8% by weight of the nickel element supported on alumina and it has nickel oxide crystallites with an average diameter of 4.8 nm.
Example 8 (invention): Preparation of a catalyst G by successive impregnation of acid
2-oxopropanoic (pyruvic acid) then nickel nitrate
Catalyst G is prepared by impregnating pyruvic acid on said alumina support and then by impregnating Ni nitrate using a molar ratio {pyruvic acid / nickel} equal to 0.6.
To do this, an aqueous solution G ’is prepared by dissolving 4.07 g of pyruvic acid (CAS 127-17-3, supplier Sigma Aldrich, 98% purity) in 20 mL of demineralized water. This solution G ’is then dry impregnated on said alumina support. The solid G1 thus obtained is then dried in an oven overnight at 120 ° C. Then, the solution S2 prepared in Example 1 is impregnated to dryness on 10 g of the solid G1 previously prepared. 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 G thus prepared contains 13.8% by weight of the nickel element supported on alumina and it has nickel oxide crystallites with an average diameter of 6.2 nm.
Example 9 (invention): Preparation of a catalyst H by successive impregnation of 2oxopropanoic acid (pyruvic acid) then nickel nitrate, without final calcination
Catalyst H is prepared by impregnating pyruvic acid on said alumina support and then by impregnating Ni nitrate using a molar ratio {pyruvic acid / nickel} equal to 0.6.
To do this, an aqueous solution H ’is prepared by dissolving 4.07 g of pyruvic acid (CAS 127-17-3, supplier Sigma Aldrich, 98% purity) in 20 mL of demineralized water. This solution H ’is then impregnated dry on said alumina support. The solid H1 thus obtained is then dried in an oven overnight at 120 ° C. Then, the solution prepared in Example 1 is impregnated to dryness on 10 g of the solid H1 previously prepared. The solid thus obtained is then dried in an oven overnight at 120 ° C., without any other heat treatment. Catalyst H is obtained.
To carry out the characterizations, part of this catalyst H is calcined under an air flow of 1 L / h / g of catalyst at 450 ° C for 2 hours, to obtain the calcined catalyst Hcalci. The calcined catalyst Hcalci contains 13.8% by weight of the nickel element supported on alumina and it has crystallites of nickel oxide with an average diameter of 5.9 nm.
Example 10 (invention): Preparation of a catalyst I by successive impregnation of nickel nitrate then 2,2'-oxobis-ethanoic acid (diglvcolic acid)
Catalyst I is prepared by impregnating Ni nitrate on said alumina support and then by impregnating diglycolic acid using a molar ratio {diglycolic acid / nickel} equal to 0.6.
To do this, the solution S1 prepared in Example 1 is impregnated dry on said alumina support. The solid 11 thus obtained is then dried in an oven overnight at 120 ° C.
Then, an aqueous solution I ’is prepared by dissolving 6.20 g of diglycolic acid (CAS 110-99-6, supplier Alfa Aesar, purity 98%) in 20 ml of demineralized water. This solution I 'is then impregnated to dryness on 10 g of the solid 11 previously prepared. 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 I thus prepared contains 13.8% by weight of the nickel element supported on alumina and it has nickel oxide crystallites with an average diameter of 4.8 nm.
Example 11 (invention): Evaluation of the catalytic properties of catalysts A to I in selective hydrogenation of a mixture containing styrene and isoprene
The catalysts A to I described in the examples above are tested against the selective hydrogenation reaction of a mixture containing styrene and isoprene.
The composition of the filler to be selectively hydrogenated is as follows: 8% by weight styrene (supplier Sigma Aldrich®, purity 99%), 8% by weight isoprene (supplier Sigma Aldrich®, purity 99%), 84% by weight n-heptane (solvent ) (supplier VWR®, purity> 99% chromanorm HPLC). This feed also contains sulfur compounds in very low content: 10 ppm by weight of sulfur introduced in the form of pentanethiol (supplier Fluka®, purity> 97%) and 100 ppm by weight of sulfur introduced in the form of thiophene (supplier Merck®, purity 99 %). This composition corresponds to the initial composition of the reaction mixture. This mixture of model molecules is representative of a pyrolysis essence.
The selective hydrogenation reaction is carried out in a 500 mL stainless steel autoclave, equipped with mechanical agitation with magnetic drive and capable of operating under a maximum pressure of 100 bar (10 MPa) and temperatures between 5 ° C and 200 ° C.
Prior to its introduction into the autoclave, an amount of 3 ml of catalyst is reduced ex situ under a hydrogen flow of 1 L / h / g of catalyst, at 400 ° C. for 16 hours (temperature rise ramp of 1 ° C / min) then it is transferred to the autoclave, protected from air. After adding 214 mL of n-heptane (supplier VWR®, purity> 99% chromanorm HPLC), the autoclave is closed, purged, then pressurized under 35 bar (3.5 MPa) of hydrogen, and brought to temperature of the test equal to 30 ° C. At time t = 0, about 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 the 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.
The progress of the reaction is followed by taking samples of the reaction medium at regular time intervals: the styrene is hydrogenated to ethylbenzene, without hydrogenation of the aromatic cycle, and the isoprene is hydrogenated to methyl butenes. If the reaction is continued longer than necessary, the methyl butenes are in turn hydrogenated to isopentane. The consumption of hydrogen is also followed over time by the reduction 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 10 gram of Ni.
The catalytic activities measured for catalysts A to I are reported in Table 1 below. They are related to the catalytic activity measured for catalyst A (A _HY di) ·
Table 1: Comparison of the performance in selective hydrogenation of a mixture containing styrene and isoprene.
Catalyst Additive used Method of introducing the additive Average NiO crystallite size (nm) Ahydi (%) A (non-compliant) - - 19.1 100 B(compliant) Malonic acid Steps i) then ii) 3.8 457 VS(compliant) Malonic acid Steps ii) then i) 4.5 386 D(compliant) Lactic acid Steps i) then ii) 5.1 363 E(compliant) Lactic acid Steps i) then ii) - Additive / Ni molar ratio = 0.3 6.0 319 F(compliant) Lactic acid Steps i) then ii) - Additive molar ratio / Ni = 1.2 4.8 384 G(compliant) Pyruvic acid Steps ii) then i) 6.2 308 H(compliant) Pyruvic acid Steps ii) then i) - Without calcination 5.9 327 1(compliant) Diglycolic acid Steps i) then ii) 4.8 376
The results appearing in Table 1 demonstrate that catalysts B to I, prepared in the presence of an organic compound (having at least one function of carboxylic acid type), are more active than catalyst A prepared in the absence of this type of organic compound. This effect is linked to the decrease in the size of the Ni particles.

权利要求:
Claims (15)
[1" id="c-fr-0001]
1. 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, contained in a charge of hydrocarbons having a lower final boiling point or equal to 300 ° C., the process being carried out at a temperature between 0 and 300 ° C., at a pressure between 0.1 and 10 MPa, at a hydrogen / hydrogen (polyunsaturated compounds to be hydrogenated) ratio between 0, 1 and 10 and at an hourly volume speed of between 0.1 and 200 h ^-1 when the process is carried out in the liquid phase, or at a hydrogen / hydrogen (polyunsaturated compounds to be hydrogenated) ratio between 0.5 and 1000 and at an hourly volume speed between 100 and 40,000 h ^-1 when the process is carried out in the gas phase, in the presence of a catalyst comprising an alumina support and an active phase comprising nickel, said active phase does not include taking no group VIB metal, said catalyst being prepared by a process comprising at least:
i) a step of bringing said support into contact with at least one solution containing at least one nickel precursor;
ii) a step of bringing said support into contact with at least one solution containing at least one organic compound comprising at least one carboxylic acid function;
iii) a step of drying said impregnated support at a temperature below 250 ° C; steps i) and ii) being carried out separately, in any order.
[2" id="c-fr-0002]
2. Method according to claim 1, characterized in that it further comprises at least one step iv) of calcination of said catalyst obtained in step iii) at a temperature between 250 and 1000 ° C.
[3" id="c-fr-0003]
3. Method according to claims 1 or 2, characterized in that step i) is carried out before step ii).
[4" id="c-fr-0004]
4. Method according to claims 1 or 2, characterized in that step ii) is carried out before step i).
[5" id="c-fr-0005]
5. Method according to claims 1 or 2, characterized in that steps i) and / or ii) is (are) carried out by dry impregnation.
[6" id="c-fr-0006]
6. Method according to any one of the preceding claims, characterized in that the content of nickel element is between 1 and 35% by weight relative to the total weight of the catalyst.
[7" id="c-fr-0007]
7. Method according to any one of the preceding claims, characterized in that said organic compound comprises between 1 and 10 carbon atoms.
[8" id="c-fr-0008]
8. Method according to any one of the preceding claims, characterized in that said organic compound is chosen from monocarboxylic acids, dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids.
[9" id="c-fr-0009]
9. Method according to any one of the preceding claims, characterized in that said organic compound comprising at least one carboxylic acid function also comprises at least one second functional group chosen from ethers, hydroxyls, ketones, esters.
[10" id="c-fr-0010]
10. Method according to claim 9, characterized in that when said organic compound comprises at least one carboxylic acid function and at least one ketone function, step ii) is carried out before step i).
[11" id="c-fr-0011]
11. Method according to claim 9, characterized in that when said organic compound comprises at least one carboxylic acid function and at least one hydroxyl function, step i) is carried out before step ii).
[12" id="c-fr-0012]
12. Method according to claim 9, characterized in that said organic compound comprises at least three different functional groups chosen from at least one carboxylic acid function, at least one hydroxyl function and at least one ether function or ketone function.
[13" id="c-fr-0013]
13. Method according to any one of the preceding claims, characterized in that the molar ratio between said organic compound and nickel is between 0.01 and 5.
[14" id="c-fr-0014]
14. Method according to any one of claims 1 to 13, characterized in that the filler is chosen from a C2 steam cracking section or a C2-C3 steam cracking section, and in which process the molar ratio (hydrogen) / (compounds polyunsaturated to be hydrogenated) is between 0.5 and 1000, the temperature is between
5 between 0 and 300 ° C, the hourly volume speed (V.V.H.) is between 100 and 40,000 h-1, and the pressure is between 0.1 and 6.0 MPa.
[15" id="c-fr-0015]
15. Method according to any one of claims 1 to 13, characterized in that the filler is chosen from steam cracking essences and in which process the molar ratio (hydrogen) / (polyunsaturated compounds to be hydrogenated) is between 0.5
10 and 10, the temperature is between 0 and 200 ° C the hourly space velocity (V.V.H.) is between 0.5 and 100 h-1, and the pressure is between 0.3 and 8.0 MPa.

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优先权:

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申请号 | 申请日 | 专利标题

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FR1663091A|FR3061194B1|2016-12-22|2016-12-22|SELECTIVE HYDROGENATION PROCESS USING A PREPARED NICKEL CATALYST USING AN ADDITIVE COMPRISING A CARBOXYLIC ACID FUNCTION|

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FR1663091|2016-12-22|FR1663091A| FR3061194B1|2016-12-22|2016-12-22|SELECTIVE HYDROGENATION PROCESS USING A PREPARED NICKEL CATALYST USING AN ADDITIVE COMPRISING A CARBOXYLIC ACID FUNCTION|

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PCT/EP2017/082023| WO2018114396A1|2016-12-22|2017-12-08|Selective hydrogenation method using a nickel-based catalyst produced using an additive comprising a carboxylic acid function|

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US16/473,061| US10927310B2|2016-12-22|2017-12-08|Selective hydrogenation method using a nickel-based catalyst produced using an additive comprising a carboxylic acid function|

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EP17832476.0A| EP3559165A1|2016-12-22|2017-12-08|Selective hydrogenation method using a nickel-based catalyst produced using an additive comprising a carboxylic acid function|

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CN201780079515.7A| CN110072977A|2016-12-22|2017-12-08|Using the process for selective hydrogenation for the catalyst based on nickel for using the Additive Production containing carboxylic acid functional|

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KR1020197017883A| KR20190090816A|2016-12-22|2017-12-08|Selective Hydrogenation Process Using Nickel-Based Catalysts Prepared Using Additives Containing Carboxylic Acid Functional Groups|