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    • 专利摘要:
    The invention describes a mass of capture of arsenic and other heavy metals particularly suitable for the treatment of olefinic gasoline sections and loaded with sulfur such as gasoline from catalytic cracking. The capture mass comprises an active phase based on nickel sulphide particles less than or equal to 20 nm in size, deposited on a porous support selected from the group consisting of aluminas, silica, silica aluminas and titanium oxides. alone or in admixture with alumina or silica alumina, magnesium oxides alone or in admixture with alumina or silica alumina. The invention also relates to a method for implementing said capture mass.
    公开号:FR3080048A1
    申请号:FR1853149
    申请日:2018-04-11
    公开日:2019-10-18
    发明作者:Nathalie Crozet；Anne-Claire Dubreuil；Philibert Leflaive；Michel Thomas
    申请人:IFP Energies Nouvelles IFPEN；
    IPC主号:
    专利说明:

    Field of the invention
    The present invention relates to the field of hydrotreating petrol cuts, in particular petrol cuts from catalytic cracking units in a fluidized bed. More particularly, the present invention relates to a mass for the capture of organometallic impurities such as organometallic impurities of heavy metals, silicon or phosphorus, and more particularly of arsenic in hydrocarbon fractions of gasoline type rich in olefins and in sulfur. , as well as a method implementing said capture mass.
    The invention is particularly applicable to the treatment of gasoline cuts containing olefins and sulfur, such as gasolines from catalytic cracking, for which it is sought to extract the arsenic, without hydrogenating the olefins and the aromatics.
    The specifications for automotive fuels provide for a significant reduction in the sulfur content in these fuels, and in particular in gasoline. This reduction is intended to limit, in particular, the content of sulfur and nitrogen oxide in automobile exhaust gases. The specifications currently in force in Europe since 2009 for petrol fuels set a maximum content of 10 ppm by weight (parts per million) of sulfur. Such specifications are also in force in other countries such as for example the United States and China where the same maximum sulfur content has been required since January 2017. To reach these specifications, it is necessary to treat gasolines with desulfurization processes.
    The main sources of sulfur in gasoline bases are the so-called cracked gasolines, and mainly, the gasoline fraction resulting from a catalytic cracking process of a residue from the atmospheric or vacuum distillation of crude oil. The fraction of petrol resulting from catalytic cracking, which represents on average 40% of petrol bases, contributes in fact for more than 90% to the supply of sulfur in petrol. Consequently, the production of low sulfur gasolines requires a step of desulfurization of catalytic cracked gasolines. Other sources of gasoline which may contain sulfur include coking, visbreaking (coker or visbreaker according to English terminology) or, to a lesser extent, gasoline from atmospheric distillation or steam cracking gasoline.
    The elimination of sulfur in gasoline cuts consists in specifically treating these sulfur-rich gasolines by desulfurization processes in the presence of hydrogen. We then speak of hydrodesulfurization (HDS) processes. However, these gasoline cuts and more particularly gasolines originating from the FCC contain a significant proportion of unsaturated compounds in the form of mono-olefins (approximately 20 to 50% by weight) which contribute to a good octane number, of diolefins (0.5 at 5% by weight) and aromatics. These unsaturated compounds are unstable and react during the hydrodesulfurization treatment. The diolefins form gums by polymerization during hydrodesulfurization treatments. This formation of gums leads to a gradual deactivation of the hydrodesulfurization catalysts or a gradual blockage of the reactor. Consequently, the diolefins must be eliminated by hydrogenation before any treatment of these essences. Traditional treatment processes desulfurize gasolines in a non-selective manner by hydrogenating a large part of the mono-olefins, which causes a high loss in octane number and a high consumption of hydrogen. The most recent hydrodesulfurization processes make it possible to desulfurize cracked gasolines rich in mono-olefins, while limiting the hydrogenation of mono-olefins and consequently the loss of octane. Such methods are for example described in documents EP-A-1077247 and EP-A-1174485.
    Hydrodesulfurization processes are carried out continuously for periods of at least 3 to 5 years. The catalysts used to carry out the hydrodesulfurization of sulfur gasolines must therefore exhibit good activity, good selectivity and good stability over time in order to be operated continuously for several years. However, the presence of heavy metals such as mercury or arsenic, or of contaminants such as phosphorus and silicon in the form of organometallic in the hydrocarbon feedstocks to be desulfurized causes rapid deactivation of the hydrotreatment catalysts. It is therefore necessary to remove these contaminants from the feed before bringing it into contact with these hydrodesulfurization catalysts.
    State of the art
    Different solutions have been proposed in the literature for extracting these compounds and more particularly arsenic in hydrocarbon fractions. However, there is still a need to have more efficient capture masses for the selective extraction of heavy metals such as arsenic, in the presence of olefins, with the aim of limiting the responsible hydrogenation reactions in this context. '' a decrease in the octane number of the species concerned.
    Many patents describe arsenic capture masses using different active phases based on transition metals, generally partially in sulphide form.
    Thus, US Pat. No. 4,046,674 describes a process for eliminating arsenic using a capture mass containing at least one nickel compound in sulphide form in an amount between 30% and 70% by weight (relative to the NiO form), and at least one molybdenum compound, also in the form of sulphide, in an amount of between 2% and 20% by weight (relative to the form M0O3). Patent CN107011939A also describes a process for eliminating arsenic using a capture mass comprising nickel and molybdenum but in an amount respectively between 2% and 20% by weight of NiO and between 2% and 10% by weight of MOO3.
    The patent FR 2617497 describes a process for removing arsenic from hydrocarbon cuts by contacting them with a capture mass containing nickel, at least 50% by weight of which is in metal form. A person skilled in the art is well aware of the hydrogenating properties of Ni and therefore expects that the direct application of such a capture mass will lead to a more or less significant hydrogenation of a large part of the olefins present in the cut. hydrocarbon to be treated, which does not respond to the problem that the present invention seeks to solve.
    Patent EP 0 611 182 B1 describes a process for removing arsenic using a capture mass containing at least one metal from the group nickel, cobalt, molybdenum, tungsten, chromium and palladium, 5 to 50% by weight of said or said metals being in the form of sulfide.
    Patent FR2876113 describes a process for eliminating arsenic using a capture mass comprising at least one metallic element chosen from the group consisting of iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), lead (Pb) or zinc (Zn) deposited on a porous support chosen from the group consisting of aluminas, silica, silica aluminas, or even titanium or magnesium oxides used alone or mixed with alumina or silica alumina, the metallic element being in sulphide form with a sulphurization rate at least equal to 60%, and preferably greater than 70%.
    US Pat. No. 5,024,683 describes a process for at least partial elimination of trialkylarsines contained in a charge containing them, comprising the step of bringing this charge into contact with a solid capture mass comprising at least one copper sulfide and a support material. inorganic.
    The US patent 6,759,364 and the patent application US2016008795 describe for their part catalysts adapted to the capture of arsenic in hydrocarbon cuts containing nickel, molybdenum and phosphorus.
    Patent application CN105562000 describes an arsenic capture agent based on copper and nickel, the metals being in oxide form.
    Objects of the invention
    The present invention relates to a capture mass comprising an active phase based on nickel sulphide particles of size less than or equal to 20 nm, said active phase not comprising other metallic elements of group VIB or group VIII, deposited on a porous support chosen from the group consisting of aluminas, silica, aluminas silicas, or alternatively titanium or magnesium oxides used alone or as a mixture with alumina or silica alumina.
    It has in fact been surprisingly discovered that the use of this capture mass makes it possible to efficiently capture organometallic impurities, and in particular arsenic contained in a gasoline containing olefins and sulfur, while limiting the rate of hydrogenation of olefins to values generally less than 30%, preferably less than 20%, and even more preferably less than 10%.
    According to a variant, the active phase consists of particles of nickel sulfide of size less than or equal to 20 nm.
    According to a variant, the size of the nickel sulfide particles is between 1 and 12 nm.
    According to a variant, the nickel content, expressed as a nickel element, is between 5 and 65% by weight, and preferably between 12 and 34% by weight relative to the total mass of the capture mass.
    According to one variant, the total pore volume is greater than or equal to 0.45 ml / g.
    According to a variant, the BET specific surface is at least 40 m 2 / g.
    According to a variant, the invention also relates to a process for the preparation of said capture mass comprising the following steps:
    i) a step of bringing said support into contact with at least one solution containing at least one nickel precursor, ij a step of bringing said support into contact with at least one solution containing at least one organic compound comprising oxygen and / or nitrogen and / or sulfur, steps i) and ij being carried out separately, in any order, or simultaneously, ii) a step of drying said impregnated support at a temperature below 250 ° C., so as to obtain a mass of dried captaticn,
    v) a step of sulfurization of the capture mass.
    According to another variant, the invention relates to a process for the preparation of said capture mass comprising the following steps:
    i) a step of bringing said support into contact with at least one solution containing ammonium ions and containing at least one nickel precursor, ii) a step of drying said impregnated support at a temperature below 250 ° C., so as to obtain a mass of dried captaticn,
    v) a step of sulfurization of the capture mass.
    According to a variant, the two preparation methods can also comprise at least one of the following steps:
    iii) a step of heat treatment of the dried capture mass;
    iv) a step of reducing treatment of the capture mass, dried or resulting from step iii).
    The invention also relates to a process for capturing organometallic impurities contained in a hydrocarbon feedstock using said capture mass in which said capture mass is brought into contact with the feed to be treated and a flow of hydrogen at a temperature comprised between 200 and 400 ° C, a pressure between 0.2 and 5 MPa and a ratio of the flow rate of hydrogen to the flow rate of hydrocarbon feedstock between 50 and 800 Nm 3 / m 3 . According to a variant, the organometallic impurities are chosen from organometallic impurities of heavy metals, silicon, phosphorus and arsenic.
    According to a variant, the charge to be treated is a catalytic cracking gasoline containing between 5% and 60% by weight of olefins, 50 ppm to 6000 ppm by weight of sulfur, as well as traces of arsenic in contents of between 10 ppb and 1000 ppb weight.
    According to a variant, said capture mass is placed in a reactor located upstream of a hydrodesulfurization unit containing a hydrodesulfurization catalyst and / or a selective hydrogenation unit containing a catalyst for the selective hydrogenation of said feedstock .
    According to another variant, said capture mass is placed inside a hydrodesulfurization and / or selective hydrogenation reactor of said feed, at the head of said reactor.
    According to these variants, the volume ratio of said capture mass relative to the volume of said hydrodesulfurization and / or selective hydrogenation catalyst is between 4 and 50%.
    Detailed description of the invention
    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.
    By specific surface is meant the BET specific surface (Sbet 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 Societÿ ', 1938, 60, 309.
    The term “total pore volume” of the capture mass or of the support used for the preparation of the capture mass according to the invention means the volume measured by intrusion with a mercury porosimeter according to standard 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 wetting angle was taken equal to 140 ° following the recommendations of the book "Engineering techniques, treatise analysis and characterization", pages 1050-1055, written by Jean Charpin and Bernard Rasneur. In order to obtain better accuracy, 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 the mercury porosimeter measured on the same sample for a pressure corresponding to 30 psi (about 0.2 MPa).
    The term “size of the nickel sulphide particles” is understood to mean the size of the coherence domain of the nickel crystallites in sulphide form. This coherence domain size of the nickel crystallites in sulphide form is determined by X-ray diffraction, from the width of one or more diffraction lines using the Scherrer relationship. This method, used in X-ray diffraction on powders or polycrystalline samples which relates the width at mid-height of the diffraction peaks to the size of the particles, is described in detail in the reference: J. 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.
    The measurement of the size of each species of nickel sulfide present is carried out by decomposition of the line of interest using Pseudo-Voigt type functions with 5 a contribution of the Gaussian and Lorentzian forms equal to 0.5, this treatment is conventionally used by a person skilled in the art.
    For each species of nickel sulphide, the lines of interest listed below will be preferred to carry out the size measurement. This selection was made on the basis of intensity and isolation criteria from ίο crystallographic databases (in this case according to the ICDD or International Center for
    Diffraction Data). In the case of a mixture of nickel sulfide phases or strong interference of the lines of interest with the support lines, other more isolated lines can be selected.
    Angle Miller's clues(H, k, l) NiS hexagonal 53.21 1,1,0 Rhombohedral / Millerite NiS 18,45 1,1,0 NiS 2 cubic / Vaesite 31,45 2,0,0 N13S2 rhombo / Heazlewoodite 31,13 1,1,0 N13S4 Cubic Polydymite 54.79 0,4,4 Orthorhombic Nies 21.62 0,0,4 Ni 7 S 6 alpha / orthorhombic 18.97 0,2,2 Ni 9 S 8 tetragonal godlevskite 15,51 1,1,2 Ni 9 S 8 orthorombic godlevskite 27.36 1,3,1
    Characteristics of the capture mass
    The capture mass according to the invention is in the form of a supported capture mass comprising an active phase based on nickel sulfide particles of size less than or equal to 20 nm and a porous support chosen from the group consisting of aluminas, silica, silica aluminas, or even titanium or magnesium oxides used alone or as a mixture with alumina or silica alumina. Said active phase does not include other metallic elements of group VIB or group VIII. Preferably, the active phase consists of particles of nickel sulfide of size less than or equal to 20 nm.
    The nickel sulfide phase diagram shows a large number of sulfur-rich and nickel-rich phases at low temperatures. Different phases and stoichiometries of nickel sulfide are therefore possible, ranging from nickel-rich compounds such as Ni 3 S 2 , Ni 6 S 5 , Ni 7 S 6 , Ni 9 S 8 and NiS to sulfur-rich compounds such as N13S4 and N1S2 . Note that NiS is also known to exist in two main phases, namely Ι'α-NiS hexagonal, stable at high temperatures, and rhombohedral β-NIS stable at low temperature. The existence of these numerous phases makes the synthesis of nickel sulfide in the form of a single phase complex, the products therefore often being mixtures of two or more phases.
    The expression “nickel sulfide” designates in the present application the chemical compounds of the Ni x S y type , with 0.5 <x / y <2, preferably x = 1 and y = 1 or also x = 3 and y = 2. The most common compounds are NiS in hexagonal or rhombohedral form or Ni 3 S2.
    Nickel is in the form of nanoparticles of nickel sulfide deposited on said support. The size of the nickel sulfide nanoparticles in the capture mass is less than or equal to 20 nm, preferably less than or equal to 15 nm, more preferably between 1 and 12 nm. When several species of nickel sulfide are present, "the size of the particles of nickel sulfide" is the weighted average of the sizes of each species of nickel sulfide, the amount of each of the phases being determined by structural refinement by the Rietveld method. .
    The nickel content, expressed as a nickel element, is between 5 and 65% by weight relative to the total mass of the capture mass, preferably between 8 and 55% by weight, even more preferably between 12 and 40 % by weight, and particularly preferably between 12 and 34% by weight. The Ni content is measured by X-ray fluorescence.
    The capture mass according to the invention has a total pore volume greater than or equal to 0.45 ml / g, preferably greater than or equal to 0.48 ml / g, and in a particularly preferred manner between 0.55 and 0, 95 mL / g.
    The capture mass according to the present invention has a BET specific surface of at least 40 m 2 / g, preferably at least 50 m 2 / g, and even more preferably between 55 and 250 m 2 / g , preferably between 60 and 225 m 2 / g.
    Said collection mass according to the invention is in the form of grains having an average diameter of between 0.5 and 10 mm. The grains can have all the shapes known to a person skilled in the art, for example the shape of beads (preferably having a diameter between 1 and 6 mm), extrudates, tablets, hollow cylinders. Preferably, the capture mass (and the support used for the preparation of the capture mass) are either in the form of extrudates with an average diameter of between 0.5 and 10 mm, preferably between 0.8 and 3.2 mm and with an average length of between 0.5 and 20 mm, or in the form of balls with an average diameter of between 0.5 and 10 mm, preferably between 1.4 and 4 mm. The term “mean diameter” of the extrudates means the mean diameter of the circle circumscribed in the cross section of these extrudates. The capture mass can advantageously be presented in the form of cylindrical, multi-lobed, three-lobed or four-lobed extrudates. Preferably its shape will be three-lobed or four-lobed. The shape of the lobes can be adjusted according to all the methods known from the prior art.
    The support for the capture mass according to the invention is an inorganic support selected from the group consisting of aluminas, silica, silica-aluminas, titanium oxides alone or in mixture with alumina or silica-alumina, magnesium oxides alone or as a mixture with alumina or silica alumina. Preferably, the support is selected from the group consisting of aluminas, silica and silica-aluminas. Very preferably, the support essentially consists of at least one alumina, that is to say that it comprises at least 51% by weight, preferably at least 60% by weight, very preferably at least 80% by weight , or even at least 90% by weight of alumina relative to the total weight of said support. Preferably, said support has an alumina content greater than or equal to 90% by weight relative to the total weight of said support, optionally supplemented with silica and / or phosphorus at a total content of at most 10% by weight in equivalent SiO 2 and / or P2O5, preferably less than 5% by weight, and very preferably less than 2% by weight relative to the total weight of the support. Silica and / or phosphorus can be introduced by any technique known to those skilled in the art, during the synthesis of the alumina gel or by impregnation of the support used for the preparation of the capture mass according to the invention.
    Even more preferably, the support consists of alumina. Preferably, the alumina present in said support is a transition alumina such as a gamma, delta, theta, chi, rho or eta alumina, alone or as a mixture. More preferably, the alumina is a transition gamma, delta or theta alumina, alone or as a mixture.
    The characteristics of the following support correspond to the characteristics of the support used for the preparation of the capture mass according to the invention before impregnation of the active phase.
    The support used for the preparation of the capture mass according to the invention preferably has a total pore volume greater than or equal to 0.68 ml / g, preferably greater than or equal to 0.70 ml / g, and particularly preferred between 0.70 and 1.0 mL / g.
    The support used for the preparation of the capture mass according to the invention has a BET specific surface of at least 40 m2 / g, preferably at least 50 m2 / g, and even more preferably between 60 and 300 m 2 / g, preferably between 80 and 250 m 2 / g.
    Method for preparing the capture mass
    The present invention also relates to methods for preparing said collection mass according to the invention.
    The Applicant has discovered that the small size of the nickel sulfide particles obtained after sulfurization is due to the process for preparing the capture mass.
    Without being bound to any theory, it seems that the small size of the nickel sulphide particles obtained after sulphurization makes it possible to provide a dispersion of the active phase which is particularly suitable for efficiently capturing organometallic impurities, and in particular the arsenic contained in an essence containing olefins and sulfur. In addition, nickel sulfide particles limit the rate of hydrogenation of olefins and therefore the loss of octane number.
    Obtaining a small size of the nickel sulfide particles obtained thanks to the preparation processes described below is all the more remarkable since the mass is loaded with nickel. Indeed, it is well known to those skilled in the art, that obtaining small particles is more difficult when the mass contains more and more nickel. This effect is accentuated when the specific surface of the support is smaller and smaller.
    According to a first variant, the small size of the nickel sulfide particles obtained after sulfurization is due to the preparation process including the introduction of an organic compound.
    According to a second variant, the small size of the nickel sulphide particles obtained after sulphurization is due to the preparation process including the introduction of nickel by a solution containing ammonium ions, also called the introduction of nickel by the ammonia route.
    Once the active phase is introduced into the support according to one of the two variants, a drying step and a sulfurization step are carried out which are identical according to the two variants.
    According to the two variants, the method can also include, without limitation, in addition at least one of the following steps:
    iii) an optional step of heat treatment of the dried capture mass;
    iv) an optional step of reducing treatment of the capture mass.
    First variant: preparation of the capture mass using an organic compound
    According to a first variant, the capture mass according to the invention 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, i ') a step of bringing said support into contact with at least one solution containing at least one organic compound comprising oxygen and / or nitrogen and / or sulfur, steps i) and i ') being carried out separately, in an indifferent order, or simultaneously, ii) a step of drying said impregnated support at a temperature below 250 ° C. , so as to obtain a dried capture mass,
    v) a step of sulfurization of the capture mass.
    Step i) Bringing the nickel precursor into contact with the support
    According to step i) of the first variant of the method according to the invention, the support is brought into contact with a solution comprising the salt (s) of the precursor (s) of the nickel-based active phase.
    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 else by deposition - precipitation, 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 else by bringing said support into contact with at least one colloidal solution of at least one nickel precursor, in oxidized form (nanoparticles of oxide, of oxy (hydroxide) or of nickel hydroxide), in sulphurized form (nanoparticles of nickel sulfide) or in reduced form (metallic nanoparticles of nickel in the reduced state). Preferably, the solution is aqueous. The pH of this solution may 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 ions NH 4 + .
    Preferably, said step i) is carried out by dry impregnation, which consists in bringing the support of the capture mass 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, sulphate, 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 nickel content, expressed as the nickel element, is between 5 and 65% by weight, preferably between 8 and 55% by weight, so preferred between 12 and 40% by weight, and particularly preferably between 12 and 34% by weight relative to the total mass of the capture mass. The nickel contents, expressed in nickel element, are generally adapted to the targeted arsenic capture as described above in the paragraph of the description of the capture mass.
    Any other additional element can be introduced during this stage: When it is desired to introduce phosphorus, a solution of phosphoric acid can be introduced into the impregnation solution.
    Step i ’) Contacting the organic compound with the support
    According to step i ') of the first variant of the method according to the invention, said support is brought into contact with at least one solution containing at least one organic compound comprising oxygen and / or nitrogen and / or sulfur.
    The introduction of an organic compound comprising oxygen and / or nitrogen and / or sulfur makes it possible to increase the dispersion of the active phase thus leading to particles of small nickel sulfide after sulfurization.
    The contacting of said support with at least one solution containing at least one organic compound comprising oxygen and / or nitrogen and / or sulfur, 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 according to methods well known to those skilled in the art. Preferably, said step i ’) 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.
    Said solution containing at least one organic compound can be aqueous or organic (for example methanol or ethanol or phenol or acetone or toluene or dimethyl sulfoxide (DMSO)) or alternatively consists 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 i ') 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 advantageously be carried out via at least two impregnation cycles, using identical or different organic compounds in each cycle. In this case, each impregnation is advantageously followed by drying and possibly a heat treatment.
    The molar ratio of said organic compound introduced during step i ') relative to the nickel element introduced in step i) is between 0.01 and 5.0 mol / mol, preferably between 0.05 and 2.0 mol / mol.
    Generally, the organic compound comprising oxygen and / or nitrogen and / or sulfur is chosen from a compound comprising one or more chemical functions chosen from a carboxylic acid, alcohol, thiol, thioether, sulfone, sulfoxide, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, oxime, urea and amide.
    Preferably, the organic compound is chosen from a 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.
    In an embodiment according to the invention, said organic compound comprises at least one carboxylic acid function. Preferably, said organic compound is chosen from monocarboxylic acids, dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids. In this case, the organic compound is more preferably chosen from oxalic acid, malonic acid, glutaric acid, glycolic acid, lactic acid, tartronic acid, citric acid, acid tartaric, pyruvic acid and y-ketovaleric acid.
    In an embodiment according to the invention, said organic compound comprises at least one alcohol function. Preferably, said organic compound is chosen from:
    - organic compounds comprising a single alcohol function;
    - organic compounds comprising two alcohol functions;
    - the organic compounds chosen from diethylene glycol, triethylene glycol, tetraethylene glycol, or a polyethylene glycol corresponding to the formula H (OC 2 H 4 ) n OH with n greater than 4 and having an average molar mass less than 20,000 g / mol;
    - the monosaccharides of crude formula C n (H 2 O) p with n between 3 and 12;
    - disaccharides, trisaccharides, or monosaccharide derivatives.
    In this case, the organic compound is more preferably chosen from methanol, ethanol, phenol, ethylene glycol, propane-1,3-diol, butane-1,4diol, pentane-1,5- diol, hexane-1,6-diol, glycerol, xylitol, mannitol, sorbitol, pyrocatechol, resorcinol, hydroquinol, diethylene glycol, triethylene glycol, polyethylene glycol having an average molar mass less than 600 g / mol, glucose, mannose, fructose, sucrose, maltose, lactose, in any of their isomeric forms.
    In an embodiment according to the invention, said organic compound comprises at least one ester function.
    Preferably, said organic compound is chosen from:
    - linear or cyclic or cyclic or unsaturated esters of carboxylic acid;
    - organic compounds comprising at least two esters of carboxylic acid functions;
    - organic compounds comprising at least one ester function of carboxylic acid and at least one second functional group chosen from alcohols, ethers, ketones, aldehydes;
    - cyclic or linear esters of carbonic acid;
    - linear diesters of carbonic acid.
    In this case, the organic compound is more preferably chosen from yvalerolactone, methyl laurate, dialkyl succinate C1-C4 and more particularly dimethyl succinate, dimethyl malate, an acetoacid and propylene carbonate.
    In an embodiment according to the invention, said organic compound comprises at least one amide function.
    Preferably, said organic compound is chosen from:
    - acyclic amides comprising one or two amide functions;
    - cyclic amides or lactams;
    - organic compounds comprising at least one amide function and one carboxylic acid function or one alcohol function;
    - organic compounds comprising at least one amide function and an additional nitrogen heteroatom.
    In this case, the organic compound is more preferably chosen from formamide, N-methylformamide, Ν, Ν-dimethylformamide, N-ethylformamide, Ν, Ν-diethylformamide, acetamide, N-methylacetamide, N , Ndimethylmethanamide, Ν, Ν-diethylacetamide, Ν, Ν-dimethylDrooionamide, propanamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, γ-lactam, caprolactam, acetylleucine, N acid -acetylaspartic, aminohippuric acid, N-acetylglutamic acid, 4-acetamidobenzoic acid, lactamide, glycolamide, urea, N-methylurea, Ν, Ν'-dimethylurea, 1,1- dimethylurea, tetramethylurea according to any one of their isomeric forms.
    The organic sulfur-containing compound may be one or more chosen from compounds comprising one or more chemical functions chosen from a thiol, thioether, sulfone or sulfoxide function. By way of example, the organic sulfur-containing compound may be one or more chosen from the group consisting of thioglycolic acid, 2-hydroxy-4-methylthiobutanoic acid, a sulfonated derivative of a benzothiophene or a sulfoxide derivative of a benzothiophene.
    The first variant of the process for preparing the capture mass comprises several modes of implementation when it is desired to add the organic compound. They are distinguished in particular by the order of introduction of the organic compound and of the nickel precursor, it is possible for the organic compound to be brought into contact with the support either after the nickel precursor is brought into contact with the support, or before the bringing the nickel precursor into contact with the support, ie at the same time as bringing the nickel into contact with the support.
    In an embodiment according to the invention, steps i) and i ’) of the method according to the invention are carried out simultaneously.
    In another embodiment according to the invention, step i) of the method according to the invention is carried out before step i ’).
    In yet another embodiment according to the invention, step i ’) of the method according to the invention is carried out before step i).
    Each step i) and i ') of contacting 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 '1) respectively, all the possible combinations of implementation of steps i) and i') being included within the scope of the invention.
    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 step of bringing the nickel precursor into contact with the support, a step of bringing the organic compound into contact with the support, or a step of contacting the precursor of nickel and organic compound simultaneously with the support, the impregnated support can be left to mature, optionally 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.
    Second variant: preparation of the ammonia capture mass
    According to a second variant, the capture mass according to the invention 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 ammonium ions and containing at least one nickel precursor;
    ii) a step of drying said impregnated support at a temperature below 250 ° C, so as to obtain a dried capture mass;
    v) a step of sulfurization of the capture mass.
    According to step i) of this second variant of the process according to the invention, the support is brought into contact with a solution containing ammonium ions and comprising the salt (s) of the precursor (s) of the active phase based on nickel at least partially in the dissolved state.
    The term “solution containing ammonium ions” means any water / ammonia mixture or an aqueous solution prepared by dissolving one or more ammonium salts such as ammonium carbonate or ammonium hydrogen carbonate or ammonium bicarbonate in a water / ammonia mixture. Said nickel precursor is introduced into the solution containing ammonium ions by introducing a nickel salt, for example nickel carbonate, nickel chloride, nickel sulphate, nickel hydroxide or nickel hydroxycarbonate. Advantageously used as nickel precursor, nickel carbonate, nickel hydroxide or nickel hydroxycarbonate.
    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 else by deposition - precipitation, according to methods well known to those skilled in the art.
    Preferably, said step i) is carried out by dry impregnation, which consists in bringing the support of the capture mass 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.
    The quantities of nickel precursor (s) introduced into the solution are chosen such that the total nickel content, expressed as the nickel element, is between 5 and 65% by weight, preferably between 8 and 55% by weight, so preferred between 12 and 40% by weight, and particularly preferably between 12 and 34% by weight relative to the total mass of the capture mass. The nickel contents, expressed in nickel element, are generally adapted to the targeted arsenic capture as described above in the paragraph of the description of the capture mass.
    Any other additional element can be introduced during this step. When it is desired to introduce phosphorus, a solution of phosphoric acid can be introduced into the impregnation solution.
    Once the active phase is introduced into the support according to the two variants (organic compound or ammonia route), a drying step is carried out.
    Step ii) Drying of the impregnated support
    According to the invention, the impregnated support obtained at the end of step i), or, when an organic compound has been introduced obtained at the end of step i) or ij, undergoes a drying step il) 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.
    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.
    A dried capture mass is obtained.
    Step iii) Heat treatment of the dried capture mass (optional)
    The capture mass thus dried can then undergo an additional heat treatment step iii) at a temperature between 250 and 1000 ° C and preferably between 250 and 750 ° C, for a period typically between 15 minutes and 10 hours, under an inert atmosphere or an atmosphere containing oxygen, in the presence of water or not.
    “Thermal or hydrothermal treatment” is understood to mean temperature treatment respectively without the presence or presence of water. In the latter case, contact with water vapor can take place at atmospheric pressure or autogenous pressure (autoclaving). Several combined cycles of thermal or hydrothermal treatments can be carried out. After this or these treatments, the capture mass precursor comprises nickel in oxide form, that is to say in NiO form.
    In the case of hydrothermal treatment, 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.
    A calcined collection mass is obtained.
    Step iv) reduction treatment of the capture mass (optional)
    Prior to the sulfurization of the capture mass, at least one step of reducing treatment is optionally carried out in the presence of a reducing gas after steps ii) or iii) so as to obtain a capture mass comprising nickel at least partially under metallic form. This treatment makes it possible to form metallic particles, in particular nickel in the zero-value state. The reducing gas is preferably hydrogen. Hydrogen can be used pure or as a mixture (for example a hydrogen / nitrogen, hydrogen / argon, hydrogen / methane mixture). In the case where hydrogen is used as a mixture, all the proportions are possible.
    Said reducing treatment is preferably carried out at a temperature between 120 and 500 ° C, preferably between 150 and 450 Ό. 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.
    A reduced capture mass is obtained.
    Step v) Sulfurization of the capture mass
    After step ii) or after optional steps iii) and iv), the product obtained (dried, calcined or reduced capture mass) must be sulfurized so as to form nickel sulfide. This sulphurization is carried out by methods well known to those skilled in the art, and advantageously under a sulpho-reducing atmosphere in the presence of hydrogen and hydrogen sulphide. Sulfurization is carried out by injecting onto the capture mass a stream containing H 2 S and hydrogen, or else a sulfur compound capable of decomposing into H 2 S in the presence of the capture mass and the hydrogen. Polysulphides such as dimethyldisulphide are precursors of H 2 S commonly used to sulphide the capture masses. The temperature is adjusted so that the H 2 S reacts with the nickel to form nickel sulfide. This sulfurization can be carried out in situ or ex situ (inside or outside the reactor of the capture process). Advantageously, it is carried out ex-situ. Generally it is carried out at temperatures between 200 and 600 ° C and more preferably between 250 and 500 ° C. To be active, the nickel must preferably be substantially sulfurized. The operating conditions of the sulfurization, in particular the nature of the sulfurizing agent, the H 2 S / hydrogen ratio, the temperature and the duration of the sulfurization will preferably be adapted as a function of the product obtained after step ii) or after the optional steps iii) and iv), so as to obtain good sulfurization of the nickel, that is to say that the nickel is largely and preferably entirely sulfurized. The active phase therefore consists of nickel sulfide particles of size less than or equal to 20 nm.
    After sulphurization, the capture mass according to the invention is ready for use in a process for the adsorption of arsenic and of hydrodesulphurization of a hydrocarbon feed comprising unsaturated compounds.
    Ace capture process
    Another object of the invention is a process for the capture of organometallic impurities such as heavy metals, silicon or phosphorus, and more particularly arsenic, contained in a hydrocarbon feedstock using the capture mass defined above. , wherein said capture mass is brought into contact with the hydrocarbon feedstock in the presence of hydrogen. In the sense of the present invention, the capture method according to the invention is a method of at least partial capture of arsenic and optionally silicon of the hydrocarbon feedstock in the presence of hydrogen to produce an effluent containing heavy metals and in particular reduced arsenic, with a limited loss of octane number. The capture process according to the invention makes it possible to eliminate the arsenic and also to limit the rate of hydrogenation of the monoolefins. The rate of hydrogenation of olefins is advantageously less than 50%, preferably less than 30%, and even more preferably less than 20%.
    The hydrocarbon feed to be treated is a catalytic cracking gasoline from catalytic cracking, thermal cracking or steam cracking units. The process can also be applied to the treatment of mixtures of direct distillation gasolines which may contain heavy metals obtained from crude oil with cracked gasolines comprising mono-olefins and diolefins. Preferably, the hydrocarbon feed to be treated is a catalytic cracking gasoline comprising between 5% and 60% by weight of mono-olefins, between 50 ppm and 6000 ppm by weight of sulfur-containing compounds and between 10 and 1000 ppb by weight of arsenic. The sulfur compounds contained in the hydrocarbon feedstock to be treated can be organic sulfur compounds such as, for example, mercaptans, thiophenic, benzothiophenic and other aromatic sulfur compounds, disulfide compounds, etc. The arsenic compounds contained in the hydrocarbon feed to be treated can be organic arsenic compounds such as, for example, trimethylarsine or triethylarsine. Mono-olefins denote hydrocarbon molecules having a single carbon-carbon double bond and diolefins are hydrocarbon molecules comprising at least two carbon-carbon double bonds. The mono-olefins and the diolefins can be linear, branched and / or cyclic hydrocarbon molecules.
    The capture mass according to the invention is advantageously used under operating conditions such that the rate of capture of arsenic is maximized, while limiting the rate of hydrogenation of olefins. The contacting is generally carried out at a temperature between 200 and 400 ° C, at a pressure between 0.2 and 5 MPa and with a ratio of the flow rate of hydrogen to the flow rate of hydrocarbon feedstock between 50 and 800 Nm3 / m3. The hydrogen used can come from any source of hydrogen. Preferably, fresh hydrogen from the refinery and / or recycled hydrogen from a hydrodesulfurization unit, preferably from the hydrodesulfurization unit of the hydrocarbon fraction to be purified, are used.
    Several reactor technologies can be envisaged to carry out the capture of arsenic from a hydrocarbon feedstock in the presence of the capture mass according to the invention. The most classic and widespread technology is fixed bed technology. In this case, a reactor is loaded with the capture mass according to the invention and a hydrodesulfurization catalyst, operating in adsorption of arsenic and in hydrodesulfurization, in principle until the appearance of arsenic in the effluent. exit (phenomenon known to those skilled in the art under the term piercing). In some cases the total quantity of poisoned capture mass can be replaced by an equivalent quantity of fresh capture mass. The choice of a technology for replacing the capture mass according to the invention is not considered in the context of the present invention as a limiting element. The capture mass can be used in a moving bed reactor, that is to say that the used capture mass is drawn off continuously, and replaced by fresh capture mass. This type of technology makes it possible to maintain the capture of arsenic by the capture mass and to avoid the piercing of the latter in the effluents produced. Among other solutions, let us cite the use of reactors in an expanded bed which also allows withdrawal and continuous topping up of the capture mass in order to maintain the hydrodesulfurization activity of the capture mass.
    The capture process according to the invention is preferably coupled with at least one step of catalytic hydrodesulfurization or additional selective hydrogenation which is carried out on the effluent from contacting with the capture mass according to the invention. Thus, the step of treatment of the hydrocarbon feedstock by the capture mass is considered to be a pretreatment which in particular makes it possible to preserve the catalytic activity of the catalyst used in the step of hydrodesulfurization or subsequent selective hydrogenation. Thus, the capture process according to the invention comprises one or more other complementary stages of hydrodesulfurization or selective hydrogenation in which (s) the effluent from contacting the charge is brought into contact. hydrocarbon with the capture mass according to the invention, with at least one other hydrodesulfurization or selective hydrogenation catalyst of the diolefins present in the olefin feed. The so-called (additional) hydrodesulfurization step (s) makes it possible to eliminate the residual sulfur compounds contained in the effluent depleted in arsenic and with a lower sulfur content. Some of these residual sulfur-containing compounds can result from the addition of H 2 S to the olefins present in the feed. H 2 S can form during the contacting of the hydrocarbon charge with the capture mass, that is to say, during the capture of arsenic. The said (additional) hydrodesulfurization step (s) is (are) used when the effluent resulting from the contacting of the hydrocarbon feedstock with the capture mass generally has a sulfur content greater than 10 ppm and that it is necessary to produce gasolines with low sulfur content meeting the current specifications which are in many countries below 10 ppm. The effluent freed of arsenic and of part of the sulfur compounds is then treated in at least one of said complementary steps of selective hydrodesulfurization. In the said step (s), said effluent is brought into contact with at least one other hydrodesulfurization catalyst under operating conditions which may be identical or different from those of bringing the hydrocarbon charge into contact with the mass of capture.
    The catalyst (s) used in the said (additional) hydrodesulfurization step (s) is (are) protected from deactivation by the arsenic present in the feed thanks to the capture mass according to the invention. Thus highly selective hydrodesulfurization catalysts which are sensitive to the presence of arsenic can be used in the (said) additional step (s) of hydrodesulfurization. Any hydrodesulfurization catalyst can be used in the said (s) complementary step (s) of hydrodesulfurization. Preferably, catalysts are used which have a high selectivity with respect to hydrodesulfurization reactions with respect to the hydrogenation reactions of olefins. Such catalysts comprise at least one porous amorphous inorganic support, a group VIB metal, a group VIII metal. The group VIB metal is preferably molybdenum or tungsten and the group VIII metal is preferably nickel or cobalt. The support is generally selected from the group consisting of aluminas, silica, silica-aluminas, silicon carbide, titanium oxides alone or in admixture with alumina or silica alumina, magnesium oxides alone or as a mixture with alumina or silica alumina. Preferably, the support is selected from the group consisting of aluminas, silica and silica-aluminas. Preferably, the hydrodesulfurization catalyst used in the complementary hydrodesulfurization step (s) has the following characteristics:
    the content of elements of group VIB is between 1 and 20% by weight of oxides of elements of group VIB;
    the content of elements of group VIII is between 0.1 and 20% by weight of oxides of elements of group VIII;
    - the molar ratio (elements of group VIII / elements of group VIB) is between 0.1 and 0.8.
    A very preferred hydrodesulfurization catalyst comprises cobalt and molybdenum and has the characteristics mentioned above. Furthermore, the hydrodesulfurization catalyst can comprise phosphorus. In this case, the phosphorus content is preferably between 0.1 and 10% by weight of P 2 O 5 relative to the total weight of catalyst and the phosphorus molar ratio on elements of group VIB is greater than or equal to 0.25 , preferably greater than or equal to 0.27.
    In the so-called additional hydrodesulfurization step (s), the arsenic-depleted effluent resulting from the contacting of the hydrocarbon feedstock with the capture mass according to the invention is brought into contact with at least one other selective hydrodesulfurization catalyst under the following operating conditions:
    - A temperature between about 210 ° C and about 410 ° C, preferably between 240 and 360 ° C;
    - a total pressure between 0.2 and 5 MPa and more preferably between 0.5 and about 3 MPa;
    a ratio of the volume of hydrogen per volume of hydrocarbon feedstock, between 50 and 800 Nm 3 / m 3 and more preferably between 60 and 600 Nm 3 / m 3 . In a variant of the process according to the invention, the operating conditions for bringing the hydrocarbon feedstock into contact with the capture mass according to the invention are identical to those used in the said stage (s) ) additional hydrodesulfurization.
    According to another embodiment, the step of hydrotreating the effluent from the capture step by means of the capture mass according to the invention is a selective hydrogenation which allows the hydrogenation of diolefins to olefins and optionally unsaturated sulfur compounds but also the transformation (weighing down) of light sulfur compounds (ie having a temperature lower than that of thiophene) into sulfur compounds whose temperature is higher than that of thiophene, for example by adding mercaptans to olefins. This hydrogenation step is carried out in the presence of hydrogen and of a catalyst containing at least one metal from group Vlb and at least one non-noble metal from group VIII deposited on a porous support. Preferably, a catalyst is used, of which:
    the content by weight of oxide of the element of group Vlb is between 6 and 18% relative to the weight of the catalyst;
    the content by weight of oxide of the element of group VIII is between 4 and 12% relative to the weight of the catalyst;
    - The specific surface of the catalyst is between 200 and 270 m 2 / g;
    the density of the element of group Vlb, expressed as being the ratio between said content by weight of oxide of the element of group Vlb and the specific surface of the catalyst, is between 4 and 6.10-4 g / m 2 ;
    - The molar ratio between the metal of group VIII and the metal of group Vlb is between 0.6 and 3 mol / mol.
    The metal of group Vlb is preferably chosen from molybdenum and tungsten, very preferably the metal of group Vlb is molybdenum. The group VIII metal is preferably nickel and / or cobalt, very preferably nickel. Hydrogen is generally introduced in small excess, up to 5 moles per mole, compared to the stoichiometry, necessary to hydrogenate the diolefins (one mole of hydrogen per mole of diolefin). The mixture consisting of petrol and hydrogen is brought into contact with the catalyst at a pressure of between 0.5 and 5 MPa, a temperature between 80 and 220 ° C., with a liquid space velocity (LHSV) of between 1 and 10 h -1 , the liquid space velocity being expressed in liters of charge per liter of catalyst and per hour (L / Lh). In a variant of the process according to the invention, the capture mass according to the invention can be placed in the position of a guard bed of one or more reactor (s) containing the catalyst (s) used in the (es) called (s) step (s) complementary (s) hydrodesulfurization and / or selective hydrogenation. In another variant of the method according to the invention, the capture mass according to the invention is placed in a so-called capture reactor. This reactor is separated and is placed upstream of the reactor (s) containing the catalyst (s) used in the said step (s) complementary (s) hydrodesulfurization and / or selective hydrogenation. In all the variants of the process according to the invention, implementing at least one additional hydrodesulfurization and / or selective hydrogenation step, the volume ratio of the capture mass according to the invention relative to the volume of (des ) catalyst (s) used in said step (s) of additional hydrodesulfurization and / or selective hydrogenation is advantageously between 4 and 50%, preferably between 5 and 40 %, more preferably between 5 and 35%.
    The invention is illustrated by the following examples.
    Example 1: Mass prepared by impregnation according to the state of the art (Comparative)
    In this example, the solid A is prepared by double dry impregnation of the alumina support via an aqueous solution of nickel nitrate. Drying at 120 ° C followed by calcination at 450 ° C are carried out after each impregnation. The solid is then sulfurized according to the protocol described.
    Example 2 Mass prepared in the presence of citric acid (according to the invention)
    In this example, the solid B is prepared by dry impregnation of the alumina support via a solution of nickel nitrate in the presence of citric acid (AC), with a molar ratio AC / Ni = 0.3. Drying at 120 ° C followed by calcination at 450 ° C are carried out. The solid is then sulfurized according to the protocol described.
    Example 3: Mass Prepared by the Ammonia Route (According to the Invention)
    In this example, the solid C is prepared by dry impregnation of the alumina support via an ammoniacal solution of nickel carbonate. Drying at 150 ° C followed by final calcination at 280 ° C are carried out. The solid is then sulfurized according to the protocol described.
    Example 4: Mass Prepared by the Ammonia Route (According to the Invention)
    In this example, the solid D is prepared by a double dry impregnation of the alumina support via an ammoniacal solution of nickel carbonate. Drying at
    150 ° C followed by calcination at 280 ° C are carried out after each impregnation. The solid is then sulfurized according to the protocol described.
    The characteristics of solids A, B, C and D indicated in the table below are obtained by the following techniques:
    - BET Specific Surface: Adsorption / Desorption of nitrogen at 77 K
    - Nickel content: Fluorescence X (FX)
    - Identification of the Phases and Sizes of the Crystallites: X-ray diffraction (XRD) according to the method described.
    Example 5: Evaluation of the performance of the capture masses with respect to the capture of Arsenic.
    The performance of a nickel-based capture mass is carried out by following the rate of disappearance of an arsenic compound dissolved in a model charge brought into contact with the solid, after sulfurization, during a reaction carried out in static mode in a stirred and closed autoclave reactor, at a temperature of 210 ° C., in the presence of hydrogen and under a total pressure of 35 bar (3.5 MPa).
    A model load is used for all tests. It is composed of a volume of 250 cm 3 of toluene, or 217 g, and of triphenyl-arsine (AsPh 3 ), at a content of 500 ppm mas in equivalent “As”, or approximately 1.45 mmol of As . The mass of solid used is adjusted so as to obtain an initial Ni / As molar ratio of 5 in order to take account of the differences in nickel content on the different solids.
    Prior to its introduction into the reactor, the solid is sulfurized ex situ under a flow of an H 2 / H 2 S mixture at 15% vol H 2 S and at a temperature of 350 ° C for 2 hours, then cooled under pure hydrogen with a 2 hour level at 200 ° C.
    Mass AT(comparative) B(according to the invention) C (according to the invention) D(according to the invention) preparation classic impregnation citric acid ammonia route ammonia route Sbet support (m 2 .g _1 ) 152 152 152 180 Ni content (%) 20 13.4 13.4 19.5 mean diameter of nickel sulfide crystallites (nm) 27 8 9.5 11 relative speed of disappearance of Ace 100 121 145 156
    Example 6: Evaluation of the hydrogenation performance of olefins
    A catalytic cracking gasoline (FCC or Fluid Catalytic Cracking according to English terminology), the characteristics of which are collated in the table below, is brought into contact with the various capture masses. The reaction is carried out in a crossed-bed type reactor under the following conditions: P = 2 MPa, H 2 / HC = 360 liters / liters of hydrocarbon feedstock, VVH = 10h ' 1 , the temperature being fixed at 250 ° C. The effluents are analyzed by gas chromatography to determine the hydrocarbon concentrations.
    S ppm 392 Aromatic% wt 41.3 Paraffins% wt 27.2 Naphthenic% wt 11.0 Olefins% wt 20.5 T 5 ° C 62 T95 ° c 225
    For all of the masses tested, the hydrogenation of olefins is extremely low and less than 2% by weight relative to the total weight of olefins.
    权利要求:
    Claims (15)
    [1" id="c-fr-0001]
    1. Capture mass comprising an active phase based on nickel sulphide particles of size less than or equal to 20 nm, said active phase not comprising other metallic elements of group VIB or group VIII, deposited on a porous support chosen from the group consisting of aluminas, silica, silica aluminas, titanium oxides alone or in admixture with alumina or silica alumina, magnesium oxides alone or in admixture with alumina or silica alumina.
    [2" id="c-fr-0002]
    2. Capture mass according to claim 1, in which the active phase consists of nickel sulphide particles of size less than or equal to 20 nm.
    [3" id="c-fr-0003]
    3. Capture mass according to one of the preceding claims, in which the size of the nickel sulfide particles is between 1 and 12 nm.
    [4" id="c-fr-0004]
    4. Capture mass according to one of the preceding claims, in which the nickel content, expressed as a nickel element, is between 5 and 65% by weight relative to the total mass of the capture mass.
    [5" id="c-fr-0005]
    5. Capture mass according to one of the preceding claims, in which the nickel content, expressed as a nickel element, is between 12 and 34% by weight relative to the total mass of the capture mass.
    [6" id="c-fr-0006]
    6. Capture mass according to one of the preceding claims, in which the total pore volume is greater than or equal to 0.45 ml / g and in which the BET specific surface is at least 40 m 2 / g.
    [7" id="c-fr-0007]
    7. Method for preparing the capture mass according to one of claims 1 to 6 comprising the following steps:
    i) a step of bringing said support into contact with at least one solution containing at least one nickel precursor, i ') a step of bringing said support into contact with at least one solution containing at least one organic compound comprising oxygen and / or nitrogen and / or sulfur, steps i) and i ') being carried out separately, in an indifferent order, or simultaneously, ii) a step of drying said impregnated support at a temperature below 250 ° C. , so as to obtain a dried capture mass,
    v) a step of sulfurization of the capture mass.
    [8" id="c-fr-0008]
    8. Method for preparing the capture mass according to one of claims 1 to 6 comprising the following steps:
    i) a step of bringing said support into contact with at least one solution containing ammonium ions and containing at least one nickel precursor, ii) a step of drying said impregnated support at a temperature below 250 ° C., so as to obtain a dried capture mass,
    v) a step of sulfurization of the capture mass.
    [9" id="c-fr-0009]
    9. Preparation process according to one of claims 7 or 8 further comprising at least one of the following steps:
    iii) a step of heat treatment of the dried capture mass;
    iv) a step of reducing treatment of the capture mass, dried or resulting from step iii).
    [10" id="c-fr-0010]
    10. Method for capturing organometallic impurities contained in a hydrocarbon feedstock using the capture mass according to one of claims 1 to 6 in which said capture mass is brought into contact with the load to be treated and a flow of hydrogen at a temperature between 200 and 400 ° C, a pressure between 0.2 and 5 MPa and a ratio of the flow rate of hydrogen to the flow rate of hydrocarbon feedstock between 50 and 800 Nm 3 / m 3 .
    [11" id="c-fr-0011]
    11. Capture process according to the preceding claim, in which the organometallic impurities are chosen from organometallic impurities of heavy metals, silicon, phosphorus and arsenic.
    [12" id="c-fr-0012]
    12. Capture process according to claim 10, in which the charge to be treated is a catalytic cracking gasoline containing between 5% and 60% by weight of olefins, 50 ppm to 6000 ppm by weight of sulfur, as well as traces of arsenic in contents between 10 ppb and 1000 ppb weight.
    [13" id="c-fr-0013]
    13. A capture method according to one of claims 10 to 12, wherein said capture mass is placed in a reactor located upstream of a hydrodesulfurization unit containing a hydrodesulfurization catalyst and / or a d selective hydrogenation containing a catalyst for the selective hydrogenation of said charge.
    [14" id="c-fr-0014]
    14. Collection process according to one of claims 10 to 12, in which said collection mass is placed inside a hydrodesulfurization and / or selective hydrogenation reactor of said feed, at the head of said tank. reactor.
    [15" id="c-fr-0015]
    15. The capture method according to one of claims 13 and 14, wherein the volume ratio of said capture mass relative to the volume of said hydrodesulfurization and / or selective hydrogenation catalyst is between 4 and 50%.
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    同族专利:
    公开号 | 公开日
    WO2019197351A1|2019-10-17|
    FR3080048B1|2020-07-31|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3328316A|1966-01-24|1967-06-27|Chevron Res|Method of depositing metals on siliceous supports|
    US4046674A|1976-06-25|1977-09-06|Union Oil Company Of California|Process for removing arsenic from hydrocarbons|
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    FR2923837A1|2007-11-19|2009-05-22|Inst Francais Du Petrole|TWO-STAGE DESULFURATION PROCESS OF OLEFINIC ESSENCES INCLUDING ARSENIC.|
    WO2015189190A1|2014-06-13|2015-12-17|IFP Energies Nouvelles|Mesoporous and macroporous catalyst made from nickel having a macroporous median diameter of between 50 nm and 200 nm and use of same in hydrocarbon hydrogenation|FR3105931A1|2020-01-06|2021-07-09|IFP Energies Nouvelles|CATALYST BASED ON 2-HYDROXY-BUTANEDIOIC ACID OR 2-HYDROXY-BUTANEDIOIC ACID ESTERS AND ITS USE IN A HYDROTREATMENT AND / OR HYDROCRACKING PROCESS|FR2617497B1|1987-07-02|1989-12-08|Inst Francais Du Petrole|PROCESS FOR THE REMOVAL OF ARSENIC COMPOUNDS FROM LIQUID HYDROCARBONS|
    US5024683A|1990-06-12|1991-06-18|Phillips Petroleum Company|Sorption of trialkyl arsines|
    FR2701269B1|1993-02-08|1995-04-14|Inst Francais Du Petrole|Process for the elimination of arsenic in hydrocarbons by passage over a presulfurized capture mass.|
    FR2797639B1|1999-08-19|2001-09-21|Inst Francais Du Petrole|PROCESS FOR PRODUCING LOW SULFUR ESSENCE|
    FR2811328B1|2000-07-06|2002-08-23|Inst Francais Du Petrole|PROCESS INCLUDING TWO STAGES OF GASOLINE HYDRODESULFURATION AND AN INTERMEDIATE REMOVAL OF THE H2S FORMED DURING THE FIRST STAGE|
    US6759364B2|2001-12-17|2004-07-06|Shell Oil Company|Arsenic removal catalyst and method for making same|
    FR2876113B1|2004-10-06|2008-12-12|Inst Francais Du Petrole|METHOD OF SELECTIVELY CAPTRATING ARSENIC IN ESSENCE RICH IN SULFUR AND OLEFINS|
    WO2016007686A1|2014-07-11|2016-01-14|Shell Oil Company|A hydroprocessing catalyst for treating a hydrocarbon feed having an arsenic concentration and a method of making and using such catalyst|
    CN105562000B|2015-12-16|2019-01-22|沈阳三聚凯特催化剂有限公司|A kind of arsenic removal catalyst and the preparation method and application thereof|
    CN107011939B|2017-06-02|2019-01-22|钦州学院|A kind of method of distillate hydrogenation dearsenification|FR3106506A1|2020-01-28|2021-07-30|IFP Energies Nouvelles|Finishing hydrodesulfurization process in the presence of a catalyst obtained by additivation|
    法律状态:
    2019-04-25| PLFP| Fee payment|Year of fee payment: 2 |
    2019-10-18| PLSC| Publication of the preliminary search report|Effective date: 20191018 |
    2020-04-29| PLFP| Fee payment|Year of fee payment: 3 |
    2022-01-07| ST| Notification of lapse|Effective date: 20211205 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1853149|2018-04-11|
    FR1853149A|FR3080048B1|2018-04-11|2018-04-11|ARSENIC CAPTURE MASS BASED ON NICKEL SULPHIDE NANOPARTICLES|FR1853149A| FR3080048B1|2018-04-11|2018-04-11|ARSENIC CAPTURE MASS BASED ON NICKEL SULPHIDE NANOPARTICLES|
    PCT/EP2019/058838| WO2019197351A1|2018-04-11|2019-04-08|Mass for removing arsenic made of nickel sulphide nanoparticles|
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