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    • 专利摘要:
    The present invention relates to a process for adding an organic compound to a porous solid in which an initial batch of porous solid rich in an organic compound is placed in an open or closed enclosure with a second batch of porous solid. poor in said organic compound. The step of bringing the porous solids into contact is carried out under conditions of temperature, pressure and duration such that a fraction of said organic compound is transferred by gas from the first batch of porous solid to the second batch of porous solid.
    公开号:FR3065888A1
    申请号:FR1753922
    申请日:2017-05-04
    公开日:2018-11-09
    发明作者:Florent Guillou；P-Louis Carrette；Bertrand Guichard
    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 3 065 888 - A1 © PROCESS FOR THE INDIRECT ADDITION OF AN ORGANIC COMPOUND TO A POROUS SOLID. The present invention relates to a process for adding an organic compound to a porous solid in which there is brought into contact, in an open or closed enclosure, a first batch of porous solid rich in an organic compound with a second batch of porous solid poor in said organic compound. The step of bringing porous solids together is carried out under conditions of temperature, pressure and duration such that a fraction of said organic compound is transferred by gas from the first batch of porous solid to the second batch of porous solid.

    The present invention relates to a process for adding an organic compound to a porous solid, in particular to a porous catalyst support. The process according to the invention can be integrated into a process for the preparation of a heterogeneous catalyst called additive of an organic compound comprising a porous support on which is deposited at least one group VI metal and / or at least one group metal VIII.
    State of the art
    Conventional hydrotreatment catalysts generally comprise a support based on a metal oxide (for example aluminum) or a metalloid (for example silicon) and an active phase based on at least one metal from group VIB and / or at least one metal from group VIII in their oxide forms and optionally phosphorus. The preparation of these catalysts generally comprises a step of impregnating the metals and phosphorus on the support, optionally followed by a step of maturation, followed by drying and calcination allowing the active phase to be obtained in their forms. oxides. Before their use in a hydrotreatment and / or hydrocracking reaction, these catalysts are generally subjected to sulfurization in order to form the active species.
    The addition of an organic compound to the hydrotreatment catalysts to improve their activity has been recommended by those skilled in the art, in particular for catalysts which have been prepared by impregnation optionally followed by a maturation step, and followed by 'drying.
    Numerous documents describe the use of different ranges of organic compounds, such as nitrogen-containing organic compounds and / or oxygen-containing organic compounds.
    A family of compounds now well known in the literature relates to chelating nitrogen compounds (EP 181035, EP 1043069 and US 6,540,908) with, for example, ethylenediaminetetraacetic acid (EDTA), ethylenediamine, diethylenetriamine or nitrilotriacetic acid (NTA).
    In the family of organic compounds containing oxygen, the use of optionally etherified mono, or polyalcohols is described in documents WO96 / 41848, WO01 / 76741, US 4,012,340, US 3,954,673, EP 601722, and WO 2005/035691 . The prior art more rarely mentions compounds comprising ester functions (EP 1046424, WO2006 / 077326).
    There are also several patents which claim the use of carboxylic acids (EP 1402948, EP 482817). In particular, in document EP 482817, citric acid, but also tartaric, butyric, hydroxyhexanoic, malic, gluconic, glyceric, glycolic, hydroxybutyric acids have been described.
    The processes for preparing the additive catalysts generally use an impregnation step in which the organic compound is introduced, optionally in solution in a solvent, so as to fill all the porosity of the support impregnated or not with metal precursors in order to obtain a homogeneous distribution. This leads to using large amounts of compound or diluting the organic compound in a solvent. After impregnation, a drying step is then necessary to remove the excess compound or the solvent and thus release the porosity necessary for the use of the catalyst. In addition to the additional cost linked to the excess of the organic compound or to the use of a solvent, there is the cost of an additional step of preparation for drying, which consumes energy. During the drying step, the evaporation of the solvent can also be accompanied by a partial loss of the organic compound by vaporization and therefore a loss of catalytic activity.
    An object of the invention is to provide a process for adding an organic compound to a porous solid, in particular to a catalyst support or to a catalyst precursor and a process for preparing a catalyst which are simplified and less expensive to implement industrially.
    Summary of the invention
    A first object of the invention relates to a process for adding an organic compound to a porous solid comprising a step a) in which there is brought into contact, in a closed or open enclosure, a first batch of porous solid rich in a organic compound with a second batch of porous solid poor in said organic compound, step a) being carried out under temperature, pressure and duration conditions such that a fraction of said organic compound is transferred by gas from the first batch of porous solid to the second batch of porous solid.
    In the context of the invention, the term contacting designates the fact that the solids are present at the same time in the enclosure without there necessarily being physical contact of the two batches of solids.
    According to the invention, the term rich in organic compound translates the fact that the solid contains more than 50% of the total amount of said organic compound used in step a), preferably at least 60%, preferably at least 80%, preferably at least 90% and preferably 100%. According to one embodiment, the porous solid rich in organic compound contains 100% of the total amount used in step a) and the second batch of solid poor in organic compound therefore contains 0% of the total amount in said compound organic.
    Advantageously, step a) of contacting is carried out at a temperature below the boiling temperature of the organic compound.
    According to one embodiment, step a) of bringing said batches together is carried out by bringing the first and second batches of porous solid into physical contact. For example, it is carried out in a storage or transport container.
    According to an alternative embodiment, step a) of bringing said batches together is carried out in an enclosure comprising two separate compartments in gas communication, said zones being capable of containing the first and second batches of porous solid respectively so that the support batches are brought together without physical contact.
    In one embodiment, the following steps are carried out:
    a ') an initial batch of porous solid is provided, b') a heterogeneous impregnation of the initial batch of porous solid with the organic compound in liquid form so as to provide a first batch of porous solid rich in organic compound and a second batch of porous solid poor in organic compound, c ') said batches of porous solids from step b') are left in the presence, under temperature, pressure and duration conditions such that a fraction of said organic compound is transferred by gas from the first batch of porous solid to the second batch of porous solid.
    In another embodiment, the following steps are carried out:
    a) an initial batch of porous solid is provided;
    b) separating said initial batch into a first and a second separate fraction, c) introducing into the first solid fraction from step b) the organic compound in liquid form so as to provide the first batch of solid rich in organic compound;
    d) the first batch of support rich in organic compound from step c) is brought into contact with the second solid fraction from step b) under temperature, pressure and duration conditions such as fraction of said organic compound is transferred by gas from the first batch of porous solid to the second batch of porous solid. .
    In the context of the invention, step a) can be carried out in the presence of a circulation of a carrier gas.
    According to one embodiment, at least one fraction of the solid from step a) of contacting is separated and said fraction is recycled in step a).
    Step a) is preferably carried out at an absolute pressure of between 0 and 1 MPa.
    According to the invention, the porous solid can be chosen from a catalyst support and a catalyst support further comprising at least one metal from group VIB and / or at least one metal from group VIII. Preferably the porous support is based on a metal oxide and / or a metalloid. For example, the porous support is based on alumina and / or silica.
    The process for adding the organic compound according to the invention can be integrated into a production line for a catalyst called an additive of an organic compound.
    The present invention therefore relates to a process for the preparation of a catalyst comprising a porous support, at least one metal from group VIB and / or at least one metal from group VIII and at least one organic compound. The preparation process comprising at least the following steps:
    i) the process of adding at least one organic compound according to any one of the preceding claims is carried out by bringing the porous support into contact with a porous solid containing said organic compound so as to provide a batch of porous support containing said organic compound, ii) at least one group VIB metal and / or at least one group VIII metal is deposited on the porous support by bringing the support into contact with a solution containing at least one precursor of said group VIII metal (s) and / or at least one precursor of said group VIB metal (s), iii) the porous support from step ii) is dried, step i) being carried out separately before or after steps ii) and iii).
    The process for adding the organic compound according to the invention can be implemented one or more times in a production chain of an additive catalyst to effect the introduction of one or more organic compounds before the impregnation step of the active metallic phase, and / or to allow the introduction of one or more organic compounds on a porous support already containing an active metallic phase which can optionally be sulphurized.
    According to a first embodiment A) of the process for the preparation of a catalyst additive with an organic compound, the porous support is subjected to an impregnation step with a solution comprising at least one metal from group VIB and / or at least a group VIII metal so as to deposit an active metallic phase (step ii). The porous support impregnated with the active metallic phase is optionally subjected to a maturation step and is then dried (step iii) in order to remove the solvent supplied by step ii). The porous support containing the active and dried metallic phase is subjected to a step of adding the organic compound according to step i) so as to provide a catalyst additive to said organic compound. The catalyst support used in this embodiment A) of the preparation process may also already contain one or more organic compounds different from that which is used in step i). This or these additional organic compounds may have been incorporated into the porous catalyst support by means of the addition process according to the invention or by any other method known to those skilled in the art.
    According to another embodiment B) of preparation, the support not containing an active metallic phase is first subjected to a step of adding the organic compound according to step i) so as to provide an additivated catalyst support, which is sent to the impregnation step of the active phase (step ii). This step may consist in bringing the additive-based support into contact with a solution containing at least one precursor of at least one group VIII metal and / or at least one precursor of at least one group VIB metal. The additive catalyst thus obtained is optionally left to mature and then subjected to a drying step (step iii) in order to remove the solvent supplied during the step of impregnating the metal precursors of the active phase. In this embodiment B), the porous support used may optionally already contain one or more organic compounds different from that used in step i), the additional organic compound (s) having been incorporated into the catalyst support by means of the addition method according to the invention or according to any other method known to those skilled in the art.
    It should be noted that in the context of the invention, step ii) of introduction of the metals can use a solution containing at least one precursor of the said Group VIII metal or metals and / or at least one precursor of the or said group VIB metals and in addition one or more organic compounds different from that of step i). According to the invention, the additive catalyst obtained at the end of steps i) to iii) described above can also be treated by a several subsequent steps in order to incorporate one or more other additional organic compounds different from that used in the 'step i). The incorporation of one or more other different additional organic compounds can be carried out by means of the addition process according to the invention or by any other method known to those skilled in the art. The other additional organic compound (s) can, for example, be introduced according to one of the embodiments described in document FR 3 035 008.
    The additive catalysts prepared according to the invention may contain as active phase one or more metals from group VIB and / or from group VIII. The preferred group VIB metals are molybdenum and tungsten and the preferred group VIII metals are non-noble elements and in particular cobalt and nickel. Advantageously, the active phase is chosen from the group formed by the combinations of the elements cobalt-molybdenum, nickel-molybdenum, nickel-tungsten or nickel-cobalt-molybdenum, or nickel-molybdenum tungsten.
    According to the invention, the catalysts generally have a total content of group VIB and / or group VIII metals greater than 6% by weight expressed as oxide relative to the total weight of dry catalyst.
    Preferably, the total content of metals of group VIB is between 5 and 40% by weight, preferably between 8 and 35% by weight, and more preferably between 10 and 32% by weight expressed as metal oxide of group VIB relative to the total weight of dry catalyst.
    The total content of group VIII metals is generally between 1 and 10% by weight, preferably between 1.5 and 9% by weight, and more preferably between 2 and 8% by weight expressed as metal oxide of group VIII relative to to the total weight of dry catalyst.
    The molar ratio of group VIII metals to group VIB metals in the catalyst is preferably between 0.1 and 0.8, preferably between 0.15 and 0.6 and even more preferably between 0.2 and 0.5.
    The catalyst can also include phosphorus as a dopant. The phosphorus content in said catalyst is preferably between 0.1 and 20% by weight expressed as P2O5, preferably between 0.2 and 15% by weight expressed as P2O5, and very preferably between 0.3 and 11% by weight expressed as P2O5 relative to the total weight of dry catalyst.
    The phosphorus molar ratio on the metals of group VIB in the catalyst is greater than or equal to 0.05, preferably greater than or equal to 0.07, preferably between 0.08 and 1, preferably between 0.01 and 0.9 and very preferably between 0.15 and 0.8.
    The catalyst can advantageously also contain at least one dopant chosen from boron, fluorine and a mixture of boron and fluorine. When the catalyst contains boron, the boron content is preferably between 0.1 and 10% by weight expressed as boron oxide, preferably between 0.2 and 7% by weight, and very preferably between 0.2 and 5% by weight relative to the total weight of the dry catalyst. When the catalyst contains fluorine, the fluorine content is preferably between 0.1 and 10% by weight expressed as fluorine, preferably between 0.2 and 7% by weight, and very preferably between 0.2 and 5 % by weight relative to the total weight of dry catalyst.
    The additive catalysts thus prepared are used in particular for hydrotreatment reactions of hydrocarbon feedstocks such as petroleum fractions or for the synthesis of hydrocarbons from synthesis gas. According to the invention, the term hydrotreatment includes in particular total or selective hydrogenation reactions, hydrodenitrogenation, hydrodesaromatization, hydrodesulfurization, hydrodeoxygenation, hydrodemetallization, and hydrocracking of hydrocarbon feedstocks.
    For hydrotreatment applications, the additive catalyst generally undergoes a sulfurization step. The fillers used in the hydrotreatment process are for example gasolines, gas oils, vacuum gas oils, atmospheric residues, vacuum residues, atmospheric distillates, vacuum distillates, heavy fuels, oils, waxes and paraffins, used oils, deasphalted residues or crudes, fillers from thermal or catalytic conversion processes, lignocellulosic fillers or fillers from biomass, taken alone or as a mixture. The operating conditions used in the processes implementing the hydrotreatment reactions of hydrocarbon feedstocks described above are generally the following: the temperature is advantageously between 180 and 450 ° C, and preferably between 250 and 440 ° C pressure is advantageously between 0.5 and 30 MPa, and preferably between 1 and 18 MPa, the hourly volume speed is advantageously between 0.1 and 20 h -1 and preferably between 0.2 and 5 h ' 1 , and the hydrogen / charge ratio expressed in volume of hydrogen, measured under normal conditions of temperature and pressure, per volume of liquid charge is advantageously between 50 l / l to 5000 l / l and preferably between 80 to 2000 l / l.
    Detailed description of the invention
    The subject of the present invention is a process for adding an organic compound to a porous solid which is, for example, a porous catalyst support or to a porous support which already contains at least one metal from group VIB and / or at least one metal of group VIII which will be designated by the term catalyst precursor in the rest of the description.
    The porous support is based on at least one oxide of a metal or a metalloid. Preferably the porous support is based on alumina or silica or silica-alumina.
    When the support is based on alumina, it contains more than 50% by weight of alumina. Preferably, the alumina is gamma alumina.
    Alternatively, the support is a silica-alumina, that is to say that it contains at least 50% by weight of alumina. The silica content in the support is at most 50% by weight, most often less than or equal to 45% by weight, preferably less than or equal to 40% by weight. When the support for said catalyst is based on silica, it contains more than 50% by weight of silica and, in general, it contains only silica.
    According to a particularly preferred variant, the support consists of alumina, silica or silica-alumina.
    The support can also advantageously also contain from 0.1 to 50% by weight of zeolite. Preferably, the zeolite is chosen from the group FAU, BEA, ISV, IWR, IWW, MEI, UWY and preferably, the zeolite is chosen from the group FAU and BEA, such as the zeolite Y and / or beta.
    In certain particular cases, the support can contain at least one doping element, such as for example phosphorus.
    The porous solid has a total pore volume of between 0.1 and 1.5 cm 3 / g, preferably between 0.4 and 1.1 cm 3 / g. The total pore volume is measured by mercury porosimetry according to standard ASTM D4284 with a wetting angle of 140 °, as described in the work Rouquerol F .; Rouquerol J .; Singh K. "Adsorption by Powders & Porous Solids: Principle, methodology and applications", Academie Press, 1999, for example using an Autopore III ™ model device from the Microméritics ™ brand.
    The specific surface of the porous solid is advantageously between 5 and 400 m 2 / g, preferably between 10 and 350 m 2 / g, more preferably between 40 and 350 m 2 / g. The specific surface is determined in the present invention by the BET method according to standard ASTM D3663, method described in the same work cited above.
    The porous solid is generally in the form of beads, extrudates, pellets, or irregular and non-spherical agglomerates whose specific shape can result from a crushing step.
    As mentioned above, the process for adding the organic compound can be carried out on a porous solid which is a catalyst precursor, that is to say on a porous support further comprising at least one metal from group VIB and / or at least one group metal
    VIII. The groups of chemical elements are given according to the CAS classification (CRC Handbook of Chemistry and Physics, CRC press editor, editor-in-chief D.R. Lide, 81st 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.
    In the context of the invention, the catalyst precursor can be a fresh catalyst precursor, that is to say one which has not been used before in a catalytic unit and in particular in hydrotreating and / or hydrocracking.
    The catalyst precursor according to the invention can also be a so-called regenerated catalyst. The term regenerated catalyst means a catalyst which has been previously used in a catalytic unit and in particular in hydrotreatment and which has been subjected to at least one calcination step in order to burn the coke (regeneration).
    The method of adding the organic compound according to the invention consists in bringing into contact, in an open or closed enclosure, a first batch of porous solid rich in an organic compound which has been previously deposited on said solid in the liquid state with a second batch of porous solid poor in said organic compound. The objective of this bringing together of porous solids is to allow a gaseous transfer of a part of the organic compound contained in the first batch of porous solid in the second batch of porous solid. According to the invention, the term poor in organic compound covers in particular the case where the second batch of porous solid is free from said organic compound.
    The method according to the invention is based on the principle of the existence of a vapor pressure of the organic compound at a given temperature and pressure. Thus, part of the organic compound molecules of the batch of porous solid rich in organic compound passes in gaseous form (vaporization) and is then transferred (by gaseous route) to the solid poor in organic compound. According to the invention, the porous solid rich in organic compound plays the role of source of organic compound to enrich in organic compound the porous solid poor in organic compound. In the context of the invention, the porous solid (for example a porous catalyst support or a catalyst precursor) rich in organic compound is obtained by impregnation with the organic compound in the liquid state. Unlike the prior art, the organic compound is not diluted in a solvent. An advantage of the process according to the invention compared to the processes of the prior art therefore resides in the absence of a drying step which is conventionally used to remove the solvent after the impregnation step and therefore to be less energy-consuming. compared to conventional methods. This absence of a drying step makes it possible to avoid possible losses of organic compound by vaporization or even by degradation. The method according to the invention requires a smaller number of unit steps.
    The volume of organic compound used is strictly less than the total volume of the accessible porosity of the solids used in step a) and is fixed relative to the amount of organic compound targeted on the batches of solids at the end from step a) of contact. Another advantage of the invention is therefore the use of a smaller amount of organic compound compared to the case of the prior art where, in the absence of solvent, all the porosity should be filled with organic compound.
    The mass ratio (first batch of solid rich in organic compound) / (second batch of solid poor in organic compound) is a function of the porous distribution of the solids and the objective in terms of the quantity of organic compound targeted on the solids from step a) of contact. This mass ratio is generally less than or equal to 10, preferably less than 2 and even more preferably between 0.05 and 1, limits included.
    According to the invention, step a) of bringing the porous solids into contact is carried out under conditions of temperature, pressure and duration so as to achieve equilibration of the amount of organic compound on the two batches of porous solids. The term “balancing” is intended to denote the fact that at the end of step a) of bringing at least 50% by weight of the first and second batches of porous solids present an amount of said organic compound equal to more or less 50% of the targeted quantity, preferably at least 80% by weight of the first and second batches of porous solids have an amount of said organic compound equal to more or less 40% of the targeted quantity and even more preferably at least 90% by weight first and second solids have an amount of said organic compound equal to plus or minus 20% of the targeted amount.
    By way of nonlimiting example, in the case where the aim is the preparation of a porous solid comprising 5% by weight of organic compound, a first batch of porous solid containing 10% by weight can be brought together in the same quantity of organic compound with a second batch of the same solid but free of said organic compound. In this case, it will be considered that equilibration is achieved when at least 50% by weight of the porous solids have an amount of said organic compound which corresponds to a content of between 2.5 and 7.5% by weight, preferably when at least 80% by weight of the solids have an amount of said organic compound which corresponds to a content which is between 3 and 7% by weight, and even more preferably, when at least 90% by weight of the solids have an amount of said organic compound which corresponds at a content between 4 and 6% by weight.
    The determination of these contents can be done by a statistically representative sampling for which the samples can be characterized for example by assay of carbon and / or possible heteroatoms contained in the organic compound or by thermogravimetry coupled to an analyzer, for example a spectrometer mass, or an infrared spectrometer and thus determine the respective contents of organic compounds.
    The step of bringing batches of porous solids together is preferably carried out under controlled temperature and pressure conditions and so that the temperature is lower than the boiling temperature of said organic compound to be transferred by gas. Preferably, the processing temperature is less than 150 ° C and the absolute pressure is generally between 0 and 1 MPa, preferably between 0 and 0.5 MPa and more preferably between 0 and 0.2 MPa . It will thus be possible to operate the step of bringing together in an open or closed enclosure, possibly with a control of the composition of the gas present in the enclosure.
    When the step of bringing porous solids together takes place in an open enclosure, it will be ensured that the entrainment of the organic compound outside the enclosure is limited as much as possible. Alternatively, the step of bringing porous solids into contact can be carried out in a closed enclosure, for example in a container for storing or transporting the solid which is impermeable to gas exchange with the external environment.
    In the context of the invention, the contacting step can be carried out by controlling the composition of the gas making up the atmosphere by the introduction of one or more gaseous compounds and optionally with a controlled hygrometry. By way of nonlimiting example, the gaseous compound can be carbon dioxide, ammonia, air with controlled humidity, a rare gas such as argon, nitrogen, hydrogen, natural gas or a refrigerant gas under the classification published by IUPAC. According to an advantageous embodiment, the step of bringing into presence under a controlled gaseous atmosphere implements a forced circulation of the gas in the enclosure.
    According to a preferred embodiment, the step of bringing lots of porous solids together is carried out by bringing said lots into physical contact with optionally a step of mixing the lots before or during step a). This embodiment can advantageously be implemented in a container for transporting or storing the porous solid, at ambient temperature and under atmospheric pressure.
    Alternatively, the step of bringing lots of porous solids together takes place without physical contact in an enclosure equipped with compartments capable of containing the first and second lot of porous solids respectively, the compartments being in communication so as to allow passage organic compound in gaseous state between the two compartments. In this embodiment, it is advantageous to circulate a gas flow first through the compartment containing the porous solid rich in organic compound and then through the compartment containing the porous solid poor in organic compound.
    Any organic compound which is in the liquid state at the temperature and at the pressure used in the step of adding the organic compound to the porous solid in order to provide the first batch of porous solid rich in organic compound, can be used in the process according to the invention. The organic compound can for example be chosen from organic molecules containing oxygen and / or nitrogen and / or sulfur. The organic compound is for example chosen from a compound comprising one or more chemical functions chosen from a carboxylic function, alcohol, thiol, thioether, sulfone, sulfoxide, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, oxime, urea and amide. As an example, it can be chosen from triethylene glycol, diethylene glycol, ethylene glycol, propylene glycol, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, 1,4-butanediol, 1- pentanol, malonic acid, succinic acid, γ-ketovaleric acid, maleic acid, citric acid, alanine, glycine, iminodiacetic acid, nitrilotriacetic acid, orthophthalic acid , diethylformamide, dimethylformamide, methyl acetoacetate, dimethyl succinate, 2-methoxyethyl 3-oxobutanoate, 2methacryloyloxyethyl 3-oxobutanoate, γ-valerolactone, 4-hydroxyvaleric acid, 2 acid -pentenoic, 3-pentenoic acid, 4-pentenoic acid, 2-acetylbutyrolactone, 2- (2hydroxyethyl) -3-oxobutanoic acid, 3-hydroxy-2- (2-hydroxyethyl) acid - 2-butenoic, Nmethylpyrrolidone, c propylene arbonate, sulfolane, diethyl phosphite, triethyl phosphite, triethyl phosphate, acetophenone, tetramethylurea, thioglycolic acid. In the context of the invention, it is also possible to use a composition consisting of a mixture of the aforementioned organic compounds to prepare a first batch of solid rich in a mixture of organic compounds.
    According to a particular embodiment, the first batch of porous solid rich in organic compound only serves as a vector for organic compound and is separated from the batch of porous solid recovered at the end of the contacting step. In this embodiment and when the batches of solids rich and poor in organic compound are mixed, a first batch of porous solid will be used which has at least one physical characteristic which distinguishes it from the other batch of porous solid.
    The porous solid obtained at the end of step a) of contacting is advantageously used for the preparation of catalysts useful for example in processes for refining hydrocarbon charges or also for the synthesis of hydrocarbons from '' a synthesis gas (Fischer-Tropsch synthesis). Thus, the process for adding the organic compound according to the invention can be carried out one or more times in a production chain of an additive catalyst to carry out the introduction of one or more organic compounds before the step of impregnation of the active metallic phase and / or to allow the introduction of one or more organic compounds onto a porous support already containing an active metallic phase which can optionally be sulfurized. Within the framework of the invention, it is also possible to introduce, during the process for the preparation of the catalyst, one or more other additional organic compounds different from that used in step i) described above. The introduction of the additional organic compound (s) can be carried out using any method known to those skilled in the art, such as for example those described in document FR 3 035 008. For example, it is possible to use in step ii) a solution containing the metal (s) of the active phase and one or more additional organic compounds. Alternatively, it is also possible to carry out one or more stages of impregnation of the additional organic compound (s) with a solution, for example aqueous, containing one or more additional organic compounds.
    When the catalyst is intended to carry out hydrotreatment reactions, the catalyst containing the porous support, a metallic active phase and one or more organic compounds is subjected to a sulfurization step in order to transform the metal oxides into sulfides, optionally preceded by a drying step in order to remove the solvent supplied during the step of introducing the metallic phase.
    The additive catalysts thus prepared are used in particular for hydrotreatment reactions of hydrocarbon feedstocks such as petroleum fractions or for the synthesis of hydrocarbons from synthesis gas. According to the invention, the term hydrotreatment includes in particular total or selective hydrogenation reactions, hydrodenitrogenation, hydrodesaromatization, hydrodesulfurization, hydrodeoxygenation, hydrodemetallization, and hydrocracking of hydrocarbon feedstocks.
    For hydrotreatment applications, the additive catalyst generally undergoes a sulfurization step. The fillers used in the hydrotreatment process are for example gasolines, gas oils, vacuum gas oils, atmospheric residues, vacuum residues, atmospheric distillates, vacuum distillates, heavy fuels, oils, waxes and paraffins, used oils, deasphalted residues or crudes, fillers from thermal or catalytic conversion processes, lignocellulosic fillers or fillers from biomass, taken alone or as a mixture.
    Other objects and advantages of the invention will appear on reading the following description of examples of particular embodiments of the invention, given by way of nonlimiting examples, the description being given with reference to the appended figures described below. -after.
    Brief description of the figures • Figure 1 is a diagram illustrating the principle of addition of an organic compound according to current practice known to those skilled in the art;
    • Figure 2 is a diagram illustrating the method according to the invention of adding an organic compound according to a first embodiment;
    • Figure 3 shows a diagram of the process for adding an organic compound according to another embodiment;
    • Figure 4 is a diagram of the process for adding an organic compound according to a third embodiment.
    Generally, similar elements are denoted by identical references in the figures.
    FIG. 1 corresponds to a block diagram showing a known process for adding an organic compound to a porous catalyst support or a catalyst precursor as described above which is designated below by the generic term porous solid.
    The batch of solid 1 is subjected to an optional pretreatment in a pretreatment unit 2 of the solid 1 intended, if necessary, to condition the solid before the step of impregnating the organic compound. This pretreatment step can be, for example and depending on the desired effect, a preliminary drying step to adjust the residual humidity.
    This pretreatment can also be an addition by controlled addition of the same solvent, provided by line 3, as that which is used during the impregnation of the organic compound in order to avoid an overly lively reaction of the solid during phase d 'impregnation of the organic compound. The type of reaction that one wishes to avoid is for example a strong release of heat linked to the abrupt adsorption of the solvent (such as water for example) on the active sites of the solid.
    The solid batch 4 from the pretreatment step is sent to an impregnation unit 5 for the organic compound. According to the prior art, this step uses a solution containing a solvent, for example water, in which the organic compound to be impregnated is dissolved.
    In FIG. 1, the impregnation solution is supplied by line 6. The impregnation is carried out according to any method known to those skilled in the art and for example by dry impregnation. In this mode of impregnation, the solid set in motion is subjected to a jet of the impregnation solution, the volume of sprayed solution generally being equivalent to the entire pore volume of the solid to be impregnated which is accessible to the solution. In accordance with the practice of the prior art, the impregnated solid is removed via line 7 in a drying unit 8 in order to remove the solvent which has been incorporated into the solid at the same time as the organic compound. Flow 9 represents the hot utility which is used to dry the solid, which is for example hot air. This results in a dry solid 10 impregnated with the chosen organic compound.
    Depending on the organic compound chosen and its solubility in the solvent used during the impregnation step, it is possible that the quantity introduced is not sufficient after a single impregnation step. In which case, several steps of impregnation and drying described above may be used.
    After impregnation of the organic compound, the solid can undergo one or more stages of impregnation of one or more metals of group VIB and / or of group VIII in order to deposit a metallic catalytic phase. The impregnation step or steps can be followed, optionally after a maturing step, by a drying step at a moderate temperature, generally below 200 ° C.
    FIG. 2 describes the process according to the invention for adding an organic compound according to a first embodiment. The solid 1 having been, if necessary, packaged in the pretreatment unit 2 is transferred via line 4 to the unit 5 for introducing the organic compound. In accordance with the invention, this impregnation step is carried out with the organic compound which is in the liquid state supplied by line 6. The volume of liquid organic compound which is used is chosen so that it is strictly less than the pore volume of the total batch of porous solid 1 and porous solid 2 which is accessible to the liquid organic compound.
    The solid rich in organic compound is evacuated from the unit 5 for introducing the organic compound via line 7 to a unit 20 in which said solid is brought into contact, preferably under controlled conditions (pressure / temperature / composition of l 'gaseous atmosphere), with another batch of porous solid 2 poor in said organic compound, for example the amount of organic compound in the batch of porous solid 2 is zero. The objective of the step of bringing the solids into the unit 20 is to carry out the transfer by gas of part of the organic compound contained in the solid rich in organic compound to the solid poor in organic compound in order to provide, after balancing, the batch of solid 22 impregnated with said organic compound. The nature and the porous structure of the solid rich in organic compound and the solid poor in organic compound are also parameters which can be taken into account. Thus, the chemical composition of the solid rich in organic compound can be such that its adsorption capacity with respect to the organic compound is lower than that of the solid to be additivated. A similar effect can be obtained by adapting the porous structure of the solid rich in organic compound so that it has an average pore opening which is greater than that of the solid to be impregnated so as to promote the transfer to the solid poor in organic compound. , particularly in the case of a mechanism involving capillary condensation.
    As indicated in FIG. 2, when the solids are of the same nature, the solid poor in organic compound can be chosen from solid 23 before pretreatment or solid pretreated 24.
    The step of bringing the solids into contact according to the invention can be carried out with or without physical contact of the two batches of solids. When said step of bringing the solids together takes place with physical contact with the solids, the solids can be mixed before or during the contacting step.
    According to the invention, the contacting step is preferably carried out at a temperature below the boiling temperature of the organic compound at the chosen pressure. For example, the temperature can be less than 150 ° C. for an absolute pressure range of between 0 and 1 MPa. The duration of this step is chosen so as to obtain a balancing as described above. In general, the higher the temperature and the lower the pressure, the more this time will be reduced, which will be favorable for the integration of this stage in a fast production chain. Typically the duration is less than 24 hours, preferably less than 5 hours and preferably less than 1 hour.
    In the context of the invention, the unit 20 enabling the solids to be brought into contact is for example an enclosure preferably closed. To allow the solids to be brought into contact without physical contact between the solids, it is possible to use a compartmentalized enclosure so as to receive in two respective compartments the solid rich in organic compound and the solid poor in organic compound, the compartments being configured to allow the passage of the organic compound in the gaseous state between the two compartments.
    According to the invention, the contacting step can also be carried out in a suitable storage or transport container in which the mixed solids are placed in bulk. This type of implementation can be practiced when the balancing time is not critical. The pressure and temperature conditions can then be close to ambient and the time for bringing the solids into contact (from several days to several weeks) corresponds to the time required to transport the solids from the production site to the production site. use of solids with possible additional storage time at the end user.
    FIG. 3 represents another embodiment of the process for adding the organic compound according to the invention which differs from that of FIG. 2 in that the lots of solid rich in organic compound and solid poor in organic compound are obtained at the same time at the end of the step of impregnating a fraction of an initial batch of porous solid. With reference to FIG. 3, a stream of conditioned solid withdrawn from the solid pre-treatment unit 2 is sent via line 4 to the step of introducing the organic compound in the liquid state. The introduction step which is carried out in unit 5 differs from that of FIG. 2 in that it is operated so that only a fraction of the solid is brought into contact with the liquid organic compound supplied by the line 6. At the end of this step, two fractions of solids A and B are obtained having different contents of organic compound. By way of nonlimiting example, the impregnation step according to the embodiment of FIG. 3 can consist in spreading the organic compound in the liquid state, for example by means of a dispersing device, on the surface of the batch of solid so as to provide a fraction of solid A rich in organic compound and a fraction of solid B poor in organic compound. For example, this step of impregnating the batch of solid can be carried out in a unit 5 comprising a belt conveyor for the solid and equipped with the liquid dispersing device. At the end of the impregnation step, the lots of solids A and B are left in the presence of each other. For example, the presence is carried out in the unit 5 for introducing the liquid organic compound or in a dedicated unit 20 as indicated in FIG. 3. Preferably, the fractions A and B are mixed after the introduction step liquid organic compound.
    Another embodiment of the process for adding an organic compound to a solid (a porous catalyst support or a catalyst precursor) is shown diagrammatically in FIG. 4. This embodiment according to the invention corresponds to the case where the porous solid containing the organic compound serves as a reservoir of organic compound for the step of bringing the solids into contact.
    As shown in Figure 4, a porous solid called vector 4, optionally pretreated in a conditioning unit 2 as described above, is impregnated in the impregnation unit 5 with a liquid organic compound provided by line 6. The solid vector 7 rich in said organic compound is transferred to unit 20 in which said solid vector is placed in the presence of a porous solid said to be of poor interest in organic compound brought by line 21. For example, the porous solid may have a zero amount of said organic compound.
    At the end of the step of bringing the solids into contact, the unit is withdrawn from line 22, a mixture of carrier solids and of interest each containing said organic compound. The mixture of solids is then sent to a separation unit 25 which performs physical separation of the carrier solids and of interest. Thanks to the implementation of the separation, two streams of solids are obtained, namely the carrier solid 26 containing the organic compound and the solid of interest 27 also containing the organic compound.
    In accordance with this embodiment, the solid vector still containing the organic compound 26 is recycled to the unit for introducing the liquid organic compound for subsequent use. In this embodiment, the solid vector has at least one physical characteristic which discriminates against the solid of interest in order to allow their separation. For example and without limitation, this physical characteristic can be:
    - the size of the particles of the solid: the separation can be carried out on a sieve
    - magnetism: the separation is done by the application of a magnetic field
    - the density of the solid: in conjunction or not with the size of the particles, this difference in density can for example be used for separation by elutriation.
    The nature and the porous structure of the vector solid and of the solid of interest are also parameters to be taken into account. Thus, the solid vector has a chemical composition adapted to disadvantage the adsorption of the compound to be impregnated compared to the adsorption of the compound to be impregnated on the solid of interest. A similar effect can be obtained by adapting the porous structure of the solid vector so that it has an average opening of its pores which is greater than that of the solid of interest so as to favor the transfer of the organic compound onto the solid of advantage, particularly in the case of capillary condensation.
    Examples
    The examples which follow specify the interest of the invention without however limiting its scope.
    Example 1: Preparation of CoMoP catalysts on alumina without organic compound C1 and C2 (according to the prior art)
    On an alumina support in the “extruded” form, having a BET surface area of 230 m 2 / g, a mesoporous volume measured by mercury porosimetry of 0.78 ml / g and a volume median diameter by mercury porosimetry of 11.5 nm, cobalt, molybdenum and phosphorus are added. The impregnation solution is prepared by dissolving molybdenum oxide (21.1 g) and cobalt hydroxide (5.04 g) in 11.8 g of an aqueous acid solution at 90 ° C phosphoric at 85% by weight. After dry impregnation, the extrudates are left to mature in a water saturated atmosphere for 24 h at room temperature, then they are dried at 90 ° C. for 16 hours. The dried catalytic precursor thus obtained is denoted C1. The calcination of the catalytic precursor C1 at 450 ° C for 2 hours leads to the calcined catalyst C2. The metal composition of the catalyst precursor C1 and the calcined catalyst C2 is: Mo03 = 19.5 ± 0.2% by weight, CoO = 3.8 ± 0.1% by weight and P 2 O 5 = 6.7 ± 0 , 1% by weight, the percentages being expressed relative to the weight of dry catalyst.
    Example 2 Preparation of the CoMoP catalyst additivated with citric acid on C3 alumina (according to the prior art) by co-impregnation
    Cobalt, molybdenum and phosphorus are added to the alumina support described in Example 1 and which is in the "extruded" form. The impregnation solution is prepared by dissolving molybdenum oxide (28 £ 8 g) and cobalt hydroxide (6.57 g) in 15.85 g of an aqueous acid solution at 90 ° C phosphoric at 85% by weight. After homogenization of the above mixture, 38 g of citric acid were added before adjusting the volume of solution to the total pore volume of the support by adding water. The amount of citric acid used is such that the molar ratio (citric acid) / Mo is equal to 1 mol / mol and that (citric acid) / Co is equal to 2.7 mol / mol. After dry impregnation, the extrudates are left to mature in a water-saturated atmosphere for 24 h at room temperature, then they are dried at 120 ° C for 16 hours. The citric acid additive catalyst thus obtained is denoted C3. The final metal composition of catalyst C3 relative to the mass of dry catalyst is then as follows: Mo03 = 19.6 ± 0.2% by weight, CoO = 3.7 ± 0.1% by weight and P 2 O 5 = 6 , 7 ± 0.1% by weight.
    Example 3 Preparation of the CoMoP catalyst additivated with 2-methoxvethyl 3-oxobutanoate on C4 alumina (according to the prior art) by post-impregnation
    3.2 g of 2-methoxyethyl 3-oxobutanoate diluted in water so as to obtain a volume solution are added to 18 g of catalyst C1 described in example 1 and which is in the form of extrudates total equal to the pore volume of the catalyst. The amount of organic compound added is such that the molar ratio (2-methoxyethyl 3-oxobutanoate) / Mo is 0.8 mol / mol or either 2.2 moles of (2-methoxyethyl 3-oxobutanoate) per mole of cobalt. The extrudates are left to mature in an atmosphere saturated with water for 16 h at room temperature. The catalyst is then dried at 120 ° C for 2 hours. The final metal composition of catalyst C4 expressed in the form of oxides is: Mo03 = 19.5 ± 0.2% by weight, CoO = 3.8 ± 0.1% by weight and P 2 O 5 = 6.7 ± 0 , 1% by weight relative to the weight of dry catalyst.
    Example 4 Preparation of the CoMoP catalyst on C5 alumina (according to the invention) by introduction, after the impregnation of the metals, of an organic compound without solvent at a volume lower than that of the porosity of the solid to be impregnated.
    In a closed enclosure is placed a batch of 12 g of the catalyst precursor C1. 2.3 g (i.e. 1.9 mL) of 2-methoxyethyl 3-oxobutanoate in liquid form are dispersed on the surface of the batch of catalyst precursor C1 at ambient temperature and pressure. As in Example 3, the amount of 2-methoxyethyl 3-oxobutanoate added is such that the molar ratio (2-methoxyethyl 3-oxobutanoate) / Mo is 0.8 mol / mol or 2.2 moles of ( 2-methoxyethyl 3-oxobutanoate) per mole of cobalt. It will also be noted that the volume of 1.9 ml of organic compound introduced is less than the total pore volume of the batch of catalyst precursor C1 used, which is approximately 6.5 ml. A batch of catalyst precursor rich in organic compound and a batch of catalyst precursor poor in organic compound are thus obtained at the end of the dispersion step.
    The closed enclosure is placed in an oven at 120 ° C for 6 hours. 14.1 g of catalyst C5 impregnated with the organic compound are thus obtained. The final metal composition of catalyst C5 is: Mo03 = 19.5 ± 0.2% by weight, CoO = 3.8 ± 0.1% by weight and P 2 O 5 = 6.7 ± 0.1% by weight relative to by weight of dry catalyst. Catalyst C5 also has a molar ratio (2-methoxyethyl 3-oxobutanoate) / Mo of 0.8 mol / mol
    Example 5 Preparation of the CoMoP catalyst on C6 alumina (according to the invention) by introduction before the impregnation of the metals of an organic compound without solvent at a volume lower than that of the porosity of the solid to be impregnated.
    In a closed enclosure is placed a batch of 8.4 g of the same support in the form of extrudates as that used in Example 1. 2.3 g (or 1.9 ml) of 2-methoxyethyl 3-oxobutanoate in liquid form are dispersed on the surface of the support batch at ambient temperature and pressure. In this example, the volume of organic compound introduced is less than the total pore volume of the support batch, which is approximately 7.4 ml_. A batch of catalyst precursor rich in organic compound and a batch of precursor poor in organic compound are thus obtained at the end of the dispersion step. A batch of catalyst support rich in organic compound and a batch of catalyst support poor in organic compound is thus obtained at the end of the dispersion step.
    The closed chamber is placed in an oven at 120 ° C for 6 hours. At the end of this step, 10.5 g of support impregnated with the organic compound are thus obtained. As in Example 4, the amount of 2-methoxyethyl 3-oxobutanoate introduced onto the support is fixed so as to obtain, after impregnation of the metals, a molar ratio (2-methoxyethyl 3oxobutanoate) / Mo of 0.8 mol / mol or 2.2 moles of (2-methoxyethyl 3-oxobutanoate) per mole of cobalt.
    The support added with 2-methoxyethyl 3-oxobutanoate is then impregnated with an impregnation solution prepared by hot dissolution of molybdenum oxide (2.4 g) and cobalt hydroxide (0.6 g) in 1.4 g of an 85% by weight aqueous phosphoric acid solution. Water is added to the metal impregnation solution so that its volume is equal to the total pore volume of the batch of additive carrier. After dry impregnation, the extrudates were left to mature in a water saturated atmosphere for 24 h at room temperature, then dried at 120 ° C. for 16 hours to yield the catalyst C6. The final metal composition of catalyst C6 expressed as oxides is as follows: Mo03 = 19.6 ± 0.2% by weight, CoO = 3.9 ± 0.1% by weight and P 2 O 5 = 6.8 ± 0.1% by weight relative to the weight of dry catalyst. Catalyst C6 also has a molar ratio (2-methoxyethyl 3oxobutanoate) / Mo of 0.8 mol / mol.
    Example 6 Evaluation in Hydrodesulfurization (HDS) of Diesel Fuel of Catalysts C1, C2, C3 and C4 (Prepared According to the Prior Art) and C5 and C6 (Prepared by the Process According to the Invention) Catalysts C1, C2, C3 and C4 (comparative) and C5 and C6 (prepared according to the invention) were tested in hydrodesulfurization of a diesel fuel.
    The characteristics of the diesel charge used are as follows:
    - Density at 15 ° C: 0.8522 g / crrf,
    - Total sulfur content: 1.44% by weight.
    Simulated distillation:
    • PI : 155 ° C • 10% : 247 ° C • 50% : 315 ° C • 90% : 392 ° C • PF : 444 ° C
    The test is carried out in an isothermal pilot reactor with a fixed bed traversed, the fluids flowing from bottom to top. The catalysts are previously sulfurized in situ at 350 ° C. in the pressurized unit by means of test gas oil to which 2% by weight of dimethyldisulphide is added.
    The hydrodesulfurization tests of the diesel feed were carried out under the following operating conditions: a total pressure of 7 MPa, with a volume of catalyst of 30 cm 3 , at a temperature between 330 to 360 ° C and a / ec un hydrogen flow rate of 24 l / h and a charge flow rate of 60 cm 3 / h.
    The catalytic performances of the catalysts tested are given in Table 1. They are expressed in degrees Celsius starting from a comparative catalyst chosen as reference (catalyst C2): they correspond to the temperature difference to be applied to reach 50 ppm of sulfur in the effluent. A negative value means that the sulfur content target is reached for a lower temperature and that there is therefore a gain in activity. A positive value means that the sulfur content target is reached at a higher temperature and therefore there is a loss of activity.
    Catalyst (comparative or according to the invention) Organic compound used Organic compound / Mo molar ratio Method of introducing the organic compound ActivityHDS C1 (comp) - - - Based+ 1.0 ° C C2 (comp) - - - Based C3 (comp) Citric acid 1.0 Co-impregnation of the organic compound Base -2.9 ° C
    C4 (comp) 2-methoxyethyl 3-oxobutanoate 0.8 Post-impregnation of the organic compound Base -5.7 ° C C5 (inv) 2-methoxyethyl 3-oxobutanoate 0.8 Post-impregnation of the organic compound without solvent to a volume lower than that of the porosity of the solid to be impregnated Base -6.9 ° C C6 (inv) 2-methoxyethyl 3-oxobutanoate 0.8 Pre-impregnation of the organic compound without solvent to a volume lower than that of the porosity of the solid to be impregnated Base -6.5 ° C
    Table 1
    Table 1 clearly shows that the mode of introduction of the organic compound according to the invention makes it possible to avoid the use of a solvent and therefore of a drying step while introducing the adequate amount of organic compound to obtain catalysts at least as efficient as those prepared according to the prior art. Indeed, the catalysts C5 and C6 according to the invention are more efficient than all the other comparative catalysts. The gain is very significant in comparison with catalysts not using an organic molecule (C1 and C2) or citric acid (C3) commonly used by those skilled in the art. In addition, catalysts C5 and C6 are more efficient than catalyst C4 using the same organic molecule introduced according to a protocol well known to those skilled in the art based on post-additivation in aqueous solution. The organic compound can therefore be introduced according to the invention both before and after the impregnation of metals. These examples 15 therefore clearly show the feasibility and the relevance of the method of introducing an organic compound according to the invention, in particular for preparing catalysts which can have performances at least as high as those of the catalysts of the prior art.
    权利要求:
    Claims (18)
    [1" id="c-fr-0001]
    1) Process for adding an organic compound to a porous solid comprising a step a) in which is placed in an open or closed enclosure, a first batch of porous solid rich in an organic compound with a second batch of porous solid poor in said organic compound, step a) being carried out under conditions of temperature, pressure and duration such that a fraction of said organic compound is transferred by gas from the first batch of porous solid to the second batch of solid porous.
    [2" id="c-fr-0002]
    2) The method of claim 1, wherein the temperature of step a) is lower than the boiling temperature of the organic compound.
    [3" id="c-fr-0003]
    3) Method according to claims 1 or 2, wherein the amount of said organic compound of the second batch of porous solid is zero.
    [4" id="c-fr-0004]
    4) Method according to one of the preceding claims, in which step a) is carried out by bringing the first and second batches of porous solid into physical contact.
    [5" id="c-fr-0005]
    5) Method according to claim 4, wherein step a) is carried out in a storage or transport enclosure.
    [6" id="c-fr-0006]
    6) Method according to one of claims 1 to 3, wherein step a) of bringing said batches together is carried out in an enclosure comprising two separate compartments in gas communication, said compartments being capable of respectively containing the first and second batches of porous solid so that the support batches are made without physical contact.
    [7" id="c-fr-0007]
    7) Method according to one of the preceding claims comprising the following steps:
    a ') an initial batch of porous solid is supplied, b') the initial batch of porous solid is impregnated heterogeneously with the organic compound in the liquid state so as to provide a first batch of porous solid rich in organic compound and a second batch of porous solid poor in organic compound, c ') said batches of porous solids from stage b') are left in the presence according to step a) under conditions of temperature, pressure and duration such that a fraction of said organic compound is transferred by gas from the first batch of porous solid to the second batch of porous solid.
    [8" id="c-fr-0008]
    8) Method according to one of claims 1 to 6 comprising the following steps: a) an initial batch of porous solid is provided;
    b) separating said initial batch into a first and second distinct fraction, c) introducing into the first solid fraction from step b) the organic compound in the liquid state so as to provide the first batch of rich solid organic compound;
    d) the first batch of support rich in organic compound from step c) is brought into contact according to step a) with the second fraction of solid from step b) under temperature, pressure and of such duration that a fraction of said organic compound is transferred by gas from the first batch of porous solid to the second batch of porous solid.
    [9" id="c-fr-0009]
    9) Method according to one of the preceding claims wherein step a) is carried out at an absolute pressure between 0 and 1 MPa.
    [10" id="c-fr-0010]
    10) Method according to one of the preceding claims wherein step a) is carried out in the presence of a circulation of a carrier gas.
    [11" id="c-fr-0011]
    11) Method according to one of the preceding claims wherein at least one fraction of the porous solid from step a) is separated and said fraction is recycled in step a).
    [12" id="c-fr-0012]
    12) Method according to one of the preceding claims wherein the porous solid is chosen from a porous catalyst support and a porous catalyst support further comprising at least one metal from group VIB and / or at least one metal from group VIII.
    [13" id="c-fr-0013]
    13) The method of claim 12, wherein the porous support is based on a metal oxide and / or a metalloid.
    [14" id="c-fr-0014]
    14) Method according to one of the preceding claims, wherein the organic compound is chosen from organic molecules containing oxygen and / or nitrogen and / or sulfur.
    [15" id="c-fr-0015]
    15) Process for the preparation of a catalyst comprising a porous support, at least one metal from group VIB and / or at least one metal from group VIII and at least one organic compound, the process comprising at least the following steps:
    i) the process of adding at least one organic compound according to any one of the preceding claims is carried out by bringing the porous support into contact with a porous solid containing said organic compound so as to provide a batch of porous support containing said organic compound, ii) at least one metal from group VIB and / or at least one metal from group VIII is deposited on the porous support by bringing the support into contact with a solution containing at least one precursor of at least one metal from group VIII and / or at least one precursor of at least one metal from group VIB, iii) the porous support from step ii) is dried, step i) being carried out separately before or after steps ii) and iii ).
    5
    [16" id="c-fr-0016]
    16) A method of preparation according to claim 15, wherein the solution of step ii) further comprises at least one additional organic compound different from the organic compound used in step i).
    [17" id="c-fr-0017]
    17) Preparation process according to one of claims 15 to 16, further comprising at least one step of impregnating the porous support with a solution comprising
    10 an organic compound different from the organic compound used in step i).
    [18" id="c-fr-0018]
    18) Process for hydrotreating a hydrocarbon feedstock in which hydrogen, the hydrocarbon feedstock and a catalyst are brought into contact, at a temperature between 180 and 450 ° C., at a pressure between 0.5 and 30 MPa, with an hourly volume speed between 0.1 and 20 h -1 and with a ratio
    15 hydrogen / charge expressed in volume of hydrogen, measured under normal conditions of temperature and pressure, by volume of liquid charge between 50 l / l to 5000 l / l, said catalyst having been prepared a process according to one of claims 15 to 17 and subjected to at least one sulfurization step.
    1/2
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    CA2540286C|2003-10-03|2014-04-15|Albemarle Netherlands B.V.|Process for activating a hydrotreating catalyst|
    FR2880823B1|2005-01-20|2008-02-22|Total France Sa|HYDROTREATING CATALYST, PROCESS FOR PREPARING THE SAME AND USE THEREOF|FR3083131A1|2018-06-27|2020-01-03|IFP Energies Nouvelles|CATALYST BASED ON IMIDAZOLIDINONES, IMIDAZOLIDINEDIONES, PYRIMIDINONES AND / OR PYRIMIDINETRIONES AND ITS USE IN A HYDROPROCESSING AND / OR HYDROCRACKING PROCESS|
    FR3083132A1|2018-06-27|2020-01-03|IFP Energies Nouvelles|CATALYST BASED ON 1--2-PYRROLIDONE AND / OR 1--2,5-PYRROLIDINEDIONE AND ITS USE IN A HYDROTREATMENT AND / OR HYDROCRACKING PROCESS|
    FR3083134A1|2018-06-27|2020-01-03|IFP Energies Nouvelles|CATALYST BASED ON 1-VINYL-2-PYRROLIDONE AND / OR 1-ETHYL-2-PYRROLIDONE AND ITS USE IN A HYDROTREATMENT AND / OR HYDROCRACKING PROCESS|
    FR3083139A1|2018-06-27|2020-01-03|IFP Energies Nouvelles|CATALYST BASED ON PIPERIDINONES, PIPERIDINEDIONES AND / OR AZEPANONES AND ITS USE IN A HYDROTREATMENT AND / OR HYDROCRACKING PROCESS|
    FR3087787B1|2018-10-25|2020-12-18|Ifp Energies Now|HYDROGENATION PROCESS INCLUDING A CATALYST PREPARED BY ADDITION OF AN ORGANIC COMPOUND IN GASEOUS PHASE|
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    优先权:
    申请号 | 申请日 | 专利标题
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    FR1753922|2017-05-04|FR1753922A| FR3065888B1|2017-05-04|2017-05-04|PROCESS FOR THE INDIRECT ADDITION OF AN ORGANIC COMPOUND TO A POROUS SOLID.|
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    US16/610,217| US20210283591A1|2017-05-04|2018-04-24|Method for the indirect addition of an organic compound to a porous solid|
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    PCT/EP2018/060407| WO2018202468A1|2017-05-04|2018-04-24|Method for the indirect addition of an organic compound to a porous solid|
    JP2019559372A| JP2020518448A|2017-05-04|2018-04-24|Indirect addition of organic compounds to porous solids|
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