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    • 专利摘要:
    Process for the preparation of a catalyst or a capture mass, the following steps: contacting a porous oxide support with a metal salt comprising at least one metal belonging to groups VIB, VIIB, VIIIB, IB or IIB, of which the melting point of said metal salt is between 20 and 150 ° C for a period of between 5 minutes and 5 hours to form a solid mixture, the mass ratio between said metal salt and said porous oxide support being between 0.1 and 1; - Heating with stirring of the solid mixture at a temperature between the melting temperature of said metal salt and 200 ° C and for 5 minutes and 12 hours; - Calcination of the solid obtained in the previous step at a temperature above 200 ° C and less than or equal to 1100 ° C under an inert atmosphere or under an atmosphere containing oxygen.
    公开号:FR3085284A1
    申请号:FR1857940
    申请日:2018-09-04
    公开日:2020-03-06
    发明作者:Elodie TELLIER；Dominique DECOTTIGNIES；Antoine FECANT
    申请人:IFP Energies Nouvelles IFPEN；
    IPC主号:
    专利说明:

    PROCESS FOR THE PREPARATION OF A CATALYST OR A CAPTATION MASS FROM MOLTEN SALTS
    Technical area
    The present invention relates to the field of the preparation of catalysts or capture masses with a high rate of charge in metallic active phase obtained from molten metal salts. The present invention also relates to the use of such catalysts or capture masses in industrial processes.
    State of the art
    Many synthetic methods are known from the prior art for improving the reducibility of the metallic phase or even for controlling the particle sizes. Among these methods, the use of molten salts as precursors of the active phase of a catalyst or of a capture mass is known from the literature.
    For example, document US Pat. No. 5,036,032 discloses a method for preparing a cobalt-based supported catalyst by bringing a support into contact (on the order of a few tens of seconds) in a bath of molten salt of cobalt nitrate, followed by a drying and reduction stage without intermediate calcination. This method allows the preferential localization of the cobalt phase at the periphery of the support. However, the method does not allow precise control of the amount of active phase (here the cobalt) deposited due to the very short contact time and on the other hand the type of catalyst obtained is not suitable for use in a reactor operating in the liquid phase with a suspended catalyst (called slurry reactor or slurry according to English terminology) due to the loss of metal by excessive attrition. On the other hand, the absence of a calcination step is risky since the reaction between the reduction element and the nitrates in the solid is very exothermic. Finally, this method requires handling large quantities of cobalt nitrate (toxic) in liquid form and at temperature, with ratios of approximately 4 grams of active phase precursors per 1 gram of support. The catalysts obtained by this preparation route are used for the synthesis of Fischer-Tropsch hydrocarbons.
    He is known to Chem. Mater., 1999, 11, p.1999-2007 to prepare mixed phosphates by a molten salt type route. The reaction mixture contains a metal precursor salt (in particular Ni (NO 3 ) 2 or Co (No 3 ) 2 ), a source of phosphorus (NH 4 HPO 4 ), and an alkali metal nitrate (Na or K). These preparations are carried out at high temperatures of the order of 400 to 450 ° C. Solids of mixed phosphate type are obtained, for example Na 3 Ni2 (P 2 O7) PO4, K 2 Ni4 (PO4) 2P 2 O7 or Na 9 Co 3 (P0 4 ) 5. These solids can find applications in ion exchange, ionic conduction at high temperature or in catalysis.
    The document GB 191308864 discloses a process for the synthesis of a mass catalyst based on nickel or on cobalt for the production of hydrogen by steam reforming ("steam-reforming" according to English terminology). These catalysts can be obtained by liquefying metal salts at moderate temperatures, then poured into a mold before calcination heat treatment.
    The publication by J.-Y. Tilquin entitled “Intercalation of CoCI 2 into graphite: Mixing method vs molten salt method” published in Carbon, 35 (2), p. 299-306, 1997, proposes the use in the form of molten salt of a CoCI 2 -NaCI mixture at high temperature (450-580 ° C) for the intercalation between graphite sheets. These graphite intercalation compounds find applications in catalysis for the reduction of oxygen in fuel cells with polymer electrolyte.
    The document EP 2921227 discloses a Fischer-Tropsch catalyst based on a group VIIIB metal deposited on an oxide support comprising alumina, silica, a spinel and phosphorus as well as its manufacturing process. This process includes the preparation of the oxide support as well as the impregnation of this support with an aqueous solution of a metal precursor followed by drying and calcination. In the case of high metal contents, the impregnation / drying / calcination of active phase in several stages is preferred.
    Objects of the invention
    The Applicant has surprisingly discovered that it is possible to prepare a catalyst or a capture mass comprising an active phase with a high metal content by carrying out a minimum of steps, by carrying out an optimized control of the quantity of metal deposited on the catalyst and by reducing the dangerousness and the cost of said process by minimizing the quantities of metallic precursor used.
    An object according to the invention relates to a process for the preparation of a catalyst or a capture mass comprising an active phase based on at least one metal from the group
    VIB, VIIB, VII IB, IB or I IB and a porous oxide support, said catalyst being prepared by at least the following steps:
    a) bringing said porous oxide support into contact with at least one metal salt comprising at least one metal belonging to groups VIB, VIIB, VIIIB, IB or HB, the melting temperature of said metal salt being between 20 and 150 ° C. for a time of between 5 minutes and 5 hours to form a solid mixture, the mass ratio between said metal salt and said porous oxide support being between 0.1 and 1;
    b) the solid mixture obtained at the end of step a) is heated with stirring to a temperature between the melting temperature of said metal salt and 200 ° C. and with a residence time of between 5 minutes and 12 hours;
    c) optionally, the solid obtained at the end of step b) is dried at a temperature below 200 ° C;
    d) the solid obtained at the end of step b) or c) is calcined at a temperature greater than 200 ° C. and less than or equal to 1100 Ό under an inert atmosphere or under an oxygen-containing atmosphere.
    Preferably, said metal is chosen from Zn, Cu, Ni, Fe, Co, Mn.
    Preferably, the metal salt is a hydrated nitrate salt.
    Preferably, said metal salt is chosen from zinc nitrate trihydrate, zinc nitrate hexahydrate, copper nitrate trihydrate, copper nitrate hexahydrate, nickel nitrate hexahydrate, iron nitrate nonahydrate, cobalt nitrate hexahydrate , manganese nitrate tetrahydrate, manganese nitrate hexahydrate, taken alone or as a mixture.
    Preferably, the mass ratio between said metal salt and the porous support is between 0.3 and 0.9.
    Preferably, step a) is carried out for 10 minutes to 4 hours.
    Preferably, the porous support of said catalyst or capture mass is chosen from alumina, silica or silica-alumina.
    Preferably, the calcination time of step d) is less than 16 hours.
    Preferably, said porous support is in the form of a powder with a particle size between 10 and 500 μm.
    Preferably, said porous support comprises a specific surface of between 5 and 500 m 2 / g.
    Preferably, said porous support has a total pore volume of between 0.3 and 3 ml / g.
    Another object according to the invention relates to the use of the catalyst or of the capture mass prepared according to the invention in the field of catalytic processes or in the context of processes for the purification of gaseous or liquid effluents.
    Preferably, the catalytic processes are chosen from reactions of hydrogenations of aromatic or polyaromatic compounds, of selective hydrogenation of polyunsaturated compounds, the Fischer-Tropsch synthesis.
    Preferably, the methods for purifying gaseous or liquid effluents are chosen from the purification of charges of liquid hydrocarbons, natural gases, synthesis gases containing sulfur impurities or halogenated impurities.
    Description of the figures
    FIG. 1 is a schematic representation of a process for preparing a catalyst or a capture mass according to the invention. In this preparation process, the active phase of the catalyst or of the capture mass is supplied to the support in a single step, the precursor of the active phase being in the form of a metal salt comprising at least one metal belonging to VIB, VIIB, VIIIB, IB or IIB groups whose melting temperature of said metal salt is between 20 and 150 ° C
    FIG. 2 is a schematic representation of a process for the preparation of a catalyst or a capture mass according to the prior art. In this preparation process, the active phase of the catalyst or of the capture mass is supplied on the catalyst support in the same proportions as in FIG. 1, but in two distinct stages and with a precursor of the active phase occurring under form of aqueous solution.
    Detailed description of the invention
    Definitions
    In the following description, 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 VIIIB according to the CAS classification corresponds to the metals in columns 8, 9 and 10 according to the new IUPAC classification.
    The textural and structural properties of the support, the catalyst or the capture mass described below are determined by the characterization methods known to those skilled in the art. The total pore volume and the pore distribution are determined in the present invention by mercury porosimetry (cf. Rouquerol F .; Rouquerol J .; Singh K. "Adsorption by Powders & Porous Solids: Principle, methodology and applications", Academic Press, 1999).
    More particularly, the total pore volume is measured by mercury porosimetry according to standard ASTM D4284-92 with a wetting angle of 140 °, for example by means of an Autopore III ™ model apparatus of the Micromeritics ™ brand.
    The specific surface is determined in the present invention by the B.E.T method, method described in the same reference work as porosimetry with mercury, and more particularly according to standard ASTM D3663-03.
    Preparation process
    According to the invention, the catalyst or the capture mass comprises an active phase based on at least one metal from group VIB, VIIB, VIIIB, IB or IIB and a porous oxide support prepared by a preparation process comprising at least the following steps :
    a) said porous oxide support is brought into contact with at least one metal salt comprising at least one metal belonging to groups VIB, VIIB, VIIIB, IB or IIB whose melting temperature of said metal salt is between 20 and 150 ° C for a time of between 5 minutes and 5 hours to form a solid mixture, the mass ratio between said metal salt and said porous oxide support being between 0.1 and 1;
    b) the solid mixture obtained at the end of step a) is heated with stirring to a temperature between the melting temperature of said metal salt and 200 ° C. and with a residence time of between 5 minutes and 12 hours;
    c) optionally, the solid obtained at the end of step b) is dried at a temperature below 200 ° C;
    d) the solid obtained at the end of step b) or c) is calcined at a temperature greater than 200 ° C. and less than or equal to 1100 Ό under an inert atmosphere or under an oxygen-containing atmosphere.
    The steps of the process for preparing the catalyst or the capture mass according to the invention are described in detail below.
    Step a)
    According to step a), a porous support of the oxide type is brought into contact with a metal salt comprising at least one metal belonging to groups VIB, VIIB, VIIIB, IB or IIB whose melting point of said metal salt is between 20 and 150 ° C. for a period of between 5 minutes to 5 hours to form a solid mixture, the mass ratio between said metal salt and said porous oxide support being between 0.1 and 1, preferably between 0.3 and 0, 9. In this step, the metal salt is in solid form, that is to say that the contacting between said porous support and said metal salt is carried out at a temperature below the melting temperature of said metal salt.
    According to step a), the porous support can comprise at least one refractory oxide chosen from the group consisting of magnesium, aluminum, silicon, zirconium, cerium, thorium or titanium oxides, taken alone or as a mixture between them, such as silica-alumina.
    Preferably, the support is chosen from aluminas, silicas and silica-aluminas.
    The support can also be a carbon, a silico-aluminate, a clay or any other compound known to be used as a support.
    Preferably, the support has a BET surface of between 5 and 500 m 2 / g, even more advantageously between 10 and 300 m 2 / g. The BET specific surface is measured by physisorption with nitrogen.
    The total pore volume of the support is generally between 0.1 and 3 cm 3 / g, preferably between 0.3 and 1.5 cm 3 / g.
    The support may be in the form of balls, extrudates, trilobes, pellets, irregular and non-spherical agglomerates whose specific shape may result from a crushing step, of powder with a particle size between 10 and 500 μm or monolith. Advantageously, said support is in the form of beads, extrudates or powder with a micrometric particle size.
    According to step a), at least one metal salt is provided comprising at least one metal belonging to groups VIB, VIIB, VIIIB, IB or IIB whose melting temperature of said metal salt is between 20 and 150O. Preferably, the metals are chosen from Zn, Cu, Ni, Fe, Co, Mn, taken alone or as a mixture. Preferably, the metal salt is hydrated. Preferably, the metal salt is a hydrated nitrate salt. Preferably, the metal salt is chosen from zinc nitrate trihydrate (Zn (NO 3 ) 2 , 3H 2 O, T fusion = 45.5 ° C), zinc nitrate hexahydrate (Zn (NO 3 ) 2 , 6H 2 O, T fusion = 36.4 ° C), copper nitrate trihydrate (Cu (NO 3 ) 2 , 3H 2 O, T fusion = 114.5 ° C), copper nitrate hexahydrate (Cu (NO 3) 2 .6H 2 O, T mp = 26.4 ° C), nickel nitrate hexahydrate (Ni (NO 3) 2 .6H 2 O, Tf is US i = 56.7 ° C), nitrate iron nonahydrate (Fe (NO 3 ) 3 , 9H 2 O, T fusion = 47.2 ° C), cobalt nitrate hexahydrate (Co (N0 3 ) 2 , 6H 2 O, Tf US ion = 55.0 ° C ), manganese nitrate tetrahydrate (Mn (NO 3 ) 2 , 4H 2 O, T fuS ion = 37.0O), manganese nitrate hexahydrate (Mn (NO 3 ) 2 , 6H 2 O, T fuS ion = 26 , 0 ° C), taken alone or as a mixture.
    According to step a), bringing said porous oxide support into contact with the cobalt metal salt can be carried out by any method known to those skilled in the art. Preferably, the contacting of said porous support and the metal salt is carried out with contact means chosen from convective mixers, drum mixers or static mixers. Step a) is carried out for a period of between 5 minutes to 5 hours depending on the type of mixer used, preferably between 10 minutes and 4 hours, and even more preferably between 15 minutes and 3 hours.
    In comparison with the prior art described in document US Pat. No. 5,036,032 and based on bringing a support into contact in a bath of molten salts, step a) of the process according to the invention allows:
    - optimized control of the quantity of metal deposited on the catalyst; and
    - A dangerousness and a controlled cost of the preparation process by minimizing the quantities of metallic precursor used not exceeding 1 gram of metallic precursor per 1 gram of support.
    Step b)
    According to step b), the mixture obtained at the end of step a) is heated with stirring to a temperature between the melting temperature of the metal salt and 200 ° C. and at atmospheric pressure. The residence time is between 5 minutes and 12 hours, preferably between 5 minutes and 4 hours.
    According to step b), the mechanical homogenization of the mixture can be done by any method known to those skilled in the art. Preferably, convective mixers, drum mixers or static mixers can be used.
    Step c) (optional step)
    According to the optional step c), the drying of the solid obtained in step b) is carried out at a temperature below 200 ° C, advantageously between 50 and 180 O, preferably between 70 and 150 O, very preferably between 75 and 130 ° C.
    The drying step is preferably carried out for a maximum of 4 hours, preferably under an inert atmosphere or under an atmosphere containing oxygen.
    The optional drying step can be carried out by any technique known to those skilled in the art. It is advantageously carried out at atmospheric pressure or at reduced pressure. Preferably, this step is carried out at atmospheric pressure. It is advantageously carried out using air or any other hot gas. Preferably, the gas used is either air, or an inert gas such as argon or nitrogen. Very preferably, the drying is carried out in the presence of nitrogen and / or air. Unlike step b), the drying step c) is not carried out with stirring by any means whatsoever.
    Step d)
    According to step d), the solid obtained in step b) or c) undergoes a calcination treatment at a temperature above 200 ° C and less than or equal to 1100 ° C, preferably between 250 ° C and 650 ° C, under an inert atmosphere (nitrogen for example) or under an atmosphere containing oxygen (air for example). The duration of this heat treatment is generally less than 16 hours, preferably less than 5 hours. After this treatment, the active phase is in oxide form and the solid contains little or no counter ions and water of crystallization present initially in the metal salt. The calcination step can be carried out by any technique known to those skilled in the art.
    It is advantageously carried out in a crossed bed or in a fluidized bed using air or any other hot gas.
    Catalyst or capture mass
    The catalyst or the capture mass prepared and used according to the invention contains from 1 to 60% by weight (calculated in oxide form) of one or more elements belonging to groups VIB, VIIB, VIIIB, IB or IIB by relative to the total weight of the catalyst or of the capture mass.
    Preferably, said catalyst or the capture mass has a BET surface area between 5 and 400 m 2 / g, preferably between 10 and 300 m 2 / g, and a total pore volume between 0.1 and 1.5 cm 3 / g, preferably between 0.3 and 1.0 cm 3 / g.
    Said catalyst or the capture mass is in the form of beads, extrudates, trilobes, pellets, irregular and non-spherical agglomerates whose specific shape can result from a crushing step, of powder with a particle size between 10 and 500 pm or monolith. Advantageously, said catalyst or the capture mass is in the form of beads, extrudates or powder of micrometric particle size.
    Use of catalyst or capture mass
    The present invention also relates to the use of such catalysts or capture masses in industrial processes. In a non-exhaustive manner, in the field of catalytic processes, there may be mentioned in particular the reactions of hydrogenations of aromatic or polyaromatic compounds, of selective hydrogenation of polyunsaturated compounds, the Fischer-Tropsch synthesis.
    The use of said catalyst in a hydrogenation process of at least one aromatic or polyaromatic compound contained in a hydrocarbon feed having a final boiling point less than or equal to 650 ° C. can be carried out in the gas phase or in the phase liquid, at a temperature between 20 and 350 ° C, at a pressure between 0.1 and 20 MPa, at a hydrogen / aromatic molar ratio between 0.1 and 10 and at an hourly volume speed VVH (corresponding to the volume load per volume of catalyst and per hour) between 0.05 h -1 and 50 h ' 1 .
    The use of said catalyst in selective hydrogenation of polyunsaturated compounds is carried out by bringing a filler into contact with the catalyst prepared according to the invention, said filler being able to be selected from the group consisting of cuts C3 of steam cracking, cuts C4 of steam cracking, C5 steam cracking cuts and steam cracking essences also called pyrolysis essences. The selective hydrogenation can be carried out in the gas or liquid phase, preferably in the liquid phase. Indeed, a liquid phase reaction lowers the energy cost and increases the cycle time of the catalysts.
    For a liquid phase reaction of selective hydrogenation, the pressure is generally between 1 and 5 MPa, the hourly space velocity VVH is generally between 0.5 h -1 and 50 h ' 1 , the temperature between 2 and 200 ° C and the hydrogen / polyunsaturated molar ratio between 0.1 and 4, preferably between 1 and 2.
    For a hydrogenation reaction in the gas phase, the pressure is generally between 1 and 3 MPa, the hourly volume speed is generally between 500 h -1 and 5000 h ' 1 , the temperature between 40 and 120 ° C and the ratio hydrogen / polyunsaturated molar between 0.1 and 4, preferably between 1 and 2.
    The implementation of aromatic hydrogenation processes and selective hydrogenation of polyunsaturated compounds is preferably carried out in a fixed bed.
    The use of said catalyst in Fischer-Tropsch synthesis leads to the production of essentially linear and saturated C5 + hydrocarbons. The feedstock employed for carrying out the process of the invention comprises, preferably consists, synthesis gas. The synthesis gas is a mixture of carbon monoxide and hydrogen having H 2 / CO molar ratios which can vary in a ratio of 0.5 to 4 depending on the process by which it was obtained. The H 2 / CO molar ratio of the synthesis gas is generally close to 3 when the synthesis gas is obtained from the process of steam reforming of hydrocarbons or alcohol. The H 2 / CO molar ratio of the synthesis gas is of the order of 1.5 to 2 when the synthesis gas is obtained from a partial oxidation process. The H 2 / CO molar ratio of the synthesis gas is generally close to 2.5 when it is obtained from a thermal reforming process. The H 2 / CO molar ratio of the synthesis gas is generally close to 1 when it is obtained from a gasification and CO 2 reforming process.
    The catalyst used in the hydrocarbon synthesis process according to the invention can be used in different types of reactors, for example in a fixed bed, in a moving bed, in a bubbling bed or even in a three-phase fluidized bed. The use of the catalyst in suspension in a three-phase fluidized reactor, preferably of the bubble column type, is preferred. In this preferred implementation of the catalyst, said catalyst is divided into a very fine powder, particularly of the order of a few tens of microns, this powder forming a suspension with the reaction medium. This technology is also known by the slurry process terminology by a person skilled in the art.
    The process for synthesizing hydrocarbons according to the invention is carried out under a total pressure of between 0.1 and 15 MPa, preferably between 0.5 and 10 MPa, at a temperature between 150 and 350 ° C, preferably between 180 and 270 ° C. The hourly space velocity is advantageously between 100 and 20,000 h -1 and preferably between 400 and 10,000 h ' 1 .
    Here again in a non-exhaustive manner, in the field of processes for the purification of gaseous or liquid effluents, mention may be made in particular of the purification of feeds of liquid hydrocarbons, natural gases, synthesis gases containing inter alia sulfur impurities such as as H 2 S, COS, and / or CS 2 , or halogenated impurities such as HCI. In these methods, the charge to be treated is brought into contact with the capture mass in a reactor, which can be either a fixed bed reactor or a radial reactor, or even a fluidized bed reactor.
    In the context of the application concerning the desulfurization of gaseous or liquid charges, the conditions of use of said capture mass are preferably such that the pressure is between 0.1 and 25 MPa and the temperature between 100 and 450 ° C.
    In the context of the application relating to the removal of halogenated compounds from a gaseous or liquid charge, the conditions of use of said capture mass are preferably such that the pressure is between 0.1 and 10 MPa, and the temperature between 20 and 190 ° C.
    Examples
    To illustrate the invention and to allow a person skilled in the art to execute it, we present below various embodiments of the process for the preparation of supported cobalt-based catalysts for its use in Fischer-Tropsch synthesis; however, this should not limit the scope of the invention which is applicable to any type of catalyst or capture mass for their use in all industrial processes.
    Example 1 (compliant)
    FIG. 1 illustrates an industrial manufacturing method of a catalyst prepared by the preparation process according to the invention for a “100 kg / h” base of catalyst produced. In FIG. 1, only the main equipment is present, in particular the “annex” equipment dedicated to the transport of solids between the stages and known to those skilled in the art (pneumatic transport, dosing hoppers, feed hoppers, screw for conveying etc.) have not been shown. In this example, the (conforming) preparation process is carried out so as to deposit in one step approximately 13% by weight of Co on a silica-alumina initially containing 5% by weight of SiO 2 and 4% by weight of Co thanks to the introduction of a cobalt aluminate spinel in said support. The silica-alumina has an average particle size equal to 80 μm, a specific surface of 180 m 2 / g and a pore volume of 0.55 ml / g. The cobalt contained in the spinel phase is not reducible during the final activation of the Fischer-Tropsch catalyst (reduction). The cobalt contained in the spinel does not constitute the active phase of the catalyst.
    Referring to FIG. 1, a silica-alumina support stored in a storage unit 1 via line 7 and a cobalt nitrate salt hexahydrate (Aldrich,> 98%) is supplied to a homogenization step 3. 20% by weight of Co) stored in a storage unit 2 via line 8. The homogenization step is a drum mixer inclined at 45 ° and equipped with counter-blades to ensure a cascading movement when mixing the powders . The mixer is stirred at 60 rpm for 1 hour at room temperature and pressure. The solid mixture obtained is then sent via line 9 to a heating capacity 4 (hot impregnator) in which the temperature is increased at 5 ° C / min to 80 ° C and left for 1 hour. The solid obtained is then sent to a calcination oven 5 via line 10 operating at 400 ° C for 4 h in a crossed bed. The catalyst obtained containing 17.0% by weight of Co (in the form of Co 3 O 4 oxide) relative to the weight of the catalyst is sent to a catalyst storage unit 6 via line 11.
    The flow rates indicated in table 1 below correspond to continuous equivalent flow rates making it possible to ultimately produce a "100 kg / h" base of catalyst. Table 1 below lists the equipment and their main characteristics according to a conforming example:
    Reference Equipment description Sizing capacity(kg / h) Absorbed heat (kW) 1 Storage of the catalytic support 80 - 2 Salt storage 65 - 3 Homogenizer 145 - 4 Hot impregnator 145 5 5 Calcination oven 135 39 6 Storage of final catalyst 100 - Table 1: List of process equipment according to the invention, capacity and heat absorbed
    of the conforming process
    Example 2 (non-compliant)
    According to the prior art, the achievement of the high metal charge rate is carried out in two passes and requires the repetition of the successive stages of impregnation, drying and calcination. In terms of industrial operation, this can result in the presence of two sets of equipment (impregnator, dryer, calcination oven), each dedicated to a particular pass. In this example, the preparation process (non-conforming) is carried out so as to deposit in two stages approximately 13% by weight of Co on a silica-alumina initially containing 5% by weight of SiO 2 , and 4% by weight of Co thanks to the introduction of a cobalt aluminate spinel into said support. The silica-alumina has an average particle size equal to 80 μm, a specific surface of 180 m 2 / g and a pore volume of 0.55 ml / g. The cobalt contained in the spinel phase is not reducible during the final activation of the Fischer-Tropsch catalyst (reduction). The cobalt contained in the spinel does not constitute the active phase of the catalyst.
    Referring to FIG. 2, a silica-alumina support stored in a storage unit 12 via line 22 is supplied to a homogenization step 14. A step of impregnating an aqueous nitrate solution is then carried out. of cobalt (Orrion Chemicals Metalchem, - 13% by weight of Co) supplied via line 23 on the silica alumina support supplied via line 24 in an impregnation unit 15. The impregnated support is then sent to a drying unit 16 via line 25. After drying at 120 ° C for 3 hours, the solid is sent via line 26 to a calcination oven 17 operating at 400 ° C for 4 hours in air. The catalyst obtained at the outlet of the calcination furnace is then sent via line 27 to a second impregnation unit 18 in which an aqueous solution of cobalt nitrate (Orrion Chemicals 5 Metalchem, -13% by weight of Co) is deposited on the catalyst. ) supplied via line 23. The impregnated catalyst is then sent to a drying unit 19 via line 28. After drying at 120 ° C. for 3 hours, the solid is sent via line 29 to a calcination oven 20 operating at 400 ° C for 4 hours in air. The catalyst obtained at the outlet of the calcination furnace is then sent via line 30 to a catalyst storage unit 21. A catalyst is obtained which contains 17% by weight of Co (in the form of oxide Co 3 0 4 ) relative to the weight of the catalyst.
    FIG. 2 illustrating such a manufacturing method, presents a continuous operation on the whole of the catalyst production chain but with a number of steps and 15 of main equipment multiplied. Table 2 below lists the equipment and their main characteristics of the non-conforming example:
    Reference Equipment description Sizing capacity (kg / h) Absorbed heat (kW) 12 Catalytic support storage 80 - 13 Impregnation solution storage tank 92 - 14 Homogenizer 80 - 15 Impregnator (passel) 126 - 17 Calcination oven (pass 1) 113 24 21 Storage of final catalyst 100 - 16 Dryer (pass 1) 126 13 18 Impregnator (pass 2) 138 - 19 Dryer (pass 2) 138 13 20 Calcination oven (pass 2) 123 27
    box 2: List of process equipment according to the invention, capacity and heat absorbed from the non-compliant process
    The comparison of examples 1 (compliant) and 2 (non-compliant) shows a significant gain on:
    - the number of main equipment used. Indeed, with iso-loading of metal (17% by weight of Cobalt in the form of oxide Co 3 0 4 ) and with similar capacities, a single impregnator and a single calcination oven are necessary in the preparation process according to the invention. 'invention. In addition, according to this variant of the invention, the two drying units could be omitted because they were not necessary;
    - energy expenditure. The total process heat absorbed is reduced by a factor of between 1.5 and 2.0 (44 kW versus 77 kW). In the case of the preparation of a cobalt-based catalyst, the vaporization of "water" of the cobalt nitrate solution (drying step in the context of non-conforming example 2) requires a power considerably higher than that required for the melting of cobalt salts (Example 1 in accordance with the preparation process according to the invention).
    The preparation process according to the invention therefore allows a major gain on the number of unit operations and on energy expenditure. This results in a better efficiency of the industrial process (investment, utility expenses, maintenance, simplified operation).
    权利要求:
    Claims (14)
    [1" id="c-fr-0001]
    1. Method for preparing a catalyst or a capture mass comprising an active phase based on at least one metal from group VIB, VIIB, VIIIB, IB or IIB and a porous oxide support, said catalyst being prepared by at least the following steps:
    a) said porous oxide support is brought into contact with at least one metal salt comprising at least one metal belonging to groups VIB, VIIB, VIIIB, IB or IIB whose melting temperature of said metal salt is between 20 and 150 ° C for a time of between 5 minutes and 5 hours to form a solid mixture, the mass ratio between said metal salt and said porous oxide support being between 0.1 and 1;
    b) the solid mixture obtained at the end of step a) is heated with stirring to a temperature between the melting temperature of said metal salt and 200 ° C and with a residence time between 5 minutes and 12 hours;
    c) optionally, the solid obtained at the end of step b) is dried at a temperature below 200 ° C;
    d) the solid obtained at the end of step b) or c) is calcined at a temperature greater than 200 ° C. and less than or equal to 1100 Ό under an inert atmosphere or under an oxygen-containing atmosphere.
    [2" id="c-fr-0002]
    2. The method of claim 1, wherein said metal is selected from Zn, Cu, Ni, Fe, Co, Mn.
    [3" id="c-fr-0003]
    3. Method according to claims 1 or 2, wherein the metal salt is a hydrated nitrate salt.
    [4" id="c-fr-0004]
    4. The method of claim 3, wherein said metal salt is chosen from zinc nitrate trihydrate, zinc nitrate hexahydrate, copper nitrate trihydrate, copper nitrate hexahydrate, nickel nitrate hexahydrate, iron nitrate nonahydrate, cobalt nitrate hexahydrate, manganese nitrate tetrahydrate, manganese nitrate hexahydrate, taken alone or as a mixture.
    [5" id="c-fr-0005]
    5. Method according to any one of claims 1 to 4, wherein the mass ratio between said metal salt and the porous support is between 0.3 and 0.9.
    [6" id="c-fr-0006]
    6. Method according to any one of claims 1 to 5, in which step a) is carried out for 10 minutes to 4 hours.
    [7" id="c-fr-0007]
    7. Method according to any one of claims 1 to 6, wherein the porous support of said catalyst or capture mass is chosen from alumina, silica or silica-alumina.
    [8" id="c-fr-0008]
    8. Method according to any one of claims 1 to 7, wherein the calcination time of step d) is less than 16 hours.
    [9" id="c-fr-0009]
    9. Method according to any one of claims 1 to 8, wherein said porous support is in the form of a powder with a particle size between 10 and 500 μητ
    [10" id="c-fr-0010]
    10. Method according to any one of claims 1 to 9, wherein said porous support comprises a specific surface of between 5 and 500 m 2 / g.
    [11" id="c-fr-0011]
    11. Method according to any one of claims 1 to 10, wherein said porous support has a total pore volume of between 0.1 and 3 ml / g.
    [12" id="c-fr-0012]
    12. Use of the catalyst or the capture mass prepared according to any one of claims 1 to 11 in the field of catalytic processes or in the context of processes for purifying gaseous or liquid effluents.
    [13" id="c-fr-0013]
    13. Use according to claim 12, in which the catalytic processes are chosen from reactions of hydrogenations of aromatic or polyaromatic compounds, of selective hydrogenation of polyunsaturated compounds, Fischer-Tropsch synthesis.
    [14" id="c-fr-0014]
    14. Use according to claim 12, in which the methods for purifying gaseous or liquid effluents are chosen from the purification of charges of liquid hydrocarbons, natural gases, synthesis gases containing sulfur impurities or halogenated impurities.
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    同族专利:
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    FR3085284B1|2021-05-07|
    US20200070137A1|2020-03-05|
    引用文献:
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    GB191308864A|1912-12-04|1914-04-15|James Yate Johnson|Improvements in or connected with Catalysts and in the Manufacture of Hydrogen.|
    US5036032A|1988-03-25|1991-07-30|Exxon Research And Engineering Company|Selective catalysts and their preparation for catalytic hydrocarbon synthesis|
    US5159128A|1990-08-31|1992-10-27|Shell Oil Company|Process for cracking paraffins to olefins|
    WO2001019514A1|1999-09-17|2001-03-22|Philips Petroleum Company|Process for producing a metal aluminate catalyst support|
    EP2921227A1|2014-03-20|2015-09-23|IFP Energies nouvelles|Fischer-tropsch catalyst based on a group viiib metal and a carrier of oxides including alumina, silica, a spinel and phosphorus|
    US20150314264A1|2014-04-30|2015-11-05|Uop Llc|Metal impregnated zeolite adsorbents, methods of making, and systems for using the same|
    FR3112087A1|2020-07-03|2022-01-07|IFP Energies Nouvelles|PROCESS FOR PREPARING A CATALYST FOR HYDROGENATION OF AROMATIC COMPOUNDS OBTAINED FROM MELTED SALTS AND A NICKEL COPPER ALLOY|
    FR3112088A1|2020-07-03|2022-01-07|IFP Energies Nouvelles|PROCESS FOR THE PREPARATION OF A SELECTIVE HYDROGENATION CATALYST OBTAINED FROM MELTED SALTS AND A NICKEL COPPER ALLOY|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1857940A|FR3085284B1|2018-09-04|2018-09-04|PROCESS FOR PREPARING A CATALYST OR A COLLECTION MASS FROM MELTED SALTS|FR1857940A| FR3085284B1|2018-09-04|2018-09-04|PROCESS FOR PREPARING A CATALYST OR A COLLECTION MASS FROM MELTED SALTS|
    US16/558,597| US20200070137A1|2018-09-04|2019-09-03|Process for preparing a catalyst or a trapping mass from molten salts|
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