MESOPOROUS CATALYST OF RESIDUAL HYDROCONVERSION AND METHOD OF PREPARATION

专利摘要:
The invention relates to the preparation of a catalyst comprising: a calcined aluminum predominantly oxide support; a hydro-dehydrogenating active phase comprising at least one Group VIB metal, optionally at least one Group VIII metal, optionally phosphorus, said catalyst having: a Sbet specific surface area greater than 75 m 2 / g, a total pore volume greater than or equal to 0.55 ml / g, a median mesoporous diameter greater than or equal to 16 nm, a mesoporous volume greater than or equal to 0.50 ml / g, a macroporous volume of less than 15% of the total pore volume said process comprising at least: a) a first step of precipitating at least one basic precursor and at least one acidic precursor, at least one of which comprises aluminum, at a pH of between 8.5 and 10.5, with a progress rate of the first step of between 5 and 13%, at a temperature between 20 and 90 ° C and for 2 to 30 minutes; b) a heating step, c) a second precipitation step by adding to the suspension at least one basic precursor and at least one acidic precursor in which at least one of the basic or acidic precursors comprises aluminum, with a pH of between 8.5 and 10.5 and a progress rate of the second stage of between 87 and 95%; d) a filtration step; e) a drying step, f) a shaping step, g) a heat treatment step; h) a step of impregnating the hydro-dehydrogenating active phase on the support obtained in step g). The invention finally relates to the mesoporous catalyst obtained and its use in hydrotreating processes or hydroconversion of heavy hydrocarbon feeds.
公开号:FR3022158A1
申请号:FR1455415
申请日:2014-06-13
公开日:2015-12-18
发明作者:Malika Boualleg；Bertrand Guichard
申请人:IFP Energies Nouvelles IFPEN；
IPC主号:

专利说明:

[0001] TECHNICAL FIELD OF THE INVENTION The invention relates to hydrotreatment catalysts having a hydrodemetallation (HDM) favorable texture and formulation, while maintaining a satisfactory hydrodesulfurization (HDS) activity, their preparation and their use. The invention consists in the use of mesoporous catalysts supported on an aluminum oxide matrix comprising at least one element of group VIB and possibly of group VIII, as well as, optionally, the phosphorus element. It has been discovered that this type of formulation, associated with a support of specific textural properties, makes it possible to obtain simultaneously maximized HDM hydrodemetallation and hydrodesulphurization HDS performances, in a process for the hydrotreatment of residues, in particular in a fixed bed, on weakly charged charges. made of metals.
[0002] PRIOR ART It is known to a person skilled in the art that catalytic hydrotreating makes it possible, by bringing a hydrocarbon feedstock into contact with a catalyst whose properties, in terms of metals of the active phase and of porosity, are previously well adjusted, significantly reduce its content of asphaltenes, metals, sulfur and other impurities while improving the ratio hydrogen on carbon (H / C) and while transforming it more or less partially into lighter cuts. The fixed bed residue hydrotreating processes (commonly called "Residual Desulfurization" unit or RDS) lead to high refining performance: typically they can produce a boiling temperature cut above 370 ° C. containing less than 0 ° C. , 5% by weight of sulfur and less than 20 ppm of metals from fillers containing up to 5% by weight of sulfur and up to 250 ppm of metals (Ni + V). The different effluents thus obtained can serve as a basis for the production of heavy-duty heavy-duty fuels and / or pretreated feedstocks for other units such as catalytic cracking ("Fluid Catalytic Cracking" according to the English terminology). On the other hand, the hydroconversion of the residue into slices lighter than the atmospheric residue (gas oil and gasoline in particular) is generally low, typically of the order of 10-20% by weight. In such a process, the feed, premixed with hydrogen, circulates through a plurality of fixed bed reactors arranged in series and filled with catalysts. The total pressure is typically between 100 and 200 bar (10-20 MPa) and the temperatures between 340 and 420 ° C. The effluents withdrawn from the last reactor are sent to a fractionation section.
[0003] Conventionally, the fixed bed hydrotreating process consists of at least two steps (or sections). The first so-called hydrodemetallation (HDM) stage is mainly aimed at eliminating the majority of metals from the feedstock by using one or more hydrodemetallization catalysts. This stage mainly includes vanadium and nickel removal operations and, to a lesser extent, iron.
[0004] The second step, or so-called hydrodesulfurization (HDS) section, consists in passing the product of the first step over one or more hydrodesulfurization catalysts, which are more active in terms of hydrodesulphurization and hydrogenation of the feedstock, but less tolerant to metals.
[0005] For the hydrodemetallation (HDM) stage, the catalyst must be able to treat metal and asphaltene-rich fillers, while having a high demetallizing power associated with a high metal retention capacity and high coking resistance. Catalysts having a bimodal porous distribution making it possible to achieve high hydrodemetallation yields have been described in US Pat. No. 5,221,666. The advantage of such a porous distribution is also highlighted in US Pat. Nos. 5,089,463 and US Pat. The initial active phase of the catalyst placed in the hydrodemetallization stage is generally composed of nickel and molybdenum, and possibly of dopants such as phosphorus. This active phase is known to be more hydrogenating than a phase consisting of cobalt and molybdenum, also used sometimes, and thus limits the formation of coke in the porosity and thus the deactivation. For the hydrodesulfurization step (HDS), the catalyst must have a high hydrogenolysing potential so as to carry out a deep refining of the products: desulfurization, further demetallation, lowering of the carbon conradson (CCR) and asphaltenes content. Such a catalyst is characterized by a low macroporous volume (US 6,589,908). In addition, US Pat. No. 4,818,743 teaches that the porous distribution can be monopopulated between 1 and 13 nm or bipopulated with a relative difference between the two populations that can vary from 1 to 20 nm, as in US Pat. No. 6,589,908. The active phase of the catalyst placed in the hydrodesulfurization stage is generally cobalt and molybdenum, as described in US Pat. No. 6,332,976. When the metal content in the feed is too high (greater than 250 ppm) and / or when a large conversion (conversion of the heavy fraction 540 ° C + (or 370 ° C +) to a lighter fraction 540 ° C (or 370 ° C) is sought, processes for hydrotreatment in bed In this type of process (cf. MS Rana et al., Fuel 86 (2007), p.1216), the purification performance is lower than that of the RDS processes, but the hydroconversion of the residue fraction is high. (of the order of 45-85 (3/0 The high temperatures involved, between 415 and 440 ° C, contribute to this high hydroconversion. Thermal cracking reactions are in fact favored, the catalyst generally not having a specific hydroconversion function. In addition, the effluents formed by this type of conversion may present problems of stability (formation of sediments).
[0006] For the hydrotreating of residues, the development of polyvalent, efficient and stable catalysts is therefore essential. For bubbling bed processes, the patent application WO 2010/002699 teaches in particular that it is advantageous to use a catalyst whose support has a median pore diameter of between 10 and 14 nm and whose distribution is narrow. It specifies that less than 5% of the pore volume must be developed in pores larger than 21 nm and in the same way, less than 10% (3% of the volume must be observed in small pores of sizes less than 9 nm US Patent 5,968,348 confirms the preference of using a support whose mesoporosity remains close to 11 to 13 nm, possibly with the presence of macropores and a high BET surface, here at least 175 m 2 / g. For fixed bed processes, US Pat. No. 6,780,817 teaches that it is necessary to use a catalyst support which has at least 0.32 ml / g of macroporous volume for stable fixed bed operation. Moreover, it has a median diameter in the mesopores of 8 to 13 nm and a high specific surface area of at least 180 m2 / g.
[0007] US Pat. No. 6,919,294 also describes the use of so-called bimodal support, therefore meso and macroporous, with the use of high macroporous volumes, but with a mesoporous volume limited to not more than 0.4 ml / g.
[0008] US Pat. Nos. 4,976,848 and 5,089,463 disclose a heavy charge hydrodemetallation and hydrodesulphurisation catalyst comprising a hydrogenating active phase based on Group VI and VIII metals and an inorganic refractory oxide support, the catalyst having precisely between 5 and 11% of its porous volume in the form of macropores and mesopores with a median diameter greater than 16.5 nm.
[0009] US Pat. No. 7,169,294 describes a heavy-weight hydroconversion catalyst comprising between 7 and 20% of Group VI metal and between 0.5 and 6% by weight of Group VIII metal on an aluminum support. The catalyst has a specific surface area of between 100 and 180 m 2 / g, a total pore volume greater than or equal to 0.55 ml / g, at least 50% of the total pore volume is included in the pores larger than 20 nm, at least 5 (3/0) of the total pore volume is comprised in pores larger than 100 nm, at least 85 (3/0 of the total pore volume being included in pores between 10 and 120 nm in size less than 2% (3% of the total pore volume being contained in pores with a diameter greater than 400 nm, and less than 1% of the total pore volume being contained in pores with a diameter greater than 1000 nm. In particular, developments concern the optimization of the porous distribution of the catalyst or of catalyst mixtures by optimizing the aluminum catalyst support.
[0010] Thus, US Pat. No. 6,589,908 describes, for example, a process for the preparation of an alumina characterized by the absence of macropores, less than 5% of the total pore volume constituted by pores with a diameter greater than 35 nm, a high volume. porous greater than 0.8 ml / g, and a bimodal mesopore distribution in which the two modes are separated by 1 to 20 nm and the primary porous mode is greater than the median pore diameter. describes two stages of precipitation of alumina precursors under well-controlled conditions of temperature, pH and flow rates The first stage operates at a temperature of between 25 and 60 ° C., a pH of between 3 and 10. The suspension is then heated to a temperature between 50 and 90 ° C. Reagents are again added to the suspension, which is then washed, dried, shaped and calcined to form a catalyst support. said support is then impregnated with an active phase solution to obtain a hydrotreatment catalyst; a catalyst for hydrotreating residues on a mesoporous monomodal support of porous median diameter around 20 nm is described. US Pat. No. 7,790,652 describes hydroconversion catalysts that can be obtained by coprecipitation of an alumina gel, then introduction of metals onto the support obtained by any method known to those skilled in the art, in particular by impregnation. The resulting catalyst has a mesoporous monomodal distribution with a mesoporous median diameter of between 11 and 12.6 nm and a porous distribution width of less than 3.3 nm. In view of the prior art, it seems very difficult to obtain a catalyst having both a high total pore volume, a high mesoporous volume coupled to a minimum macroporous volume, a very high median mesopore diameter, and an active phase. hydro-dehydrogenating. Moreover, the increase in porosity is often at the expense of the specific surface area, and the mechanical strength. Surprisingly, the Applicant has discovered that a catalyst prepared from an alumina resulting from the calcination of a specific alumina gel having a low dispersibility, by impregnation of a hydro-dehydrogenating active phase on the alumina calcined had a particularly interesting porous structure while having an active phase content suitable for the hydrotreatment of heavy loads, especially for hydrodemetallation reactions. The present invention relates to the preparation of a catalyst comprising at least one element of group VI B, optionally at least one element of group VIII and optionally the phosphorus element supported on an aluminum oxide support having properties particular textures, in particular a high total pore volume (greater than or equal to 0.50 ml / g) and a high mesopore median diameter (greater than or equal to 16 nm), its BET specific surface area remaining greater than 75 m2 / g preferably, greater than 100 m 2 / g, said process comprising at least the following steps: a) a first step of precipitation, in an aqueous reaction medium, of at least one basic precursor and at least one acidic precursor in which at least one of the basic or acidic precursors comprises aluminum, at a pH of the reaction medium of between 8.5 and 10.5, the flow rate of the acidic and basic precursor (s) containing aluminum is set so as to obtain a first step advance rate of between 5 and 13 ° A, the feed rate being defined as the proportion of alumina formed in A1203 equivalent at the first step precipitation step relative to the total amount of alumina formed at the end of step c) of the preparation process, said step operating at a temperature of between 20 and 90 ° C. and for a duration of between 2 minutes and 30 minutes ; b) a step of heating the suspension; c) a second step of precipitation of the suspension obtained at the end of the heating step b) by adding to the suspension at least one basic precursor and at least one acidic precursor in which at least one of the precursors base or acid comprises aluminum, the relative flow rate of the acidic and basic precursors is chosen so as to obtain a pH of the reaction medium of between 8.5 and 10.5 and the flow rate of the acidic and basic precursor (s) containing aluminum being adjusted so as to obtain a progress rate of the second step of between 87 and 95 ° A, the feed rate being defined as the proportion of alumina formed in Al 2 O 3 equivalent during said second precipitation step relative to the total amount of alumina formed at the end of step c) of the preparation process; d) a filtration step of the suspension obtained at the end of the second precipitation step c) to obtain an alumina gel; e) a step of drying said alumina gel obtained in step d) to obtain a powder; f) a step of shaping the powder obtained at the end of step e) to obtain a green material; g) a heat treatment step of the green material obtained at the end of step f) to obtain an aluminum oxide support; h) a step of impregnating the hydro-dehydrogenating active phase on said aluminum oxide support. An advantage of the invention is to provide a new process for the preparation of a catalyst impregnated on an amorphous mesoporous alumina support from a specific alumina gel prepared according to a process comprising at least one precipitation step of at least one at least one aluminum precursor in which between 5 and 13 (3/0 weight of alumina only are formed in the first precipitation step, relative to the total amount of alumina formed in Al 2 O 3 equivalent at the end of said gel preparation, said specific alumina gel having a dispersibility advantageously less than 15%, and preferably between 6 and 13%, and very preferably between 6 and 10%.
[0011] The invention also relates to the catalyst that can be prepared by the process of preparation described. The invention finally relates to the use of this catalyst in processes for hydrotreatment or hydroconversion of heavy hydrocarbon feedstocks, preferably for feeds containing at most 50 ppm and very preferably between 20 and 50 ppm of cumulated metals, for example nickel and vanadium. DESCRIPTION OF THE INVENTION Summary The invention relates to a process for the preparation of a hydroconversion catalyst comprising: a predominantly calcined aluminum oxide support; a hydro-dehydrogenating active phase comprising at least one Group VIB metal of the periodic table of elements, optionally at least one Group VIII metal of the periodic table of the elements, optionally phosphorus, said catalyst having: a higher SBET surface area at 75 m 2 / g, a total pore volume measured by mercury porosimetry greater than or equal to 0.55 ml / g, a mesoporous median diameter in volume greater than or equal to 16 nm, a mesoporous volume as measured by intrusion into the porosimeter at mercury, greater than or equal to 0.50 ml / g, a macroporous volume of less than 15% of the total pore volume, said process comprising at least the following stages: a) a first precipitation step, in an aqueous reaction medium, of at least one basic precursor selected from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide and from at least one acid precursor selected from aluminum sulphate, aluminum chloride, aluminum nitrate, sulfuric acid, hydrochloric acid and nitric acid, wherein at least one of the basic or acidic precursors comprises of aluminum, the relative flow rate of the acidic and basic precursors is chosen so as to obtain a pH of the reaction medium of between 8.5 and 10.5 and the flow rate of the acidic and basic precursor (s) containing aluminum is adjusted so as to obtain a forwarding rate of the first step of between 5 and 13%, the rate of progress being defined as the proportion of alumina formed in equivalent A1203 during said first precipitation step relative to the quantity total alumina formed at the end of step c) of the preparation process, said step operating at a temperature between 20 and 90 ° C and for a period of between 2 minutes and 30 minutes; b) a step of heating the suspension at a temperature between 40 and 90 ° C for a period of between 7 minutes and 45 minutes; c) a second step of precipitating the suspension obtained at the end of the heating step b) by adding to the suspension at least one basic precursor chosen from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide and at least one acidic precursor selected from aluminum sulphate, aluminum chloride, aluminum nitrate, sulfuric acid, acid hydrochloric acid and nitric acid, wherein at least one of the basic or acidic precursors comprises aluminum, the relative flow rate of the acidic and basic precursors is chosen so as to obtain a pH of the reaction medium of between 8.5 and 10, 5 and the flow rate of the aluminum-containing acidic and basic precursor (s) is adjusted so as to obtain a progress rate of the second stage of between 87 and 95 ° A, the rate of progress being defined as the proportion of alumina formed in equivalent A1203 during the said second precipitation step relative to the total amount of alumina formed at the end of step c) of the preparation process, said step operating at a temperature between 40 and 90 ° C and for a period of time between 2 minutes and 50 minutes; d) a filtration step of the suspension obtained at the end of the second precipitation step c) to obtain an alumina gel; e) a step of drying said alumina gel obtained in step d) to obtain a powder; f) a step of shaping the powder obtained at the end of step e) to obtain a green material; g) a step of heat treatment of the raw material obtained at the end of step f) at a temperature of between 500 and 1000 ° C., with or without a flow of air containing up to 60% by volume of water, to obtain an aluminum oxide support; h) a step of impregnating the hydro-dehydrogenating active phase on said aluminum oxide support. Preferably, the rate of advance of the first precipitation step a) is between 6 and 12%, very preferably between 7 and 11%.
[0012] Preferably, the basic precursor is sodium aluminate. Preferably, the acidic precursor is aluminum sulphate. Advantageously, in the first precipitation step, the aqueous reaction medium is water and said step is operated with stirring, in the absence of organic additive. The invention also relates to a mesoporous hydroconversion catalyst that can be prepared by the above process.
[0013] Preferably, said catalyst has: a surface area Sbet greater than 100 m 2 / g, a mesoporous median diameter by volume greater than or equal to 18 nm, a mesoporous volume as measured by mercury porosimeter intrusion, of between 0.55 ml and a total pore volume measured by mercury porosimetry greater than or equal to 0.60 ml / g, a macroporous volume of less than 10% of the total pore volume, and an absence of micropores.
[0014] Very preferably, the macroporous volume is less than 5% of the total pore volume Preferably, the catalyst has a mesoporous median diameter in volume determined by mercury porosimeter intrusion between 20 and 25 nm Advantageously, the metal content of group VI B is between 6 and 14% by weight of group VI B metal trioxide relative to the total mass of the catalyst, the metal content of group VIII is between 0.0 and 5.0 (3/0 by weight of the Group VIII metal oxide relative to the total mass of the catalyst, the content of phosphorus element is between 0 to 7% by weight of phosphorus pentoxide relative to the total mass of the catalyst The hydro-dehydrogenating active phase may be composed of molybdenum or nickel and molybdenum or cobalt and molybdenum.
[0015] Preferably, the hydrodehydrogenating active phase also comprises phosphorus. The invention also relates to a process for the hydrotreatment of a heavy hydrocarbon feedstock chosen from atmospheric residues, vacuum residues resulting from direct distillation, deasphalted oils, residues resulting from conversion processes such as, for example, those originating from coking, hydroconversion fixed bed, bubbling bed or moving bed, taken alone or in a mixture, comprising contacting said feedstock with hydrogen and a hydroconversion catalyst as described above or prepared according to the preparation method above.
[0016] Said process can be carried out partly in a bubbling bed at a temperature of between 320 and 450 ° C., under a hydrogen partial pressure of between 3 MPa and 30 MPa, at a space velocity of between 0.1 and 10 volumes of filler. per volume of catalyst and per hour, and with a hydrogen gas ratio on hydrocarbon liquid feed advantageously between 100 and 3000 normal cubic meters per cubic meter. Said process can be carried out at least in part in a fixed bed at a temperature of between 320 ° C. and 450 ° C., at a hydrogen partial pressure of between 3 MPa and 30 MPa, at a space velocity of between 0.05 and 5. volume of charge per volume of catalyst per hour, and with a hydrogen gas ratio on a hydrocarbon liquid charge of between 200 and 5000 normal cubic meters per cubic meter. The process may be a process for hydrotreating a heavy hydrocarbon feedstock of the fixed bed residue type comprising at least: a) a hydrodemetallization step; b) a hydrodesulfurization step; wherein said hydroconversion catalyst is used in at least one of said steps a) and b).
[0017] The process can in particular be a hydrotreatment process for heavy hydrocarbon feedstock of the fixed bed residue type in which: the feedstock has a cumulative metal content, initial or after prior hydrotreatment, on one or more other hydrodemetallation catalysts, lower or equal to 50 ppm; and wherein said hydroconversion catalyst is used in the hydrodemetallization step. List of Figures The figures are presented for illustrative purposes and refer to example 5. FIG. 1 shows the evolution at 300 hours of the relative HDM hydrodemetallation performances of catalysts A 1, B 1 and C 1 on a feedstock comprising a mixture of atmospheric residue and vacuum residue (RAAM / RSVAL, previously hydrotreated). FIG. 2 shows the evolution at 300 hours of the relative HDS hydrodesulphurization performances of the catalysts A 1, B 1 and C 1 on a feedstock comprising a mixture of atmospheric residue and of residue under vacuum (RAAM / RSVAL, previously hydrotreated).
[0018] Terminology and characterization techniques Throughout the rest of the text, dispersibility is defined as the weight of solid or gel of peptised alumina that can not be dispersed by centrifugation in a 3600G polypropylene tube for 3 min. The catalyst and support of the present invention have a specific porous distribution, where the macroporous and mesoporous volumes are measured by mercury intrusion and the microporous volume is measured by nitrogen adsorption.
[0019] "Macropores" means pores whose opening is greater than 50 nm. By "mesopores" is meant pores whose opening is between 2 nm and 50 nm, limits included. By "micropores" is meant pores whose opening is less than 2 nm. In the following description of the invention, the term "specific surface" means the specific surface B.E.T. determined by nitrogen adsorption according to ASTM D 3663-78 established from the BRUNAUER-EMMETT-TELLER method described in the journal "The Journal of the American Society", 60, 309, (1938). In the following description of the invention, the total pore volume of the alumina or of the support or of the catalyst is understood to mean the volume measured by mercury porosimeter intrusion according to the ASTM D4284-83 standard at a maximum pressure of 4000. bar (400 MPa), using a surface tension of 484 dyne / cm and a contact angle of 140 °. The angle of wetting was taken equal to 140 ° following the recommendations of the book "Techniques of the engineer, treated analysis and characterization", P 1050-5, written by Jean Charpin and Bernard Rasneur. In order to obtain a better precision, the value of the total pore volume in ml / g given in the following text corresponds to the value of the total mercury volume (total pore volume measured by mercury porosimeter intrusion) in ml / g measured on the sample minus the mercury volume value in ml / g measured on the same sample for a pressure corresponding to 30 psi (approximately 0.2 MPa). The volume of macropores and mesopores is measured by mercury intrusion porosimetry according to ASTM D4284-83 at a maximum pressure of 4000 bar (400 MPa), using a surface tension of 484 dyne / cm and a contact angle of 140 °. The value at which mercury fills all the intergranular voids is fixed at 0.2 MPa, and it is considered that beyond this mercury enters the pores of the sample.
[0020] The macroporous volume of the catalyst or support is defined as the cumulative volume of mercury introduced at a pressure of between 0.2 MPa and 30 MPa, corresponding to the volume contained in the pores with an apparent diameter greater than 50 nm.
[0021] The mesoporous volume of the catalyst or support is defined as the cumulative volume of mercury introduced at a pressure of between 30 MPa and 400 MPa, corresponding to the volume contained in the pores with an apparent diameter of between 2 and 50 nm.
[0022] The micropore volume is measured by nitrogen porosimetry. The quantitative analysis of the microporosity is carried out using the "t" method (Lippens-De Boer method, 1965) which corresponds to a transformation of the starting adsorption isotherm as described in the book "Adsorption by powders and porous solids. Principles, methodology and applications "written by F. Rouquerol, J. Rouquerol and K. Sing, Academic Press, 1999. The mesoporous median diameter is also defined as a diameter such that all pores smaller than this diameter constitute 50%. total mesoporous volume determined by mercury porosimeter intrusion. Macroporous median diameter is also defined as a diameter such that all pores smaller than this diameter constitute 50% of the total macroporous volume determined by mercury porosimeter intrusion.
[0023] In the following, groups of chemical elements are given according to the CAS classification (CRC Handbook of Chemistry and Physics, publisher CRC Press, editor in chief D.R. Lide, 81st edition, 2000-2001). For example, group VIII according to the CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IUPAC classification.
[0024] DETAILED DESCRIPTION OF THE INVENTION The applicant has discovered that the combination of at least one element of group VI B, optionally at least one element of group VIII and the phosphorus element with an aluminum oxide which simultaneously has a high pore volume (> 0.75 ml / g), a median diameter of the mesopores high (greater than or equal to 16 nm), and thus a BET surface area greater than 75 m 2 / g, preferably greater than 100 m 2 / g, leads to a catalyst with particular textural properties which has a significant gain of hydrodemetallation in a fixed bed process or in a bubbling bed process treating the feeds advantageously containing a content of cumulated metals (nickel and vanadium) less than or equal to 50 ppm. The amorphous mesoporous aluminum support comes from the shaping of an alumina gel having a low dispersibility, said alumina gel being obtained by precipitation of at least one aluminum salt.
[0025] A significant gain in stability over time is also observed, when the catalyst is used on a feedstock containing at most 50 ppm of cumulated metals, nickel and vanadium, or downstream of a first hydrodemetallization catalyst, if the residue load is too heavily loaded.
[0026] As a result, this type of catalyst can also be used in a catalytic series in which it treats a residue effluent initially containing more than 50 ppm of metals, but whose pretreatment with one or more catalysts of the prior art leads to lowering the metal content between 20 and 50 ppm.
[0027] General Description of the Catalyst The catalyst that may be prepared according to the invention is in the form of a calcined, predominantly aluminum oxide support on which the metals of the active phase are distributed. The support is subject to specific characteristics which are described below, as well as, to a lesser extent, the active phase and its formulation. Also described below, according to the invention, their preparation as well as the use of the catalyst in processes for hydrotreatment of heavy hydrocarbon feeds. The Group VI B metals are advantageously selected from molybdenum and tungsten, and preferably said Group VI B metal is molybdenum. Group VIII metals are preferably selected from iron, nickel or cobalt and nickel or cobalt, or a combination of both, is preferred.
[0028] The respective quantities of group VI B metal and of group VIII metal are advantageously such that the Group VIII metal atomic ratio (aux) of groups VIII to VI (VIII: VI B) is between 0: 1 and 0.7: 1, preferably 0.05: 1 and 0.7: 1, very preferably between 0.1: 1 and 0.6: 1 and even more preferably between 0.2: 1 and 0, 5: 1. This ratio can in particular be adjusted according to the type of load and the process used. The respective quantities of group VI B metal and phosphorus are advantageously such that the atomic phosphorus to metal (A) group VI (P / VI B) atomic ratio is between 0.2: 1 and 1.0: 1, preferably between 0.4: 1 and 0.9: 1 and even more preferably between 0.5, 1.0 and 0.85: 1. The metal content of group VI B is advantageously between 6 and 14% by weight of trioxide of at least Group VI B metal relative to the total mass of the catalyst, preferably between 7 and 12% and even more preferred between 8 and 11% by weight. The metal content of group VIII is advantageously between 0 and 5.0%, preferably between 0.4 and 5.0% by weight of the oxide of at least the group VIII metal relative to the total mass catalyst, very preferably between 0.6 and 3.7%, and even more preferably between 1.2 and 2.8% by weight. The content of phosphorus element is advantageously between 0 and 7.0% by weight, preferably between 0.6 and 7.0% by weight of phosphorus pentoxide with respect to the total mass of the catalyst, very preferably between 1 and 7% by weight. , 4 and 5.3% by weight and even more preferably between 2.0 and 4.6% opoids. The porous alumina type oxide predominantly constituting the support of said catalyst according to the invention is characterized by an upper alumina content greater than or equal to 90% and a silica content in SiO 2 equivalent of at most 10% by weight relative to the final oxide, preferably with a silica content of less than 5% by weight, very preferably a content of less than 2% and even more preferably the oxide contains nothing other than alumina . Said catalyst according to the invention is generally presented in all the forms known to those skilled in the art. Preferably, it will consist of extrudates of diameter generally between 0.5 and 10 mm, preferably between 0.8 and 3.2 mm and very preferably between 1.0 and 2.5 mm. This may advantageously be in the form of extruded cylindrical, trilobed or quadrilobed. Preferably its shape will be trilobed or quadrilobed. The shape of the lobes can be adjusted according to all known methods of the prior art.
[0029] Characteristics of the support according to the invention The support of the catalyst according to the invention mainly comprises a porous aluminum oxide. Preferably, the support consists exclusively of alumina.
[0030] The porous aluminum oxide support of said catalyst according to the invention generally comprises an alumina content greater than or equal to 90% and a silica content in SiO 2 equivalent of at most 10% by weight relative to the final oxide, preferably a content silica less than 5% by weight, very preferably less than 2% by weight. The silica may be introduced by any technique known to those skilled in the art, for example during the synthesis of the alumina gel or during the comalaxing step.
[0031] The support used for the preparation of the catalyst according to the invention advantageously has a total pore volume (VPT) of at least 0.75 ml / g, preferably at least 0.78 ml / g, and very preferably at least 0.8 ml / g. The support used according to the invention advantageously has a macroporous volume, V5onm, defined as the volume of the pore diameter greater than 50 nm, less than 10 (3/0 of the total pore volume and preferably less than 5 (3/0 of the total pore volume, and very preferably less than 3% of the total pore volume.The support used according to the invention advantageously has a mesoporous volume, Vmeso, defined as the volume of pores with a diameter of between 2 and 50 nm, at least 0.50 ml / g, and preferably at least 0.70 ml / g, and very preferably between 0.70 and 0.90 ml / g.
[0032] The mesoporous median diameter of the support (or Dpmé ') is advantageously greater than or equal to 16 nm, preferably greater than or equal to 18 nm, very preferably greater than or equal to 20 nm, and even more preferably between 21 nm and 23 nm, limits included.
[0033] The support of the catalyst used according to the present invention advantageously has a BET specific surface area (SS) greater than 75 m 2 / g, preferably greater than 100 m 2 / g, very preferably greater than 130 m 2 / g. By BET surface is meant the specific surface area determined by nitrogen adsorption according to ASTM D 3663-78 established from the method BRUNAUER - EMMET - TELLER described in the journal "The Journal of the American Chemical Society", 60 , 309 (1938). Characteristics of the catalyst The finished catalyst, that is to say with the metals deposited on its surface by any method known to those skilled in the art, as described below, therefore has the textural properties to follow. The catalyst according to the invention advantageously has a total pore volume (VPT) of at least 0.55 ml / g and preferably at least 0.60 ml / g as determined by mercury porosimeter intrusion. In a preferred embodiment, the catalyst has between 0.60 and 0.85 ml / g of total pore volume, inclusive. The catalyst used according to the invention advantageously has a macroporous volume, V5onm less than 15% of the total pore volume and preferably less than 10% of the total pore volume. In a most preferred embodiment, the macroporous volume is less than 5% of the total pore volume, the mesoporous volume, V meso, of the catalyst is at least 0.50 ml / g, and preferably 0 , 55 ml / g and 0.85 ml / g, and very preferably between 0.60 ml / g and 0.80 ml / g, inclusive.
[0034] The median mesoporous diameter (Dp m ') is advantageously greater than or equal to 16 nm, preferably greater than or equal to 18 nm, and very preferably greater than or equal to 20 nm.
[0035] Advantageously, the mesoporous median diameter (Dp m ') of the catalyst is between 20 nm and 28 nm and preferably between 20 and 25 nm, inclusive. When macropores are present, the macroporous median diameter is advantageously between 60 and 200 nm, preferably between 60 and 120 nm.
[0036] The catalyst used according to the present invention advantageously has a BET specific surface area (SS) of at least 75 m 2 / g, preferably at least 100 m 2 / g and even more preferably between 110 and 150 m 2 / g.
[0037] Preparation of the oxide support of the catalyst The porous aluminum oxide used in the support of the catalyst according to the present invention is a porous aluminum oxide with controlled mesoporosity having good thermal and chemical stability, having a centered, uniform, monomodal, and controlled mesopore size distribution. The porous aluminum oxide used according to the invention advantageously has a specific surface and a pore volume and in particular mesoporous calibrated.
[0038] Preferably, the mesoporous aluminum porous oxide is free of micropores. Preferably, the porous alumina oxide advantageously has a specific surface area greater than 75 m 2 / g.
[0039] Very preferably, the specific surface area of the porous aluminum oxide is greater than 100 m 2 / g. Even more preferably, the specific surface area of the porous aluminum oxide is greater than 125 m 2 / g.
[0040] The mesoporous volume, defined as the volume included in pores having a mean diameter of between 2 and 50 nm, is measured by mercury porosimetry. According to the invention, the mesoporous volume of the porous aluminum oxide is greater than or equal to 0.5 ml / g, very preferably greater than or equal to 0.7 ml / g and even more preferably between 0, 70 ml / g and 0.90 ml / g, terminals included. The porous aluminum oxide support of said catalyst according to the invention generally comprises an alumina content of greater than or equal to 90% and a silica content of at most 10% by weight equivalent to 50% with respect to the final oxide, preferably a content silica less than 5% by weight, very preferably less than 2% by weight. The silica may be introduced by any technique known to those skilled in the art, for example during the synthesis of the alumina gel or during the comalaxing step.
[0041] Preferably, the aluminum oxide support according to the invention consists exclusively of alumina. In a very preferred manner, the aluminum oxide support according to the invention is a non-mesostructured alumina.
[0042] The process for preparing the porous aluminum oxide support of the catalyst according to the invention comprises a first step a) of precipitation, a step b) of heating, a step c) of second precipitation, a step d) filtration, a step e) drying, a f) shaping step, a g) heat treatment step.
[0043] The rate of progress for each of the precipitation steps is defined as the proportion of alumina formed in A1203 equivalent during said first or second precipitation step relative to the total amount of alumina formed in equivalent A1203 at the end of of the two precipitation stages and more generally after the steps of preparation of the alumina gel and in particular at the end of step c) of the preparation process according to the invention. Step a): first precipitation This step consists in bringing into contact, in an aqueous reaction medium, at least one basic precursor chosen from sodium aluminate, potassium aluminate, ammonia and sodium hydroxide. and potassium hydroxide and at least one acidic precursor selected from aluminum sulphate, aluminum chloride, aluminum nitrate, sulfuric acid, hydrochloric acid, and nitric acid, in which at least one of the basic or acidic precursors comprises aluminum, the relative flow rate of the acidic and basic precursors is chosen so as to obtain a pH of the reaction medium of between 8.5 and 10.5 and the flow rate of the or aluminum-containing acidic and basic precursors are set so as to obtain a first step progress rate of between 5 and 13%, the feed rate being defined as the proportion of alumina formed in equivalent A1203 during said first step of precipitation relative to the total amount of alumina formed in equivalent A1203 at the end of step c) of the preparation process, said step operating at a temperature of between 20 and 90 ° C., and for a period of time between 2 minutes and 30 minutes. The mixture in the aqueous reaction medium of at least one basic precursor and at least one acidic precursor requires that at least one of the acidic or basic precursors comprises aluminum. It is also possible that at least two of the basic and acidic precursors comprise aluminum. Basic precursors comprising aluminum are sodium aluminate and potassium aluminate. The preferred basic precursor is sodium aluminate. Acidic precursors comprising aluminum are aluminum sulphate, aluminum chloride and aluminum nitrate. The preferred acidic precursor is aluminum sulphate.
[0044] Preferably, the aqueous reaction medium is water. Preferably, said step a) operates with stirring.
[0045] Preferably, said step a) is carried out in the absence of organic additive. The acidic and basic precursors, whether they contain aluminum or not, are mixed, preferably in solution, in the aqueous reaction medium, in such proportions that the pH of the resulting suspension is between 8.5 and 10. 5.
[0046] According to the invention, the alumina acid precursors and the basic alumina precursors can be used alone or as a mixture in the precipitation step.
[0047] According to the invention, the relative flow rate of the acidic and basic precursors they contain aluminum or not, is chosen so as to obtain a pH of the reaction medium of between 8.5 and 10.5. In the preferred case where the basic and acidic precursors are respectively sodium aluminate and aluminum sulphate, the mass ratio of said basic precursor to said acidic precursor is advantageously between 1.60 and 2.05. For the other basic and acidic precursors, whether they contain aluminum or not, the base / acid mass ratios are established by a curve of neutralization of the base by the acid. Such a curve is easily obtained by those skilled in the art. Preferably, said precipitation step a) is carried out at a pH of between 8.5 and 10.0 and very preferably between 8.7 and 9.9.
[0048] Preferably, the first step a) of precipitation is carried out at a temperature between 20 and 90 ° C, preferably between 20 and 70 ° C and more preferably between 30 and 50 ° C.
[0049] Preferably, the first precipitation step a) is carried out at a pH of between 8 and 10.5, preferably between 8 and 10.5, preferably between 8.5 and 10 and very preferably between 8.7 and 10.5. and 9.9. Preferably, the first step a) of precipitation is carried out for a period of between 5 and 20 minutes, and preferably of 5 to 15 minutes. According to the invention, the rate of progress of said first precipitation step a) is between 5 and 13%, preferably between 6 and 12 (3/0 and preferably between 7 and 11%. is defined as the proportion of alumina formed in Al 2 O 3 equivalent during said first precipitation step relative to the total amount of alumina formed in Al 2 O 3 equivalent at the end of step c) of the preparation process. The acidic and basic precursors containing aluminum are therefore introduced in amounts which make it possible to obtain a suspension containing the desired quantity of alumina, as a function of the final concentration of alumina to be reached. In particular, said step a) makes it possible to obtain from 5 to 13% by weight of alumina relative to the total amount of alumina formed in Al 2 O 3 equivalent at the end of stage c) of the preparation process. . Step b): Heating According to the invention, said preparation method comprises a step b) of heating the suspension obtained at the end of the first step a) of precipitation. According to the invention, before the second precipitation step is carried out, a heating step of the suspension obtained at the end of the precipitation step a) is carried out between the two precipitation stages. Preferably, said step of heating the suspension obtained at the end of step a), carried out between said first precipitation step a) and the second precipitation step c) operates at a temperature between 40 and 90 ° C, preferably between 40 and 80 ° C, preferably between 40 and 70 ° C and very preferably between 40 and 65 ° C. Preferably, said heating step is carried out for a period of between 7 and 45 minutes and preferably between 7 and 35 minutes.
[0050] Said heating step is advantageously carried out according to all the heating methods known to those skilled in the art. Step c): Second Precipitation According to the invention, said preparation method comprises a second step of precipitation of the heated suspension obtained at the end of the heating step b), said second step operating by adding in said suspension of at least one basic precursor selected from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide and at least one acidic precursor selected from aluminum sulphate, aluminum chloride, aluminum nitrate, sulfuric acid, hydrochloric acid, and nitric acid, wherein at least one of the basic or acidic precursors comprises aluminum, the relative acidic and basic precursors is chosen in such a way as to obtain a pH of the reaction medium of between 8.5 and 10.5 and the flow rate of the acidic and basic precursor (s) containing aluminum is adjusted so as to obtain a degree of progress. of the second a step of between 87 and 95%, the degree of progress being defined as the proportion of alumina formed in Al 2 O 3 equivalent during said second precipitation step relative to the total amount of alumina formed in Al 2 O 3 equivalent at the end of step c) of the preparation process, said step operating at a temperature between 40 and 90 ° C, and for a period of between 2 minutes and 50 minutes. The basic precursor (s) and acid (s) are added in the said second co-precipitation step in aqueous solution.
[0051] As in the first precipitation step a), the addition to the heated suspension of at least one basic precursor and at least one acidic precursor requires that at least one of the basic or acid precursors comprises aluminum. It is also possible that at least two of the basic and acidic precursors comprise aluminum. Basic precursors comprising aluminum are sodium aluminate and potassium aluminate. The preferred basic precursor is sodium aluminate. Acidic precursors comprising aluminum are aluminum sulphate, aluminum chloride and aluminum nitrate. The preferred acidic precursor is aluminum sulphate. Preferably, said second precipitation step operates with stirring. Preferably, said second step is carried out in the absence of organic additive.
[0052] The acidic and basic precursors, whether they contain aluminum or not, are mixed, preferably in solution, in the suspension, in such proportions that the pH of the resulting suspension is between 8.5 and 10.5. .
[0053] As in step a) of precipitation, the relative flow rate of the acidic and basic precursors, whether they contain aluminum or not, is chosen so as to obtain a pH of the reaction medium of between 8.5 and 10. , 5, preferably between 8.5 and 10, even more preferably between 8.7 and 9.9.
[0054] In the preferred case where the basic and acidic precursors are respectively sodium aluminate and aluminum sulphate, the mass ratio of said basic precursor to said acidic precursor is advantageously between 1.60 and 2.05.
[0055] For the other basic and acidic precursors, whether they contain aluminum or not, the base / acid mass ratio is established by a curve of neutralization of the base by the acid. Such a curve is easily obtained by those skilled in the art. Preferably, said second precipitation step is carried out at a pH of between 8.5 and 10.0 and preferably between 8.7 and 9.9. The aluminum precursors are also mixed in amounts to obtain a suspension containing the desired amount of alumina, depending on the final concentration of alumina to be achieved. In particular, said second precipitation step makes it possible to obtain 87 to 95% by weight of alumina with respect to the total amount of alumina formed in A1203 equivalent at the end of the two precipitation stages. As in step a) of precipitation, it is the flow rate of the acidic and basic precursor (s) containing aluminum which is adjusted so as to obtain a progress rate of the second stage between 87 and 95 %, preferably between 88 and 94 (3/0, very preferably between 89 and 93 (3/0, the feed rate being defined as the proportion of alumina formed in equivalent A1203 during said second step of precipitation relative to the total amount of alumina formed in equivalent A1203 at the end of step c) of the preparation process.
[0056] Thus, depending on the concentration of alumina targeted after the precipitation steps, preferably between 20 and 100 g / l, the amounts of aluminum to be provided by the acid precursors and / or basic are calculated and the Precursor flow rate is adjusted according to the concentration of said added aluminum precursors, the amount of water added to the reaction medium and the rate of progress required for each of the precipitation steps. As in step a) of precipitation, the flow rates of the acid-containing precursor (s) and / or base (s) containing aluminum depend on the size of the reactor used and thus on the amount of water added to the reaction medium. By way of example, if one works in a 3 liter reactor and targets 1 liter of alumina suspension with a final concentration of Al 2 O 3 of 50 g / l, with a targeted advancement rate of 10% for the first precipitation step, 10% of the total alumina must be provided during step a) of precipitation. The alumina precursors are sodium aluminate at a concentration of 155 g / l in Al 2 O 3 and aluminum sulphate at a concentration of 102 g / l in Al 2 O 3. The precipitation pH of the first stage is set at 9, And the pH of the second step at 9. The amount of water added to the reactor is 620 ml.
[0057] For the first step a) of precipitation operating at 30 ° C and for 8 minutes, the flow rate of aluminum sulphate must be 2.1 ml / min and the flow rate of sodium aluminate is 2.6 ml / min . The weight ratio of sodium aluminate to aluminum sulfate is therefore 1.91. For the second precipitation stage, operating at 70 ° C., for 30 minutes, the flow rate of aluminum sulphate must be 5.2 ml. / min and the flow rate of sodium aluminate is 6.3 ml / min. The mass ratio of sodium aluminate to aluminum sulfate is therefore 1.84.
[0058] Preferably, the second precipitation step is carried out at a temperature between 40 and 80 ° C, preferably between 45 and 70 ° C and very preferably between 50 and 70 ° C. Preferably, the second precipitation step is carried out for a period of between 5 and 45 minutes, and preferably of 7 to 40 minutes. The second precipitation step generally makes it possible to obtain an alumina suspension having an Al 2 O 3 concentration of between 20 and 100 g / l, preferably between 20 and 80 g / l, preferably between 20 and 50 g / l. Step d) Filtration The alumina preparation process according to the invention also comprises a filtration step of the suspension obtained at the end of the second precipitation step c). Said filtration step is carried out according to the methods known to those skilled in the art. The filterability of the suspension obtained at the end of the two precipitation steps is improved by the low dispersibility of the alumina gel obtained, which makes it possible to improve the productivity of the process according to the invention as well as to allow extrapolation of the process. at the industrial level. Said filtration step is advantageously followed by at least one washing step, preferably with water and preferably from one to three washing steps, with a quantity of water equal to the amount of filtered precipitate. The sequence of the first precipitation a), the heating b) and the second precipitation c) stages and the filtration stage d) makes it possible to obtain a specific alumina gel having a dispersibility ratio of less than 15%, preferably between 5 and 15% and preferably between 6 and 14% and very preferably between 7 and 13%, and even more preferably between 7 and 10% and a crystallite size between 1 and 35 nm and preferably between 2 to 35 nm.
[0059] The alumina gel obtained also advantageously has a sulfur content, measured by the X-ray fluorescence method, of between 0.001 and 2% by weight and preferably of between 0.01 and 0.2% by weight and a sodium content. measured by ICPMS or Inductively Coupled Plasma Spectrometry between 0.001 and 2 wt%, and preferably between 0.01 and 0.1 wt%, the weight percentages being expressed relative to the mass. In particular, the alumina gel or the boehmite in powder form according to the invention is composed of crystallites whose size, obtained by the Scherrer formula in X-ray diffraction, is respectively between 2. and 20 nm and between 2 and 35 nm in crystallographic directions [020] and [120] Preferably, the alumina gel according to the invention has a crystallite size in the crystallographic direction [020] of between 1 and 15 nm and a crystallite size in the crystallographic direction [120] between 1 to 35 nm. X-ray diffraction on alumina or boehmite gels was performed using the conventional powder method using a diffractometer. Scherrer's formula is a formula used in X-ray diffraction on powders or polycrystalline samples which connects the width at half height of the diffraction peaks to the size of the crystallites. It is described in detail in the reference: Appl. Cryst. (1978). 11, 102-113 "Scherrer after sixty years: A survey and some new results in the determination of crystallite size", J. I. Langford and A. J. C. Wilson.
[0060] The low dispersibility rate of the gel thus prepared makes it possible to facilitate the step of shaping said gel according to all the methods known to those skilled in the art and in particular by extrusion kneading, by granulation and by the technique known as drop (draining) according to the English terminology. Step e): Drying In accordance with the invention, the alumina gel obtained at the end of the second precipitation step c), followed by a filtration step d), is dried in a drying step d) to obtain a powder, said drying step being carried out for example by drying, at a temperature between 20 and 200 ° C and for a period of between 8 h and 15 h, or by atomization or by any other known drying technique of the skilled person. In the case where said drying step e) is carried out by atomization, the cake obtained at the end of the second precipitation step, followed by a filtration step, is resuspended. Said suspension is then sprayed in fine droplets, in a vertical cylindrical chamber in contact with a stream of hot air to evaporate the water according to the principle well known to those skilled in the art. The powder obtained is entrained by the flow of heat to a cyclone or a bag filter which will separate the air from the powder. Preferably, in the case where said drying step e) is carried out by atomization. the atomization is carried out according to the operating procedure described in Asep Bayu Dani Nandiyanto publication, Kikuo Okuyama, Advanced Powder Technology, 22, 1-19, 2011. Step f): shaping According to the invention, the powder obtained at the end of the drying step e) is shaped in a step f) to obtain a green material. By raw material is meant the material shaped and having not undergone any heat treatment steps. Preferably, said shaping step f) is carried out by extrusion kneading, by granulation, by the technique of oil-drop (or dewatering in French), by pelletization. Very preferably, said f) shaping step is carried out by extrusion kneading. Step q): heat treatment According to the invention, the raw material obtained at the end of the shaping step f) then undergoes a step g) of heat treatment at a temperature of between 500 and 1000 ° C. , with or without a flow of air containing up to 60% water volume. Preferably, said heat treatment step g) operates at a temperature of between 540 ° C and 900 ° C. Preferably, said heat treatment step g) operates for a period of time between 2h and 10h. Said step g) heat treatment allows the transition of the boehmite to the final alumina. The heat treatment step may be preceded by drying at a temperature between 50 ° C and 200 ° C, according to any technique known to those skilled in the art. Characteristics of the amorphous aluminous porous oxide obtained The preparation method according to the invention makes it possible to obtain an amorphous aluminous porous oxide having a high porous median diameter, determined on the porous volume distribution curve by intrusion into the mercury porosimeter , advantageously greater than or equal to 16 nm, preferably greater than or equal to 18 nm, very preferably greater than or equal to 20 nm, even more preferably between 21 and 23 nm, inclusive. The mesoporous aluminum oxide support prepared according to the process of the invention is advantageously free of micropores. The absence of micropores is verified by nitrogen porosimetry. The mesoporous alumina oxide support according to the invention advantageously has a mesoporous volume, that is to say contained in pores with a diameter of between 2 and 50 nm, as measured by mercury porosimeter intrusion, greater than or equal to 0 5 ml / g, preferably greater than or equal to 0.7 ml / g. The total pore volume measured by mercury porosimetry is advantageously greater than 0.75 ml / g.
[0061] The mesoporous alumina oxide support according to the invention generally comprises a proportion of macropores, defined as pores with a diameter greater than 50 nm, of less than 10%, preferably less than 5% of the total pore volume determined by mercury porosimetry.
[0062] The mesoporous alumina support according to the invention generally has a specific surface area greater than 100 m 2 / g. The support of the catalyst according to the invention comprises for the most part (at least 90% by weight) an aluminum oxide as described above and may also contain dopants such as silicon, titanium and zirconium elements (up to a content of 10 (3/0 weight).
[0063] The support of the catalyst according to the invention described above is usually used in the form of powder, beads, pellets, granules or extrudates, the shaping operations being carried out according to the conventional techniques known to man. of career.
[0064] The support of the catalyst according to the invention mainly consisting of the aluminum oxide described above may undergo a complementary step of heat treatment or hydrothermal. By thermal or hydrothermal treatment is meant the treatment of said support in temperature respectively without the presence or presence of water. In the latter case, the contact with the water vapor can take place at atmospheric pressure ("steaming") or autogenous pressure (autoclaving). Several combined cycles of thermal or hydrothermal treatments can be carried out. The temperature of said treatments is between 200 and 1000 ° C, preferably between 450 and 1000 ° C and even more preferably between 600 and 850 ° C.
[0065] In case of hydrothermal treatment, the water content is preferably between 150 and 900 grams per kilogram of dry air, and even more preferably between 250 and 650 grams per kilogram of dry air.
[0066] Preparation of the Catalyst The catalyst according to the invention is obtained by depositing at least one Group VIB metal, optionally at least one Group VIII metal and optionally other elements such as the phosphorus element on the catalyst support according to the invention described above.
[0067] Said deposition can be carried out according to all the methods known to those skilled in the art. In particular, said deposition on alumina previously described can be achieved by all the impregnation methods known to those skilled in the art, including dry impregnation. Preferably, at least one Group VIB metal, optionally at least one Group VIII metal and optionally the phosphorus element are deposited by dry impregnation of their associated compounds on the oxide support according to the invention. The deposition can be carried out via a single step of dry impregnation of the oxide support according to the invention via the use of a solution simultaneously containing at least one compound of at least one Group VIB metal, optionally at least one compound phosphorus, and optionally at least one compound of at least one Group VIII metal. The deposit can also be advantageously achieved via at least two cycles of dry impregnation. The different elements can thus be advantageously impregnated successively or one of the elements can also be impregnated into several sequences. One of the impregnations that is carried out can in particular be used for the use of an organic compound that the skilled person wishes to introduce in addition to the constituent elements of the final catalyst.
[0068] The said solution (s) may be aqueous, consisting of an organic solvent or a mixture of water and at least one organic solvent ( for example ethanol or toluene). Preferably, the solution is aquo-organic and even more preferably aqueous-alcoholic. The pH of this solution can be modified by the possible addition of an acid.
[0069] Among the compounds which can be introduced into the solution as sources of group VIII elements, advantageously are: citrates, oxalates, carbonates, hydroxycarbonates, hydroxides, phosphates, sulphates, aluminates, molybdates, tungstates, oxides, nitrates, halides for example, chlorides, fluorides, bromides, acetates, or any mixture of the compounds set forth herein. As regards the sources of the group VIB element which are well known to those skilled in the art, there are advantageously, for example, for molybdenum and tungsten: oxides, hydroxides, molybdic and tungstic acids and their salts, in particular sodium salts. ammonium, ammonium heptamolybdate, ammonium tungstate, phosphomolybdic acid, phosphotungstic acid and their salts. Oxides or ammonium salts such as ammonium molybdate, ammonium heptamolybdate or ammonium tungstate are preferably used.
[0070] The preferred phosphorus source is orthophosphoric acid, but its salts and esters such as alkaline phosphates, ammonium phosphate, gallium phosphate or alkyl phosphates are also suitable. Phosphorous acids, for example hypophosphorous acid, phosphomolybdic acid and its salts, phosphotungstic acid and its salts can be advantageously used.
[0071] A chelating agent of organic nature may advantageously be introduced into the solution if the person skilled in the art deems it necessary.
[0072] Preferably, all of the metal phase is introduced at the end of the preparation of the support and no additional step is therefore necessary. Preferably it is chosen to impregnate at least one Group VIB metal, optionally at least one Group VIII metal and optionally the phosphorus element on the aluminum oxide support previously obtained, according to any of the impregnation methods. previously described. The product is then generally cured, dried and optionally calcined under an oxidizing atmosphere, for example in air, usually at a temperature of about 300 to 600 ° C, preferably 350 to 550 ° C. In one embodiment, the catalyst according to the invention undergoes a complementary step of heat treatment (calcination).
[0073] Preferably, this treatment is generally carried out in two stages. At first, the solid is dried at a temperature below 200 ° C. in air, preferably below 150 ° C. In a second step, calcination is carried out in air, without additional addition of water, at a temperature preferably between 300 and 600 ° C, and very preferably between 400 and 500 ° C.
[0074] In another embodiment, the catalyst does not undergo a complementary heat treatment or hydrothermal step, and the catalyst is only advantageously dried. In this case, the drying temperature is below 200 ° C.
[0075] The catalyst according to the present invention is advantageously used in totally or partially sulphurized form. It therefore undergoes before use an activation step in a sulpho-reducing atmosphere according to any method known to those skilled in the art, in situ or ex situ.
[0076] The sulphurization treatment can be carried out ex situ (before the introduction of the catalyst into the hydrotreatment / hydroconversion reactor) or in situ by means of an organosulfur precursor agent for H2S, for example DMDS (dimethyl disulfide). The invention describes the use of a catalyst comprising at least one group VI B metal, optionally at least one Group VIII metal, optionally phosphorus, and an aluminum oxide support, in which a process for the hydrotreatment of heavy loads such as petroleum residues (atmospheric or vacuum). The invention advantageously relates to charges comprising a content of metals, nickel and vanadium, less than 50 ppm, whatever the method of use and the performance target displayed. This charge can come from a pretreatment step carried out on any catalyst. The processes according to the invention advantageously use the catalyst described according to the invention in hydrotreatment processes making it possible to convert heavy hydrocarbon feeds containing sulfur impurities and metallic impurities.
[0077] In general, the hydrotreatment processes for converting heavy hydrocarbon feeds, containing sulfur impurities and metal impurities, operate at a temperature of between 320 and 450 ° C. under a hydrogen partial pressure of between 3 MPa and 30 MPa, at a space velocity advantageously between 0.05 and 10 volumes of filler per volume of catalyst and per hour, and with a hydrogen gas ratio on a hydrocarbon liquid feed advantageously between 100 and 5000 normal cubic meters per cubic meter . One objective sought by the use of the catalysts of the present invention relates to an improvement of the performance, in particular in hydrodemetallation, with respect to the catalysts known from the prior art. The catalyst described allows an improvement in hydrodemetallation and hydrodesulphalation compared to conventional catalysts, while having a high stability over time.
[0078] Charges The feedstocks treated in the process according to the invention are advantageously chosen from atmospheric residues, vacuum residues resulting from the direct distillation, deasphalted oils, residues resulting from conversion processes such as, for example, those resulting from coking, hydroconversion in fixed bed, bubbling bed, or moving bed, taken alone or in mixture. These fillers can advantageously be used as they are or else diluted by a hydrocarbon fraction or a mixture of hydrocarbon fractions which may be chosen from products derived from the FOC process, a light cutting oil (LCO according to the initials of the English name of Light Cycle Oil), a heavy cutting oil (HCO according to the initials of the English name of Heavy Cycle Oil), a decanted oil (OD according to the initials of the English name of Decanted Oil), a slurry, or From the distillation, gas oil fractions including those obtained by vacuum distillation called according to the English terminology VGO (Vacuum Gas Oil). The heavy charges can thus advantageously comprise cuts resulting from the process of liquefying coal, aromatic extracts, or any other hydrocarbon cut. The process according to the invention is advantageously intended for hydrocarbon feeds having less than 50 ppm of metals, nickel and vanadium, for example. Said heavy charges generally have more than 1% by weight of molecules having a boiling point greater than 500 ° C., a metal content (Ni + V) of greater than 1 ppm by weight, preferably greater than 20 ppm by weight, so very preferred between 30 and 50 ppm by weight, a content of asphaltenes, precipitated in heptane, greater than 0.05% by weight, preferably greater than 1% by weight, very preferably greater than 2%. The heavy fillers can advantageously also be mixed with coal in the form of powder, this mixture being generally called slurry. These charges may advantageously be by-products from the conversion of the coal and re-mixed with fresh coal. The coal content in the heavy load is generally and preferably a ratio 1/4 (Oil / Coal) and may advantageously vary widely between 0.1 and 1. The coal may contain lignite, be a sub-bituminous coal ( according to the Anglo-Saxon terminology), or bituminous. Any other type of coal is suitable for the use of the invention, both in fixed bed reactors and in bubbling bed reactors.
[0079] According to the invention, the catalyst described above is preferably used in the first catalytic beds of a process successively comprising at least one hydrodemetallization step and at least one hydrodesulfurization step. The process according to the invention is advantageously carried out in from one to ten successive reactors, wherein the catalyst (s) according to the invention can advantageously be loaded in one or more reactors and / or in all or some of the reactors. In the case where the process uses a hydrocarbon feedstock more concentrated in metals, that is to say having a cumulative content of metals (Ni + V) greater than 50 ppm, the catalyst according to the invention can be placed in downstream of one or more hydrodemetallation catalysts can be any of the catalysts described in the prior art, and known to those skilled in the art. This or these catalyst (s) then make it possible to have a partially hydrotreated feedstock which contains less than 50 ppm of metals (Ni + V) at the inlet of the catalytic bed composed of the catalyst according to the invention.
[0080] The process according to the invention may advantageously be carried out in a fixed bed with the objective of eliminating metals and sulfur and lowering the average boiling point of the hydrocarbons. In the case where the process according to the invention is carried out in fixed bed, the operating temperature is advantageously between 320 ° C. and 450 ° C., preferably 350 ° C. to 410 ° C., under a partial pressure. in hydrogen advantageously between 3 MPa and 30 MPa, preferably between 10 and 20 MPa, at a space velocity advantageously between 0.05 and 5 volumes of filler per volume of catalyst per hour, and with a gaseous hydrogen gas on charge ratio hydrocarbon liquid advantageously between 200 and 5000 normal cubic meters per cubic meter, preferably 500 to 1500 normal cubic meters per cubic meter.
[0081] The process according to the invention can also advantageously be implemented partly in bubbling bed on the same charges. In the case where the process according to the invention is carried out in an ebullated bed, the catalyst is advantageously used at a temperature of between 320 and 450 ° C. under a hydrogen partial pressure advantageously between 3 MPa and 30 ° C. MPa, preferably between 10 and 20 MPa, at a space velocity advantageously between 0.1 and 10 volumes of filler per volume of catalyst and per hour, preferably between 0.5 and 2 volumes of filler by volume of catalyst and by hour, and with a gaseous hydrogen gas on hydrocarbon liquid charge advantageously between 100 and 3000 normal cubic meters per cubic meter, preferably between 200 to 1200 normal cubic meters per cubic meter. According to a preferred embodiment, the method according to the invention is implemented in a fixed bed.
[0082] Before they are used in the process according to the invention, the catalysts of the present invention are preferably subjected to a sulphurization treatment making it possible, at least in part, to convert the metallic species into sulphide before they come into contact with the charge. treat. This activation treatment by sulphurisation is well known to those skilled in the art and can be performed by any previously known method already described in the literature. A conventional sulphurization method well known to those skilled in the art consists in heating the mixture of solids under a stream of a mixture of hydrogen and hydrogen sulphide or under a stream of a mixture of hydrogen and of hydrocarbons containing sulfur-containing molecules at a temperature of temperature between 150 and 800 ° C, preferably between 250 and 600 ° C, generally in a crossed-bed reaction zone. The sulfurization treatment can be carried out ex situ (before the introduction of the catalyst into the hydrotreating / hydroconversion reactor) or in situ by means of an organosulfur precursor of H25, for example DMDS (dimethyl disulphide).
[0083] The following examples illustrate the invention without, however, limiting its scope.
[0084] EXAMPLES Example 1 Preparation of Catalyst Supports A and B (Compliant) The synthesis of an alumina according to the invention is carried out on a conventional station with a 5L reactor in 3 steps. The concentration of the precursors is as follows: aluminum sulphate Al 2 (SO 4) 3 at 102 g / l in Al 2 O 3 and sodium aluminate NaAl 3 at 155 g / l in Al 2 O 3. The alumina according to the invention is manufactured according to the following steps: a) A first co-precipitation of aluminum sulphate Al2 (SO4) 3 and sodium aluminate NaA100 at 30 ° C. and pH = 9.1 in 8 min: the progress rate is 8%. The rate of progress corresponds to the proportion of alumina formed during the first stage, ie a final alumina concentration of 45 g / l. If one works in a reactor of 5 1 and that one aims 4 1 suspension of alumina of final concentration in A1203 of 45 g / 1, with a targeted rate of advancement of 8 (3/0 for the first stage 8% (3%) of the total alumina must be added during the precipitation stage a) The precipitation pH of the first stage is set at 9.1. For the first step a) of precipitation operating at 30 ° C and for 8 minutes, the flow rate of aluminum sulphate should be 6.1 ml / min, the flow rate of sodium aluminate is 7 ml. 6 ml / min and the water flow rate 69.7 ml / min. The mass ratio of sodium aluminate to aluminum sulfate is therefore 1.91. b) A rise in temperature of 30 to 70 ° C in 20 to 30 min; c) A second co-precipitation of aluminum sulphate Al2 (504) 3 and sodium aluminate NaA100 at 70 ° C. and pH = 9.1 in 30 min, with a degree of progress of 92%; For the second precipitation stage, operating at 70 ° C, for 30 minutes, the precipitation pH of the second stage is set to 9.1, the flow rate of aluminum sulphate must be 19 ml / min, the flow rate of sodium aluminate is 23 ml / min and the water flow rate is 24.7 ml / min. The mass ratio of sodium aluminate to aluminum sulfate is therefore 1.84. d) Filtration by displacement on a Buchner tool type sintered P4 and wash 3 times with 5L of distilled water at 70 ° C. e) Drying overnight at 120 ° C. f) Shaping of the raw material: The dried alumina gel is introduced into a Brabender type mixer. Acidified water with nitric acid at a total acid content of 3%, expressed by weight relative to the mass of dried gel introduced into the kneader, is added in 10 minutes, during mixing 20 turns / min. The acid kneading is continued for 5 minutes. A neutralization step is then carried out by adding an ammoniacal solution in the kneader, at a neutralization rate of 200%, expressed by weight of ammonia relative to the amount of nitric acid introduced into the kneader for the stage. acidification. The kneading is continued for 3 minutes. The paste obtained is then extruded through a 2 mm trilobal die. g) Heat treatment: The extrudates obtained are dried at 100 ° C. overnight and then calcined: either 2 hours at 800 ° C. under a moist air flow in a tubular furnace (VVH = 1 1 / h / g with 30% v / v water): these extrusions give the support A; - Or 2h at 700 ° C under moist air flow tubular furnace (VVH = 1I / h / g with 30% v / v of water, which leads to the extruded support B. The porous distribution of alumina obtained is characterized by mercury porosimeter intrusion according to ASTM D4284-83 at a maximum pressure of 4000 bar (400 MPa), using a surface tension of 484 dyne / cm and a contact angle of 140 °.
[0085] The absence of microporosity is verified by nitrogen porosimetry. Table 1: Synthesized sugars ABCD Total pore volume (m 1 / g) 0.78 0.74 0.87 1.02 Mesoporous volume (ml / g) 0.75 0.71 0.87 0.81 Macroporous volume (ml / g) 0.03 0.03 0.00 0.21% Vmacro 4% 4% 0% 21% Dp meso (nm) 20.4 17.6 15.4 28.4 SBET (m2 / g) 128 146 EXAMPLE 2 Preparation of a Catalyst Support C (Non-Conforming) A synthesis of a non-conformal alumina gel is first carried out in that Example 2 is carried out according to the preparation method described in FIG. US Pat. No. 7,790,562. The synthesis is carried out in a 7L reactor and a final suspension of 5L in two precipitation stages. The amount of water added to the reactor is 3960 ml. The final alumina concentration is 30 g / L.
[0086] A first step of co-precipitation of aluminum sulphate Al2 (504) and of sodium aluminate NaA100 is carried out at 30 ° C. and pH = 9.3 for a period of 8 minutes. The concentrations of aluminum precursors used are as follows: Al2 (504) = at 1 02g / L in A1203 and NaA100 at 1 55g / L in Al2O3. The agitation is 350 rpm throughout the synthesis. A solution of aluminum sulphate Al2 (504) is added continuously for 8 minutes at a flow rate of 19.6 ml / min to a solution of sodium aluminate NaA100 in a weight ratio base / acid = 1.80 to adjust the pH to a value of 9.3. The temperature of the reaction medium is maintained at 30 ° C. A suspension containing a precipitate of alumina is obtained. The final concentration of alumina targeted being 30 g / l, the flow rate of aluminum sulphate precursors Al 2 (504) and aluminum aluminate NaA 100 containing aluminum introduced in the first precipitation stage are respectively 19.6 ml / min. and 23.3 ml / min. These flow rates of acid and basic precursors containing aluminum make it possible to obtain at the end of the first precipitation step a degree of progress of 30%. The suspension obtained is then subjected to a temperature rise of 30 to 57 ° C. A second step of co-precipitation of the suspension obtained is then carried out by adding aluminum sulphate Al 2 (504) at a concentration of 102 g / l of Al 2 O 3 and of sodium aluminate NaAl 3 at a concentration of 155 g / l. in A1203. A solution of aluminum sulphate Al2 (SO4) is therefore added continuously to the heated suspension obtained at the end of the first precipitation step for 30 minutes at a flow rate of 12.8 ml / min at an aluminate solution. of sodium NaA100 in a mass ratio base / acid = 1.68 so as to adjust the pH to a value of 8.7. The temperature of the reaction medium in the second step is maintained at 57 ° C. A suspension containing a precipitate of alumina is obtained.
[0087] The final concentration of alumina targeted being 30 g / l, the flow rate of aluminum sulphate precursors Al 2 (SO 4) and aluminum aluminate NaA 100 containing aluminum introduced in the second precipitation stage are respectively 12.8 ml / min. and 14.1 ml / min. These flow rates of aluminum-containing basic and basic precursors make it possible to obtain at the end of the second precipitation stage a 70% degree of advance.
[0088] The suspension obtained is then filtered by displacement of water on a sintered Buchner type tool and the alumina gel obtained is washed 3 times with 5 L of distilled water at 70 ° C. Shaping of the raw material: The dried alumina gel is introduced into a Brabender type mixer. Acidified water with nitric acid at a total acid content of 3%, expressed by weight relative to the mass of dried gel introduced into the kneader, is added in 10 minutes, during mixing 20 turns / min. The acid kneading is continued for 5 minutes. A neutralization step is then carried out by adding an ammoniacal solution in the kneader, at a degree of neutralization of 80%, expressed by weight of ammonia relative to the amount of nitric acid introduced into the kneader for the stage. acidification. The kneading is continued for 3 minutes. The paste obtained is then extruded through a 2 mm trilobal die. The extrudates obtained are dried at 100 ° C. overnight and then calcined for 2 hours at 600 ° C. g) Heat treatment: The extrudates obtained are dried at 100 ° C. overnight and then calcined for 2 hours at 800 ° C. under a moist air flow in a tubular furnace (VVH = 1 1 / h / g with 30% v / v d 'water).
[0089] The porous distribution of the obtained alumina is characterized by mercury porosimeter intrusion according to ASTM D4284-83 at a maximum pressure of 4000 bar, using a surface tension of 484 dyne / cm and a contact angle of 1400.
[0090] The absence of microporosity is verified by nitrogen porosimetry. EXAMPLE 3 Preparation of a Catalyst Support D, According to Example B of Patent EP1392431 (Non-Conforming) The synthesis of this support is carried out according to the protocol described in patent EP 1 392 431. In a reactor, are simultaneously added aluminum sulphate and sodium aluminate to reach a pH of 8.5 and the whole is heated at 80 ° C for 70 minutes. The suspension obtained is filtered and washed with hot water to remove impurities. The paste is then kneaded for 20 minutes and then extruded through a cylindrical die 0.9 mm in diameter. The extrudates obtained are dried at 120 ° C. for 16 hours and then calcined for 2 hours at 800 ° C. EXAMPLE 4 Preparation of Catalysts A1, B1 (Conforming), Cl, and D1 (Comparative) Supports A, B, C and D were dry-impregnated from a No. 1 stock solution prepared by dissolving water of molybdenum oxide, nickel hydroxide and phosphoric acid purchased from Sigma Aldrich®, in order to prepare the catalysts Ai, Bi, Ci, Di. The mother solution has the following molar concentration: 1.8 mol / l of phosphorus, 3.4 mol / l of molybdenum and 1.3 mol / l of nickel. This is diluted so that the different catalysts resulting from the dry impregnation of the supports have the same target metal contents, namely 10% by weight of molybdenum trioxide, 1.95% by weight of nickel oxide and 2, 60% by weight of phosphorus pentoxide which corresponds to the following molar ratios: Ni / Mo = 0.38 and P / Mo = 0.53. The final contents of the catalysts thus prepared are summarized in the table below. Table 2: Catalysts synthesized Al B1 Cl D1 according to the invention (3 / 0Ni0 (wt) 1.87 1.92 1.98 1.92 (3 / 0Mo03 (wt) 10.02 10.17 10.20 10.07% P205 (wt) 2.64 2.57 2.53 2.61 Example 5: Hydroprocessing (HDT) assessment of Al catalyst residues 131, in comparison with the catalysts C1, D1 The catalysts A1 and B1 prepared according to the invention, but also the comparative catalysts C1 and D1, were subjected to a catalytic test in a perfectly stirred batch reactor, on a load of the RSV Arabian type. Light (see characteristics in Table 3) Table 3: Characteristics of RSV Arabian Light Load Used RSV Arabian Light Density 15/4 0.9712 Viscosity at 100 ° C mm2 / s 45 Sulfur (3/0 wt) 3.38 Nitrogen ppm 2257 Nickel ppm 10.6 Vanadium ppm 41.0 Aromatic carbon (3/0 24.8 Carbon conradson% w 10.2 Asphaltenes C7 (3/0 wt 3.2 SARA Saturated% wt 28.1 Aromatics (3/0 wt. 46.9 Resins% w / w 20.1 Asphaltenes (3/0 wt.) 3.5 Simulated distillation PI ° C 219 5% ° C 299 10 ° / 0 ° C 342 20% ° C 409 30% ° C 463 40% ° C 520 50% 576 DS: PF ° C ° C 614 DS: resisted% 57 To do this, after an ex-situ sulphurization step by circulation of a gas mixture H2S / H2 for 2 hours at 350 ° C, 15 ml of catalyst is charged in the absence of air in the batch reactor and is covered with 90 ml of filler. The operating conditions applied are then as follows: Table 4: Operating conditions used in a batch reactor Total pressure 9.5 MPa Test temperature 370 ° C. Test duration 3 hours At the end of the test, the reactor is cooled and after triple stripping the atmosphere under nitrogen (10 minutes at 1 MPa), the effluent is collected and analyzed by X-ray fluorescence (sulfur and metals) and by simulated distillation (ASTM D7169). The HDS ratio is defined as follows: HDS (° / 0) = ((° / 0 wt S) load- (° / 0 wt S) recipe) / (° / 0 wt S) load x 100 De in the same way, the HDM rate is defined as follows: HDM (° / 0) = ((ppm wt Ni + V) load- (ppm wt Ni + V) recipe) / (ppm wt Ni + V) load x 100 The performance of the catalysts is summarized in Table 5.
[0091] Table 5: HDS and HDM performances of the catalysts Ai, B1 in comparison with the catalysts Ci, D1 Catalysts HDS (° / 0) HDM (° / 0) Al (according to the invention) 48.5 81.8 B1 (according to US Pat. 50.8 83.1 Cl (Comparative) 50.2 70.2 D1 (Comparative) 44.1 74.9 It can be deduced from Table 5 that the use of the catalysts of the present invention results in a significant increase in hydrodemetallation HDM which is never observed for the different textures of the prior art. The differences in hydrodesulfurization HDS remain negligible.
[0092] EXAMPLE 6 Evaluation in fixed bed hydrotreatment of catalysts A1, 131 according to the invention and comparison with catalytic performances of catalyst C1 The catalysts Al and B1 prepared according to the invention were compared in petroleum residue hydrotreating test in comparison with the performance of the catalyst Ci. The feed consists of a mixture between an atmospheric residue (RA) of Middle East origin (Arabian medium) and a vacuum residue (Arabian Light) which has previously been hydrotreated by a catalyst of commercial hydrodemetallation. The feedstock is characterized by high levels of Conradson carbon (9.6 (3/0 by weight) and asphaltenes (2.1 (3/0 by weight) and a nickel content of 21% by weight, a quantity of vanadium 10% by weight and an amount of sulfur of 2.25% by weight The complete characteristics of the feed used are reported in Table 6.
[0093] Table 6: Characteristics of the load used for Mix RA AM / RSV AL hydrotreated tests Density 15/4 0.9610 Sulfur (3/0 wt. 2.25 Nitrogen ppm 2300 Nickel ppm 21 Vanadium ppm 10 Conradson carbon (3/0 wt. 9, 6 Asphaltenes C7 (3/0 wt. 2,1 Simulated distillation PI ° C 193 10% ° C 378 25% ° C 453 50% ° C 549 65% ° C 601 66% ° C 605 67% ° C 609 68% ° C. After a sulphurization step by circulation in the reactor of a gas oil fraction supplemented with DMDS at a final temperature of 350 ° C., the unit is operated with the above mixture of charges under the operating conditions of Table 7.
[0094] Table 7: Operating conditions implemented in a fixed bed reactor Total pressure 15 MPa Test temperature 370 ° C Hourly space velocity of the residue 1.2 h -1 Hydrocarbon flow 1200 std load I. H2 / I. The charge is injected and then the temperature of the test is raised. After a stabilization period of 300 hours, the hydrodesulphurization (HDS) and hydrodemetallation (HDM) performances are recorded, as well as hydroconversion of the residue under vacuum RSV (540 ° C + cut). In the following, the performances are presented in conversions relative to the reference (set to zero in Table 8) or on a relative scale where the activity is normalized to 100 (arbitrarily) in Figures 1 and 2.
[0095] The results of Example 5, that is to say the increase of the hydrodemetallation performances of the catalysts according to the invention with respect to the reference catalyst C1, are confirmed. The gain relative to the catalyst Cl is 2 to 3. ppm less metal in the effluent, which is a significant improvement for the refiner. This gain is also accessible with a sulfur content in the effluent which remains fairly close to that obtained with the catalyst Ci. Table 8: Hydrodesulphurization performance HDS, hydrodemetallation HDM catalyst Ai, Bi, and Cl at 300 hours in fixed bed HDS HDM catalysts (3/0 converted% S effluent% converted ppm effluent metals Al (according to the invention) Base -13% Base + 0.29% Base + 8% Base - 3ppm B1 (according to the invention) Base - 4% Base + 0.09% Base + 12% Base - 2 ppm Cl Base Base Base Base25

权利要求:
Claims (18)
[0001]
REVENDICATIONS1. A process for the preparation of a hydroconversion catalyst comprising: - a predominantly calcined aluminum oxide support; a hydro-dehydrogenating active phase comprising at least one Group VIB metal of the periodic table of the elements, optionally at least one Group VIII metal of the periodic table of the elements, optionally phosphorus, said catalyst having: a Sbet specific surface greater than 75 m 2 / g, a total pore volume measured by mercury porosimetry greater than or equal to 0.55 ml / g, a mesoporous median diameter by volume greater than or equal to 16 nm, a mesoporous volume as measured by mercury porosimeter intrusion, greater than or equal to 0.50 ml / g, a macroporous volume of less than 15% (3% of the total pore volume, said process comprising at least the following stages: a) a first precipitation step, in an aqueous reaction medium, at least one basic precursor chosen from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide and at least one acid precursor selected from aluminum sulphate, aluminum chloride, aluminum nitrate, sulfuric acid, hydrochloric acid and nitric acid, wherein at least one of basic precursors or acid comprises aluminum, the relative flow rate of the acidic and basic precursors is chosen so as to obtain a pH of the reaction medium of between 8.5 and 10.5 and the flow rate of the acidic and basic precursor (s) containing the aluminum is adjusted so as to obtain a first step progress rate of between 5 and 13%, the feed rate being defined as the proportion of alumina formed in Al 2 O 3 equivalent during said first precipitation step with respect to the total amount of alumina formed in A1203 equivalent at the end of step c) of the preparation process, said step operating at a temperature of between 20 and 90 ° C. and for a duration of between 2 minutes and 30 min utes; b) a step of heating the suspension at a temperature between 40 and 90 ° C for a period of between 7 minutes and 45 minutes, c) a second precipitation step of the suspension obtained at the end of the step of heating b) by adding to the suspension at least one basic precursor chosen from sodium aluminate, potassium aluminate, aqueous ammonia, sodium hydroxide and potassium hydroxide and at least one precursor acid selected from aluminum sulphate, aluminum chloride, aluminum nitrate, sulfuric acid, hydrochloric acid and nitric acid, wherein at least one of the basic or acidic precursors comprises aluminum, the relative flow rate of the acidic and basic precursors is chosen so as to obtain a pH of the reaction medium of between 8.5 and 10.5 and the flow rate of the acidic and basic precursor (s) containing aluminum is adjusted so as to get a rate of advancement of the second the step is between 87 and 95 ° A, the advancement rate being defined as the proportion of Al 2 O 3 formed in Al 2 O 3 equivalent during said second precipitation step relative to the total quantity of Al 2 O 3 formed in Al 2 O 3 equivalent. the result of step c) of the preparation process, said step operating at a temperature between 40 and 90 ° C and for a time between 2 minutes and 50 minutes; d) a filtration step of the suspension obtained at the end of the second precipitation step c) to obtain an alumina gel; e) a step of drying said alumina gel obtained in step d) to obtain a powder; f) a step of shaping the powder obtained at the end of step e) to obtain a green material; g) a step of heat treatment of the raw material obtained at the end of step f) at a temperature of between 500 and 1000 ° C., with or without a flow of air containing up to 60% by volume of water, to obtain an aluminum oxide support; h) a step of impregnating the hydro-dehydrogenating active phase on said aluminum oxide support.
[0002]
2. The method of claim 1 wherein the rate of advance of the first precipitation step a) is between 6 and 12%.
[0003]
3. Method according to one of claims 1 or 2 wherein the rate of advance of the first precipitation step a) is between 7 and 11%.
[0004]
4. Method according to one of claims 1 to 3 wherein the basic precursor is sodium aluminate.
[0005]
5. Method according to one of claims 1 to 4 wherein the acidic precursor is aluminum sulfate.
[0006]
6. Method according to one of claims 1 to 5 wherein in the first step of precipitation the aqueous reaction medium is water and said step operates with stirring, in the absence of organic additive.
[0007]
7. mesoporous hydroconversion catalyst capable of being prepared by the method according to one of claims 1 to 6.
[0008]
A mesoporous hydroconversion catalyst according to claim 7 having: an SBET surface area greater than 100 m 2 / g, a median mesoporous volume diameter greater than or equal to 18 nm, a mesoporous volume as measured by mercury porosimeter intrusion, between 0.55 ml / g and 0.85 ml / g, a total pore volume measured by mercury porosimetry greater than or equal to 0.60 ml / g, a macroporous volume of less than 10% of the total pore volume. absence of micropores.
[0009]
The mesoporous hydroconversion catalyst of claim 8 having a macroporous volume of less than 5% of the total pore volume.
[0010]
10. Hydroconversion catalyst according to one of claims 8 or 9 having a median mesoporous volume diameter determined by mercury porosimeter intrusion between 20 and 25 nm.
[0011]
11. Hydroconversion catalyst according to one of claims 7 to 10 wherein the group VI B metal content is between 6 and 14% by weight of Group VI B metal trioxide relative to the total mass of the catalyst, the group VIII metal content is between 0.0 and 5.0% by weight of the Group VIII metal oxide with respect to the total weight of the catalyst, the phosphorus content is between 0.degree. at 7% by weight of phosphorus pentoxide relative to the total mass of the catalyst.
[0012]
12. A hydroconversion catalyst according to one of claims 7 to 11 wherein the hydro-dehydrogenating active phase is composed of molybdenum or nickel and molybdenum or cobalt and molybdenum.
[0013]
13. A hydroconversion catalyst according to claim 12 wherein the hydrodehydrogenating active phase also comprises phosphorus.
[0014]
14. Process for the hydrotreatment of a heavy hydrocarbon feedstock chosen from atmospheric residues, vacuum residues from direct distillation, deasphalted oils, residues resulting from conversion processes such as, for example, those originating from coking, from hydroconversion in a fixed bed, in an ebullated bed or in a moving bed, taken alone or as a mixture, comprising contacting said feed with hydrogen and a hydroconversion catalyst according to one of claims 7 to 13 or prepared according to one of claims 1 to 6.
[0015]
15. Hydrotreatment process according to claim 14 partially made in a bubbling bed at a temperature between 320 and 450 ° C, under a hydrogen partial pressure of between 3 MPa and 30 MPa, at a space velocity between 0, 1 and 10 volumes of filler per volume of catalyst per hour, and with a gaseous hydrogen gas on liquid hydrocarbon charge of between 100 and 3000 normal cubic meters per cubic meter.
[0016]
16. Hydroprocessing process according to claim 14 or 15 made at least partly in fixed bed at a temperature between 320 ° C and 450 ° C, at a hydrogen partial pressure of between 3 MPa and 30 MPa, at a speed of of space between 0.05 and 5 volume of charge per volume of catalyst per hour, and with a gaseous hydrogen ratio on hydrocarbon liquid charge of between 200 and 5000 normal cubic meters per cubic meter.
[0017]
17. Process for the hydrotreatment of a heavy hydrocarbon feedstock of the fixed bed residue type according to claim 16 comprising at least: a) a hydrodemetallization step; b) a hydrodesulfurization step; wherein said hydroconversion catalyst is used in at least one of said steps a) and b).
[0018]
18. A process for the hydrotreatment of heavy hydrocarbon feedstock of the fixed bed residue type according to claim 17, in which: the feedstock has a cumulative metal content, initial or after hydrotreatment, on one or more other hydrodemetallation catalysts, lower or equal to 50 ppm; and wherein said hydroconversion catalyst is used in the hydrodemetallization step.

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2015-12-18| PLSC| Publication of the preliminary search report|Effective date: 20151218 |

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2021-06-25| PLFP| Fee payment|Year of fee payment: 8 |

优先权:

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申请号 | 申请日 | 专利标题

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FR1455415A|FR3022158B1|2014-06-13|2014-06-13|MESOPOROUS CATALYST OF RESIDUAL HYDROCONVERSION AND METHOD OF PREPARATION|

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FR1455415|2014-06-13|FR1455415A| FR3022158B1|2014-06-13|2014-06-13|MESOPOROUS CATALYST OF RESIDUAL HYDROCONVERSION AND METHOD OF PREPARATION|

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US15/318,527| US10130942B2|2014-06-13|2015-06-09|Mesoporous catalyst for hydroconversion of residues and method for preparing the latter|

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PCT/EP2015/062821| WO2015189195A1|2014-06-13|2015-06-09|Mesoporous residuum hydroconversion catalyst and method for preparing same|

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EP15736795.4A| EP3154682B1|2014-06-13|2015-06-09|Mesoporous catalyst for hydrotreating petroleum residue and preparation method thereof|

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CN201580043388.6A| CN106573228B|2014-06-13|2015-06-09|Medium-pore catalyst for hydro-conversion residual oil and the method that is used to prepare the latter|

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DK15736795.4T| DK3154682T3|2014-06-13|2015-06-09|MESOPOROUS CATALYST FOR HYDROCONVERSION OF RESIDUAL PRODUCTS AND PROCEDURE FOR MANUFACTURING|

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RU2017100959A| RU2687100C2|2014-06-13|2015-06-09|Mesoporous catalyst for hydroconversion of residues and method for production thereof|