METHOD FOR HYDROPROCESSING DISTILLATE CUP USING A CATALYST BASED ON AMORPHOUS AMORPHOUS ALUMINA HAVI

专利摘要:
A process for the hydrotreatment of at least one hydrocarbon feed having a weighted average temperature (TMP) greater than 380 ° C using at least one catalyst comprising at least one Group VIB metal and / or at least one Group VIII metal is described of the periodic table and a support comprising an amorphous mesoporous alumina having a connectivity (Z) greater than 2.7, said hydrotreatment process operating at a temperature between 250 ° C and 430 ° C, at a total pressure of between 4 MPa and 20 MPa with a volume ratio of hydrogen per volume of hydrocarbon feedstock of between 200 and 2000 liters per liter and at a Hourly Volumetric Velocity (VVH) defined by the ratio of the volume flow rate of the liquid hydrocarbon feedstock by the volume of charged catalyst in the reactor between 0.5 and 5 h -1.
公开号:FR3022255A1
申请号:FR1455425
申请日:2014-06-13
公开日:2015-12-18
发明作者:Malika Boualleg；Antoine Hugon
申请人:IFP Energies Nouvelles IFPEN；
IPC主号:

专利说明:

[0001] TECHNICAL FIELD The invention relates to processes for hydrotreatment of hydrocarbon feeds having a weighted average temperature (TMP) greater than 380 ° C. Preferably, the hydrocarbon feedstock used in the process according to the invention is a vacuum distillate type feedstock (DSV). The objective of the process according to the invention is essentially the purification of said hydrocarbon feeds and in particular of distillates. In particular, the present invention relates to the use in a hydrotreatment process of a hydrocarbon feedstock having a weighted average temperature (TMP) greater than 380 ° C, of a catalyst comprising at least one Group VIB metal and or at least one Group VIII metal of the Periodic Table and a support comprising an amorphous mesoporous alumina having a very high connectivity as well as advantageously a specific porous distribution with respect to the alumina of the prior art. Said amorphous mesoporous alumina is advantageously shaped from an alumina gel having a high dispersibility, said alumina gel being itself obtained by precipitation of at least one aluminum salt according to a specific process. More particularly, the present invention relates to the use in a hydrotreatment process of said hydrocarbon feedstock of a catalyst comprising a support comprising an amorphous mesoporous alumina shaped from an alumina gel, said gel of alumina being prepared according to a method of preparation by specific precipitation, making it possible to obtain at least 40% by weight of alumina in equivalent Al 2 O 3 with respect to the total amount of alumina formed at the end of the step or steps of precipitation and more generally at the end of the steps of preparation of the alumina gel, from the first precipitation step, the amount of alumina formed at the end of the first precipitation step can even reach 100%. State of the Prior Art In general, it is accepted that a hydrotreatment catalyst with a high catalytic potential is characterized by an optimized hydro-dehydrogenating function, that is to say a fully dispersed active phase on the surface of the support and having a high metal content. Ideally, whatever the nature of the hydrocarbon feedstock to be treated, the catalyst must be able to provide an accessibility of the active sites with respect to the reagents and reaction products while developing a high active surface, which leads to specific constraints. in terms of structure and texture specific to the constituent oxide support of said catalysts. The composition and use of conventional hydrotreatment catalysts for hydrocarbon feedstocks are well described in "Hydrocracking Science and Technology", 1996, J. Scherzer, AJ Gruia, Marcel Dekker Inc. and in the article by BS Clausen, HT
[0002] 10 Topsoe, F. E. Massoth, from "Catalysis Science and Technology", 1996, Volume 11, Springer-Verlag. Thus, these catalysts are generally characterized by the presence of an active phase based on at least one Group VIB metal and / or at least one Group VIII metal of the periodic table of the elements. The most common formulations are cobalt-molybdenum (CoMo), nickel-molybdenum (NiMo) and nickel-tungsten (NiW). These catalysts may be in mass form or in the supported state, thus involving a porous solid of different nature. In the latter case, the porous support is generally an amorphous or poorly crystallized oxide, such as for example an alumina, or an aluminosilicate, optionally combined with a zeolite material or not. After preparation, the Group VIB metal and / or the group VIII metal constituting said catalysts is often in oxide form. The active and stable form of said catalysts for the hydrotreatment processes being the sulphurized form, these catalysts must undergo a sulphurization step. This can be carried out in the unit of the associated process, it is called in-situ sulfurization, or prior to the loading of the catalyst in the unit, it is called ex-situ sulfurization.
[0003] The usual methods leading to the formation of the active phase of the hydrotreatment catalysts consist in depositing the molecular precursor (s) of at least one Group VIB metal and / or at least one Group VIII metal on an oxide support by the so-called "dry impregnation" technique followed by the maturation, drying and calcination steps leading to the formation of the oxidized form of the said metal (s) employed. Then comes the final stage of sulfuration generating the active phase as mentioned above. In particular, US Pat. No. 7,790,652 discloses a novel alumina support having a very specific porous distribution, which can be used as a catalyst support in a process for hydroconversion of heavy hydrocarbon feeds. Said support comprising alumina has an average pore diameter of between 100 and 140 A, a size distribution whose width is less than 33 Å, a pore volume of at least 0.75 ml / g in which less 5% of the pore volume of said support is present in pores with a diameter greater than 210 Å. Said support used in combination with a hydrogenating active phase makes it possible to obtain unexpected catalytic performances in the case where it is used in hydroconversion of heavy charges preferably having a majority of its components boiling at a temperature above 343 ° C. In particular, the heavy charge hydroconversion process according to US Pat. No. 7,790,652 makes it possible to obtain a conversion of the hydrocarbon compounds boiling at a temperature above 524 ° C. which is greatly improved compared with conversions obtained with conventional catalysts. prior art. Said alumina support is prepared according to a method comprising a first step of forming an alumina dispersion by mixing, in a controlled manner, a first aqueous alkaline solution and a first aqueous acid solution, at least one of said acidic and basic solutions, or both comprising an aluminum compound. The acidic and basic solutions are mixed in such proportions that the pH of the resulting dispersion is between 8 and 11. The acidic and basic solutions are also mixed in amounts to obtain a dispersion containing the desired amount of alumina. in particular, the first step makes it possible to obtain 25 to 35% by weight of alumina with respect to the total amount of alumina formed at the end of the two precipitation stages. The first stage operates at a temperature of between 20 and 40 ° C. When the desired amount of alumina is formed, the temperature of the slurry is raised to a temperature between 45 and 70 ° C, and then the heated slurry is then subjected to a second precipitation step by contacting said slurry with a second alkaline aqueous solution and a second acidic aqueous solution, at least one or both of the two solutions comprising an aluminum compound. Similarly, the pH is adjusted to between 8 and 10.5 by the proportions of the acid and basic solutions added and the remaining amount of alumina to be formed in the second step is provided by the amounts of the second acid and basic solutions added. The second step operates at a temperature of between 20 and 40 ° C. The alumina gel thus formed comprises at least 95% of boehmite. The dispersibility of the alumina gel thus obtained is not mentioned. The alumina gel is then filtered, washed and optionally dried according to the methods known to those skilled in the art, without a heat treatment step or prior curing, to produce an alumina powder which is then shaped according to methods known to those skilled in the art and then calcined to produce the final alumina support. The first precipitation step of the preparation process of US Pat. No. 7,790,652 is limited to a low alumina production of between 25 and 35% by weight, since a higher alumina production at the end of the first stage does not allow optimal filtration of the gel obtained. Moreover, the increase in the production of alumina in the first step of US Pat. No. 7,790,652 would not allow the shaping of the gel thus obtained.
[0004] The applicant has discovered that the use in a hydrotreatment process of at least one carbonaceous filler having a weighted average temperature (TMP) greater than 380 ° C., of at least one catalyst comprising at least one group VIB metal. and / or at least one Group VIII metal of the Periodic Table and a support comprising an amorphous mesoporous alumina having a very high connectivity, allowed to obtain an improved catalytic activity compared to hydrotreatment catalysts of the prior art. In particular, in the case where said process according to the invention is placed upstream of a hydrocracking unit of said feedstock, the process according to the invention using said catalyst (s) comprising the specific alumina support allows a better deazotation of said feedstock than the processes of the prior art using conventional hydrotreating catalysts, as well as a better hydrogenation of aromatics contained in said feedstock. Similarly, in the case where said process according to the invention is placed upstream of a catalytic fluidized bed cracking unit of said feedstock, the process according to the invention using said catalyst (s) comprising the alumina support. Specific allows a better desulfurization of said charge compared to the methods of the prior art. An object of the present invention is therefore to provide a process for the hydrotreatment of at least one hydrocarbon feedstock having a weighted average temperature (TMP) greater than 380 ° C. using at least one catalyst having improved catalytic performance, in particular in terms of denitrogenation of said feedstock and hydrogenation of the aromatics contained in said feedstock in the case where said hydrotreatment process according to the invention is placed upstream of a hydrocracking unit of said feedstock and in terms of hydrodesulfurization said feedstock in the case where said process according to the invention is placed upstream of a fluidized catalytic cracking unit of said feedstock. SUMMARY AND INTEREST OF THE INVENTION The subject of the present invention is a process for the hydrotreatment of at least one hydrocarbon feedstock having a weighted average temperature (TMP) greater than 380 ° C. using at least one catalyst comprising at least one metal of at least one group VIB and / or at least one Group VIII metal of the Periodic Table and a support comprising an amorphous mesoporous alumina having connectivity (Z) greater than 2.7, the connectivity being determined from the adsorption / desorption isotherms nitrogen, said hydrotreatment process operating at a temperature between a temperature between 250 ° C and 430 ° C, at a total pressure of between 4 MPa and 20 MPa with a volume ratio of hydrogen per volume of load hydrocarbon mixture of between 200 and 2000 liters per liter and at a Hourly Volumetric Velocity (VVH) defined by the ratio of the volume flow rate of the liquid hydrocarbon feedstock p ar the volume of catalyst loaded into the reactor between 0.5 and 5 h-1. One of the advantages of the present invention resides in the implementation, in a hydrotreatment process of at least one hydrocarbon feed having a weighted average temperature (TMP) greater than 380 ° C, of a catalyst based on a support comprising an alumina whose porosity is very connected, that is to say having a number of pores adjacent to a very important pore. High connectivity represents an important advantage for the diffusion of the molecules of said charge to be treated during the implementation of the hydrotreatment process according to the invention using this material.
[0005] A better diffusion of the reagents makes it possible to have a more homogeneous concentration within the catalyst and thus enables a greater majority of the catalytic sites to work to the best of its ability. Throughout the rest of the text, the connectivity of the alumina according to the invention is defined as being the number of pores adjacent to a given pore. The connectivity of the alumina according to the invention is representative of the totality of the porosity of the alumina and in particular of the totality of the mesoporosity of the alumina, that is to say of all the pores having a average diameter between 2 and 50 nm.
[0006] Connectivity is a relative quantity measured according to the procedure described in the Seaton publication (Liu H., Zhang L., Seaton N.A., Chemical Engineering Science, 47, 17-18, pp.4393-4404, 1992). This is a Monte Carlo simulation from nitrogen adsorption / desorption isotherms. These connectivity parameters are based on the theory of percolation. Connectivity is related to the numbers of adjacent pores and high connectivity represents an advantage for diffusion during catalytic reactions of the molecules to be treated. Another subject of the invention is also a process for the hydrotreatment of at least one hydrocarbon feedstock having a weighted average temperature (TMP) greater than 380 ° C., operating at a temperature of between 250 ° C. and 430 ° C. at a total pressure of between 4 MPa and 20 MPa with a ratio of volume of hydrogen per volume of hydrocarbon feedstock of between 200 and 2000 liters per liter and at a rate per hour volume (VVH) defined by the ratio of hydrocarbon feedstock volume flow rate liquid by the volume of catalyst charged to the reactor of between 0.5 and 11-1, said process using at least one catalyst comprising at least one Group VIB metal and / or at least one Group VIII metal of the classification. and a support comprising an amorphous mesoporous alumina, said alumina being prepared according to at least the following steps: a) at least a first step a) of precipitating alumina, in mili aqueous reaction 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 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 in such a way as to to obtain a first stage progress rate of between 40 and 100%, the feed rate being defined as the proportion of alumina formed in Al 2 O 3 equivalent during said step a) of precipitation with respect to the quantity total of alumina formed at the end of the or the precipitation steps and more generally after the steps of preparation of the alumina gel, said step a) operating at a temperature between 10 and 50 ° C, and for a period of between 2 minutes and 30 minutes, B) a step of heat treatment of the suspension obtained at the end of step a), at a temperature of between 50 and 200 ° C. for a duration of between 30 minutes and 5 hours, C) a filtration step of the suspension obtained at the end of the thermal treatment step b), followed by at least one washing step of the gel obtained, d) a step of drying the alumina gel obtained at the end of the step c) to obtain a powder, e) a step of shaping the powder obtained at the end of step d) to obtain the green material, f) a heat treatment step of the raw material obtained at the result of step e) at a temperature between 500 and 1000 ° C, with or without a flow of air containing up to 60% by volume of water. An advantage of the invention is to provide a hydrotreatment process using a catalyst whose alumina support is prepared according to a very specific preparation process, allowing the shaping of a highly dispersible alumina gel, itself prepared. from a precipitation stage in which at least 40% by weight of Al 2 O 3 equivalent relative to the total amount of alumina formed at the end of said gel preparation process are formed from the first precipitation stage . This process is carried out by virtue of the implementation of a heat treatment step and in particular a rolling step which makes it possible to obtain an alumina gel having improved filterability and facilitating its shaping. Definitions and Measuring Methods Throughout the rest of the text, the dispersibility index is defined as the weight percentage of peptised alumina gel that can be dispersed by centrifugation in a 3600 G polypropylene tube for 10 minutes. Dispersibility is measured by dispersing 10% boehmite or alumina gel in a water slurry also containing 10% nitric acid based on the boehmite mass. Then, the suspension is centrifuged at 3600G rpm for 10 min. The collected sediments are dried at 100 ° C overnight and weighed. The dispersibility index, denoted ID, is obtained by the following calculation: ID (° / 0) = 100% -mass of dried sediments (%).
[0007] Throughout the rest of the text, the connectivity of the alumina used as a catalyst support or catalyst used in the process according to the invention is defined as being the number of pores adjacent to a given pore. The connectivity according to the invention is determined from nitrogen adsorption / desorption isotherms, is representative of the totality of the porosity of the alumina or of the catalyst and in particular of the totality of the mesoporosity of the alumina. that is to say, all the pores having a mean diameter of between 2 and 50 nm. Connectivity is a relative quantity measured according to the procedure described in the Seaton publication (Liu H., Zhang L., Seaton N.A., Chemical Engineering Science, 47, 17-18, pp.4393-4404, 1992). This is a Monte Carlo simulation from nitrogen adsorption / desorption isotherms. These connectivity parameters are based on the theory of percolation. The connectivity is related to the numbers of adjacent pores and high connectivity represents an advantage for diffusion during catalytic reactions of the molecules to be treated. The alumina and catalyst used in the process according to the present invention further has a specific porous distribution, in which the macroporous and mesoporous volumes are measured by mercury intrusion and the microporous volume is measured by nitrogen adsorption. "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.
[0008] "Micropores" means pores whose opening is less than 2 nm. In the following description of the invention, the porous distribution measured by mercury porosimetry is determined by mercury porosimeter intrusion according to ASTM standard D4284-83 at a maximum pressure of 4000 bar (400 MPa), using a voltage of surface of 484 dyne / cm and a contact angle of 140 °. The anchorage angle 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". , 2 MPa the value from which the mercury fills all the intergranular voids, and it is considered that beyond it the mercury penetrates into the pores of the alumina.
[0009] In order to obtain a better accuracy, the value of the total pore volume corresponds to the value of the total pore volume measured by mercury porosimeter intrusion measured on the sample minus the value of the total pore volume measured by mercury porosimeter intrusion. measured on the same sample for a pressure corresponding to 30 psi (about 0.2 MPa). The macroporous volume of the catalyst 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.
[0010] The mesoporous volume of the catalyst is defined as the accumulated 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.
[0011] 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. Rouquérol, J. Rouquérol and K. Sing, Academic Press, 1999.
[0012] The median diameter of the mesopores (Dp in nm) is also defined as a diameter such that all pores less than this diameter constitute 50% of the mesoporous volume, measured by mercury porosimetry.
[0013] The porous distribution measured by nitrogen adsorption was determined by the Barrett-Joyner-Halenda model (BJH). The nitrogen adsorption-desorption isotherm according to the BJH model is described in the periodical "The Journal of American Society", 73, 373, (1951) written by E.P.Barrett, L.G.Joyner and P.P.Halenda. In the following description of the invention, the term nitrogen adsorption volume means the volume measured for P / Po = 0.99, a pressure for which it is assumed that nitrogen has filled all the pores. 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 10 3022255 established from the BRUNAUER-EMMETT-TELLER method described in the journal "The Journal of American Society", 60, 309, (1938). The groups of chemical elements are given according to the CRC classification (CRC Handbook of Chemistry and Physics, publisher CRC press, editor-in-chief DR Lide, 5 81st edition, 2000-2001), for example group VIII according to the classification CASES correspond to the metals of columns 8, 9 and 10 according to the new IUPAC classification Description of the Invention The invention relates to a process for the hydrotreatment of at least one hydrocarbon feed having a weighted average temperature (TMP) greater than 380 C. Charges A wide variety of feedstocks can be treated by the hydrocracking processes according to the invention The feedstock used in the hydrocracking process according to the invention is a hydrocarbon feedstock. with a weighted average temperature (TMP) greater than 380 ° C. The TMP is defined from the temperature at which 5%, 50% and 70% of the volume of the charge distils according to the following formula: TMP = (T 5% + 2 × T 50% + 4 × T 70%) / 7. The TMP is calculated from simulated distillation values. The TMP of the feed is greater than 380 ° C and preferably less than 600 ° C, and more preferably less than 580 ° C. The treated hydrocarbon feedstock generally has a distillation range of from 250 ° C to 600 ° C, preferably from 300 to 580 ° C. In the rest of the text, we will conventionally call this vacuum distillate charge, but this designation has no restrictive character. Any hydrocarbon feedstock containing sulfur and nitrogen compounds inhibiting hydrotreatment, and a TMP similar to that of a vacuum distillate cut may be concerned by the process object of the present invention. The hydrocarbon feed may be of any chemical nature, that is to say have any distribution between the various chemical families including paraffins, olefins, naphthenes and aromatics. Preferably, said feedstock treated in the process according to the invention is a hydrocarbon feedstock of which at least 50% by weight of the compounds have an initial boiling point of greater than 340 ° C. and a final boiling point of less than 540 ° C. preferably at least 60% by weight, more preferably at least 75% by weight and more preferably at least 80% by weight of the compounds have an initial boiling point above 340 ° C and a d final boiling below 540 ° C. Said hydrocarbon feedstock is advantageously chosen from vacuum distillates (or DSV), effluents from a catalytic cracking unit FOC (Fluid Catalytic Cracking 5), light gas oils from a cracking unit. catalytic (or LCO for Light Cycle Oil according to the English terminology), heavy cutting oils (HCO for Heavy Cycle Oil according to the English terminology), paraffinic effluents from Fischer-Tropsch synthesis, effluents from vacuum distillation, such as, for example, gas oil fractions of the VGO (Vacuum Gas Oil) type, the effluents resulting from the process of liquefying coal, the feedstocks resulting from the biomass or the effluents coming from the conversion of biomass feedstock, and aromatic extracts and feedstock from aromatics extraction units, alone or as a mixture. Preferably, said hydrocarbon feed is a vacuum distillate cut. The vacuum distillate cut is generally derived from vacuum distillation of the crude oil. Said vacuum distillate cut comprises aromatic compounds, naphthenic compounds and / or paraffinic compounds. Said vacuum distillate cut may optionally comprise heteroatoms chosen from nitrogen, sulfur and the mixture of these two elements. When the nitrogen is present in said feed to be treated, the nitrogen content is greater than or equal to 300 ppm, preferably said content is between 300 and 10,000 ppm by weight, preferably between 500 and 10,000 ppm by weight, so more preferred between 700 and 4000 ppm by weight and even more preferably between 1000 and 4000 ppm. When the sulfur is present in said feed to be treated, the sulfur content is between 0.01 and 5% by weight, preferably between 0.2 and 4% by weight and even more preferably between 0.5 and 3% weight Said vacuum distillate cut may optionally also contain metals, in particular nickel and vanadium. The cumulative nickel and vanadium content of said vacuum distillate fraction is preferably less than 1 ppm by weight. The asphaltene content of said hydrocarbon feedstock is generally less than 3000 ppm, more preferably less than 1000 ppm, even more preferably less than 200 ppm.
[0014] In a preferred embodiment, said vacuum distillate type hydrocarbon feedstock (or DSV) may be used as such, that is to say alone or as a mixture with other hydrocarbon cuts, preferably chosen from effluents from a catalytic cracking unit FCC (Fluid Catalytic Cracking), light gas oils from a catalytic cracking unit (or LCO for Light Cycle Oil in English terminology), heavy-cycle oils (HCO for Heavy Cycle Oil), atmospheric residues and vacuum residues from atmospheric and vacuum distillation of crude oil, paraffinic effluents from Fischer-Tropsch synthesis, effluents resulting from vacuum distillation, such as, for example, gas oil fractions of the VGO (Vacuum Gas Oil) type, the dehalphalated oils or DAO (Deasp). halted Oil), the effluents resulting from the process of liquefying coal, the charges resulting from the biomass or the effluents resulting from the conversion of charges resulting from the biomass, and the aromatic extracts and the charges originating from aromatics extraction units, taken alone or as a mixture. In the preferred case where said hydrocarbon feedstock of the vacuum distillate type (or DSV) is used in a mixture with other hydrocarbon cuts, said hydrocarbon cuts added alone or in a mixture, are presented at at most 50% by weight of said mixture, preferably at most 40% by weight, preferably at most 30% by weight and more preferably at most 20% by weight of said mixture. According to the invention, the process for hydrotreating said hydrocarbon feedstock according to the invention is carried out at a temperature of between 250.degree. C. and 430.degree. C., preferably between 350.degree. C. and 405.degree. between 4 MPa and 20 MPa and preferably between 6 MPa and 15 MPa with a volume ratio of hydrogen per volume of hydrocarbon feedstock of between 200 and 2000 liters per liter and preferably between 250 and 1400 liters per liter and at a Time Volumetric Speed (VVH) defined by the ratio of the volume flow rate of the liquid hydrocarbon feedstock by the volume of catalyst charged to the reactor of between 0.5 and 5 h -1, and preferably between 0.7 and 3 h -1; .
[0015] According to a first embodiment, said hydrotreatment process according to the invention may advantageously be carried out upstream of a hydrocracking unit of said hydrocarbon feedstock. In this case, said hydrotreatment process according to the invention advantageously operates at a temperature of between 350 and 430 ° C., preferably between 350 and 405 ° C. at a total pressure of between 8 MPa and 20 MPa, and preferably between between 9 MPa and 15 MPa with a volume ratio of hydrogen per volume of hydrocarbon feedstock of between 200 and 2000 liters per liter and preferably between 500 and 1200 liters per liter and at a defined hourly volume velocity (VVH) the volume flow rate of the liquid hydrocarbon feedstock by the volume of catalyst charged to the reactor between 0.5 and 5 h -1, and preferably between 1 and 3 h -1. According to a second embodiment, said hydrotreatment process according to the invention can advantageously be carried out upstream of a catalytic fluidized bed cracking unit of said hydrocarbon feedstock. In this case, said hydrotreatment process according to the invention advantageously operates at a temperature of between 250 ° C. and 420 ° C., preferably between 340 ° C. and 400 ° C., at a total pressure of between 4 MPa and 15 MPa, and preferably between 4 MPa and 12 MPa with a volume ratio of hydrogen per volume of hydrocarbon feedstock of between 200 and 2000 liters per liter and preferably between 250 and 800 liters per liter and at a defined hourly volume velocity (VVH). by the ratio of the volume flow rate of the liquid hydrocarbon feedstock by the volume of catalyst charged to the reactor of between 0.5 and 5 h -1, and preferably between 0.7 and 2 h -1.
[0016] In accordance with the invention, the catalyst used in said hydrotreating process comprises at least one Group VIB metal and / or at least one Group VIII metal of the Periodic Table and a carrier comprising and preferably consisting of an alumina amorphous mesoporous having a connectivity (Z) greater than 2.7.
[0017] Preferably, the group VIII elements are selected from noble and non-noble metals of group VIII and preferably from iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium and iridium. or platinum, taken alone or in admixture and most preferably from cobalt and nickel, alone or in admixture. In the case where the elements of group VIII are chosen from non-noble metals of group VIII, the elements of group VIII are advantageously chosen from cobalt and nickel, taken alone or as a mixture. Preferably, the group VIB elements are chosen from tungsten and molybdenum, taken alone or as a mixture. In the case where the hydrogenating function comprises a group VIII element and a group VIB element, the following metal combinations are preferred: nickel-molybdenum, cobalt-molybdenum, iron-molybdenum, iron-tungsten, nickel-tungsten, cobalt-tungsten, and very preferably: nickel-molybdenum, cobalt-molybdenum, nickel-tungsten. It is also possible to use combinations of three metals such as for example nickel-cobalt-molybdenum. When a combination of Group VI and Group VIII metals is used, the catalyst is then preferably used in a sulfurous form. According to a preferred embodiment, said catalyst may also comprise tin, the tin content preferably being between 0.1 and 0.5% by weight relative to the total mass of catalyst. In the case where the catalyst comprises at least one Group VIB metal in combination with at least one Group VIII non-noble metal, the Group VIB metal content is advantageously between 5 and 45% by weight of oxide relative to to the total mass of said catalyst, preferably between 10 and 40% by weight of oxide and very preferably between 20 and 35% by weight of oxide and the non-noble metal content of group VIII is advantageously between 0 and , 5 and 10% by weight of oxide relative to the total weight of said catalyst, preferably between 1 and 8% by weight of oxide and very preferably between 1.5 and 6% by weight of oxide . Advantageously, the catalyst used in the process according to the invention may contain at least one doping element chosen from phosphorus, boron, fluorine or silicon, alone or as a mixture. In a preferred manner, the dopant is phosphorus. When the catalyst contains phosphorus, the phosphorus content in said catalyst is preferably between 0.5 and 15% by weight of P 2 O 5, more preferably between 1 and 10% by weight of P 2 O 5. very preferred between 2 and 8 (3/0 weight of P205.
[0018] According to the first embodiment in which said hydrotreatment process according to the invention is advantageously carried out upstream of a hydrocracking unit of said hydrocarbon feedstock, the catalyst used in said hydrotreatment process preferably comprises nickel and molybdenum. According to the second embodiment in which said hydrotreatment process according to the invention is advantageously carried out upstream of a fluidized catalytic cracking unit of said hydrocarbon feedstock, the catalyst used in said hydrotreatment process preferably comprises nickel and molybdenum, cobalt and molybdenum, or nickel, cobalt and molybdenum.
[0019] Preferably, the catalyst used in the process according to the invention comprises a support comprising and is preferably constituted by an amorphous mesoporous alumina, said alumina being prepared according to the invention. Preferably, the catalyst support used in the present invention comprises and is preferably constituted by an amorphous mesoporous alumina having a connectivity (Z) of between 2.7 and 10, preferably between 2.8 and 10, very preferably between 3 and 9, more preferably between 3 and 8 and even more preferably between 3 and 7, the connectivity being determined from nitrogen adsorption / desorption isotherms.
[0020] Said alumina used as a support in the catalyst and the support comprising said alumina have a specific surface area and a porous distribution calibrated and adapted to its use in a process for hydrotreating said hydrocarbon feedstock.
[0021] Said amorphous mesoporous alumina constituting the support of the catalyst and the support of the catalyst used in the process according to the invention advantageously have the following porous distribution, measured by mercury porosimetry: the percentage of volume included in the pores of size between 2 and 8 nm relative to the total pore volume, is between 20 to 40%, 20 - the percentage of volume included in the pores between 8 and 20 nm in size relative to the total pore volume is between 50 to 65% the percentage of volume comprised in the pores between 20 and 50 nm in size relative to the total pore volume is less than 10%, the percentage of volume included in the pore size between 50 and 7000 nm by relative to the total pore volume, is less than 10%, and preferably less than 6%. Preferably, the mesoporous alumina is devoid of micropores. Preferably, the mesoporous support comprising said alumina is devoid of 30 micropores. Preferably, the alumina used in the invention and said support comprising said alumina are non-mesostructured.
[0022] Preferably, said alumina and said support has a BET specific surface area of between 50 and 450 m 2 / g, preferably between 100 and 400 m 2 / g, preferably between 150 and 400 m 2 / g, and very preferably preferred between 150 and 350 m 2 / g.
[0023] Preferably, the total pore volume of said alumina and said medium measured by mercury porosimetry is between 0.6 and 0.9 ml / g. Preferably, said alumina and said support have a mesoporous volume of between 0.6 and 0.8 ml / g and preferably between 0.65 and 0.8 ml / g.
[0024] Preferably, the support and the alumina have a macroporous volume of between 0 and 0.1, preferably between 0.01 and 0.1 ml / g and preferably between 0.01 and 0.05 ml / g. . The median diameter of the mesopores (Dp in nm) measured by mercury porosimetry of said alumina and said support, determined in volume, is advantageously between 8 and 12.5 nm and preferably between 9.0 and 12.5 nm. The catalyst used in the present invention also has a connectivity (Z) advantageously greater than 2.7 and preferably between 2.7 and 10, preferably between 2.8 and 10, very preferably between 3 and 10. and 9, more preferably between 3 and 8 and even more preferably between 3 and 7, the connectivity of the catalyst being determined from nitrogen adsorption / desorption isotherms.
[0025] Said catalyst advantageously has a BET surface area of between 50 and 450 m 2 / g, preferably between 50 and 300 m 2 / g, preferably between 100 and 300 m 2 / g and very preferably between 100 and 250 m 2. m2 / g. Preferably, said catalyst has a mesoporous volume of between 0.1 and 0.6 ml / g and preferably between 0.2 and 0.5 ml / g. Preferably, said catalyst has a macroporous volume of between 0.01 and 0.1 ml / g.
[0026] Said catalyst is also advantageously characterized by the following porous distribution measured by mercury porosimetry: the percentage of volume comprised in pores less than 8 nm in size relative to the total pore volume is between 20 and 40%, percentage of volume included in the pores of size between 8 and 20 nm relative to the total pore volume, is between 40 to 65%, the percentage of volume included in the pore size of between 20 and 50 nm relative to the volume total porous, is less than 10%, the percentage of volume included in the pore size between 50 and 7000 10 nm relative to the total pore volume, is less than 10%, and preferably less than 5%. Said alumina used as support for the catalyst used in the process according to the present invention is advantageously prepared according to the preparation process comprising at least the following steps: a) at least a first step of precipitation of alumina, in an aqueous reaction medium, 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 flow rate relative 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 denoting a progress rate of said first step of between 40 and 100%, the advancement rate being defined as the proportion of alumina formed in A1203 equivalent during said first precipitation step relative to the total amount of alumina formed at the end of the precipitation step or steps, said first precipitation step operating at a temperature of between 10 and 50 ° C, and for a time of between 2 minutes and 30 minutes, b) a step of heat treatment of the suspension obtained at the end of step a) at a temperature of between 50 and 200 ° C. for a duration of between 30 minutes and 5 hours making it possible to obtain an alumina gel, c) a filtration step of the suspension obtained at the end of the heat treatment step b), followed by at least one washing step of the gel obtained, d) a step of drying the alumina gel obtained at result of step c) to obtain a powder, e) a step of shaping the powder obtained at the end of step d) to obtain the green material, f) a heat treatment step of the green material obtained at the end of the step e) at a temperature between 500 and 1000 ° C, with or without air flow containing up to 60% by volume of water. Generally speaking, the "rate of progress" of the nth precipitation step is the percentage of alumina formed in Al.sub.2 O.sub.3 equivalent in said nth stage, relative to the total amount of alumina formed at the same time. resulting from all the precipitation steps and more generally after the steps of preparation of the alumina gel. In the case where the progress rate of said precipitation step a) is 100%, said precipitation step a) generally makes it possible to obtain an alumina suspension having an Al 2 O 3 concentration of between 20 and 100. g / 1, preferably between 20 and 80 g / l, more preferably between 20 and 50 g / l. Step a) of precipitation The mixture in the aqueous reaction medium of at least one basic precursor and at least one acidic precursor requires either that at least the basic precursor or the acidic precursor comprises aluminum, or that both basic and acidic precursors include 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, the basic precursor (s) and acid (s) are added in said first precipitation step a) in aqueous solution containing said precursor (s).
[0027] Preferably, the aqueous reaction medium is water. Preferably, said step a) operates with stirring. Preferably, said step a) is carried out in the absence of organic additive.
[0028] 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. According to the invention, it is the relative flow rate of the acidic and basic precursors that they contain aluminum or not, which 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 1.6 and 2.05.
[0029] 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 and very preferably between 8.7 and 9.9.
[0030] The acidic and basic precursors are also mixed in amounts to provide a suspension containing the desired amount of alumina, depending on the final alumina concentration to be achieved. In particular, said step a) makes it possible to obtain 40 to 100% by weight of alumina in Al 2 O 3 equivalent relative to the total amount of alumina 20 formed at the end of the precipitation stage (s) and more generally to the outcome of the steps of preparation of the alumina gel. According to the invention, it is the flow rate of the acidic and basic precursor (s) containing aluminum which is adjusted so as to obtain a forwarding rate of the first stage of between 40 and 100%.
[0031] Preferably, the rate of progress of said precipitation step a) is between 40 and 99%, preferably between 45 and 90% and preferably between 50 and 85%. the amount of advance obtained at the end of the precipitation step a) is less than 100%, a second precipitation step is necessary in order to increase the amount of alumina formed. In this case, the advancement rate being defined as being the proportion of alumina formed in A1203 equivalent during said step a) of precipitation with respect to the total amount of alumina formed at the end of the two precipitation steps of method of preparation according to the invention and more generally at the end of the steps of preparation of the alumina gel.
[0032] Thus, depending on the concentration of alumina targeted at the end of the precipitation step (s), preferably between 20 and 100 g / l, the quantities of aluminum to be provided by the acid precursors and / or The flow rate of the precursors is calculated as a function of the concentration of said added aluminum precursors, the amount of water added to the reaction medium and the rate of progress required for the precipitation step (s). The flow rates of the aluminum-containing acidic and / or basic precursor (s) depend on the size of the reactor used and thus the amount of water added to the reaction medium. Preferably, said precipitation step a) is carried out at a temperature of between 10 and 45 ° C., preferably between 15 and 45 ° C., more preferably between 20 and 45 ° C. and very preferably between 20 and 45 ° C. 40 ° C.
[0033] It is important that said precipitation step a) operates at a low temperature. In the case where said preparation process according to the invention comprises two precipitation stages, the precipitation step a) is advantageously carried out at a temperature below the temperature of the second precipitation stage.
[0034] Preferably, said precipitation step a) is carried out for a period of between 5 and 20 minutes, and preferably of 5 to 15 minutes. Step b) of heat treatment According to the invention, said preparation method comprises a heat treatment step b) of the suspension obtained at the end of the precipitation step a), said heat treatment step operating at a temperature of temperature between 60 and 200 ° C for a period of between 30 minutes and 5 hours, to obtain the alumina gel. Preferably, said heat treatment step b) is a ripening step. Preferably, said heat treatment step b) operates at a temperature of between 65 and 150 ° C, preferably between 65 and 130 ° C, preferably between 70 and 110 ° C, very preferably between 70 and 95 ° C. ° C. Preferably, said heat treatment step b) is carried out for a duration of between 40 minutes and 5 hours, preferably between 40 minutes and 3 hours, and preferably between 45 minutes and 2 hours.
[0035] Optional second precipitation step According to a preferred embodiment, in the case where the advancement rate obtained at the end of the precipitation step a) is less than 100%, said method of preparation preferably comprises a second precipitation step a ') after the first precipitation step. Said second precipitation step makes it possible to increase the proportion of alumina produced. Said second precipitation step a ') is advantageously carried out between said first precipitation step a) and the heat treatment step b).
[0036] In the case where a second precipitation step is carried out, a step of heating the suspension obtained at the end of step a) of precipitation is advantageously carried out between the two precipitation steps a) and '). Preferably, said step of heating the suspension obtained at the end of step a), carried out between said step a) and the second precipitation step a ') operates at a temperature between 20 and 90 ° C, preferably between 30 and 80 ° C, preferably between 30 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. Said heating step is advantageously carried out according to all the heating methods known to those skilled in the art. According to said preferred embodiment, said preparation method comprises a second step of precipitation of the suspension obtained at the end of the heating step, said second stage operating by adding to said suspension at least one selected basic precursor among 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 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 an advancement rate of the second stage inclusive ent 60%, the rate of advance being defined as being the proportion of alumina formed in equivalent A1203 during said second precipitation step relative to the total amount of alumina formed at the end of the two stages precipitation, more generally at the end of the steps of preparation of the alumina gel and preferably at the end of step a ') of the preparation process according to the invention, said step operating at a temperature between 40 and 90 ° C, and for a period of time between 2 minutes and 50 minutes. 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 either at least the basic precursor or the acidic precursor. comprises aluminum, that the two basic precursors and acid include 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. 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. As in step a) of precipitation, it is the relative flow rate of the acidic and basic precursors that they contain aluminum or not, which is chosen so as to obtain a pH of the reaction medium of between 8, 5 and 10.5.
[0037] 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 1.6 and 2.05. 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 with 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 and preferably between 8.7 and 9.9.
[0038] The acidic and basic precursors are also mixed in amounts to provide a suspension containing the desired amount of alumina, depending on the final alumina concentration to be achieved. In particular, said second precipitation step makes it possible to obtain from 0 to 60% by weight of alumina in Al.sub.2 O.sub.3 equivalent relative to the total amount of alumina formed at the end of the two precipitation stages. Just 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 of between 0 and 60.degree. %.
[0039] Preferably, the rate of progress of said precipitation step a) is between 10 and 55% (3% and preferably between 15% and 55%), thus depending on the alumina concentration referred to at the end of the precipitation step (s), preferably between 20 and 100 g / l, the amounts of aluminum to be provided by the acid and / or basic precursors are calculated and the flow rate of the precursors is adjusted as a function of 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 rate of the acid precursor (s) and or basic containing aluminum depending on the size of the reactor used and thus the amount of water added to the reaction medium. For example, if one works in a reactor of 3 1 and that one aims at slurry of alumina with a final concentration of Al 2 O 3 of 50 g / l, the targeted rate of advancement is 50%. equivalent A1203 for the first precipitation stage. Thus, 50% of the total alumina must be provided during step a) of precipitation. The precursors of aluminas 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 second to 9. The amount of water added to the reactor is 622 ml.
[0040] For the first step a) of precipitation operating at 30 ° C. and for 8 minutes, the flow rate of aluminum sulphate should be 10.5 ml / min and the flow rate of sodium aluminate is 13.2 ml / min. The mass ratio of sodium aluminate to aluminum sulfate is therefore 1.91.
[0041] For the second precipitation stage, operating at 70 ° C., for 30 minutes, the flow rate of aluminum sulphate should be 2.9 ml / min and the sodium aluminate flow rate should be 3.5 ml / min. The mass ratio of sodium aluminate to aluminum sulfate is therefore 1.84.
[0042] 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.
[0043] 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. / 1.
[0044] In the case where said second precipitation step is carried out, said preparation process also advantageously comprises a second step of heating the suspension obtained at the end of said second precipitation step to a temperature of between 50 and 95 ° C. C and preferably between 60 and 90 ° C. Preferably, said second heating step is carried out for a period of between 7 and 45 minutes. Said second heating step is advantageously carried out according to all the heating methods known to those skilled in the art. Said second heating step makes it possible to increase the temperature of the reaction medium before subjecting the suspension obtained in step b) of heat treatment.
[0045] Filtration step c) According to the invention, the process for the preparation of alumina according to the invention also comprises a step c) of filtering the suspension obtained at the end of the heat treatment step b), followed by at least one washing step of the gel obtained. 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 step a) of precipitation or of the two precipitation steps is improved by the presence of said final heat treatment step b) of the suspension obtained, said heat treatment step favoring the The productivity of the preparation process as well as an extrapolation of the process at the industrial level. Said filtration step is advantageously followed by at least one washing step 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 steps a) b) and c) and optionally of the second precipitation step, the second heating step and the optional filtration step, makes it possible to obtain a specific alumina gel having a dispersibility number greater than 70%, a crystallite size of between 1 and 35 nm and a sulfur content of between 0.001% and 2% by weight and a sodium content of between 0.001% and 2% (3/0). weight, the percentages weight being expressed relative to the total mass of alumina gel.
[0046] The alumina gel thus obtained, also called boehmite, has a dispersibility index between 70 and 100%, preferably between 80 and 100%, very preferably between 85 and 100% and even more preferably between 90 and 100%. Preferably, the alumina gel thus obtained has a crystallite size of between 2 and 35 nm.
[0047] Preferably, the alumina gel thus obtained comprises a sulfur content of between 0.001% (3/0 and 1% by weight, more preferably between 0.001 and 0.40% by weight, very preferably between 0.003 and 0.33% by weight). (3/0 weight, and more preferably between 0.005 and 0.25 (3/0) weight.) Preferably, the alumina gel thus obtained comprises a sodium content of between 0.001 (3/0 and 1% by weight). , preferably between 0.001 and 0.15 (3/0 weight, very preferably between 0.0015 and 0.10% by weight, and 0.002 and 0.040% by weight.) In particular, the alumina gel or the boehmite under The powder form according to the invention is composed of crystallites whose size, obtained by the X-ray diffraction Scherrer formula in the crystallographic directions (020) and (120) are respectively between 2 and 20 nm and between 2 and Preferably, the alumina gel according to the invention has a crystallite size in the crystallographic direction. ique (020) between 1 to 15 nm and a crystallite size in the crystallographic direction (120) between 1 to 35 nm.
[0048] The X-ray diffraction on the alumina or boehmite gels was carried out 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. The alumina gel thus prepared and having a high degree of dispersibility 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 oil drop according to the English terminology. Step d) Drying In accordance with the invention, the alumina gel obtained at the end of step c) of filtration is dried in a drying step d) to obtain a powder. Said drying step is advantageously carried out at a temperature of between 20 and 50 ° C. and for a period of time ranging from 1 day to 3 weeks or by atomization.
[0049] In the case where said drying step d) is carried out at a temperature of between 20 and 50 ° C. and for a duration of between 1 day and 3 weeks, said drying step d) can advantageously be carried out in a closed oven and ventilated, preferably said drying step operates at a temperature between 25 and 40 ° C, and for a period of between 3 days and two weeks. In the case where said drying step d) is carried out by atomization, the cake obtained at the end of the heat treatment step optionally 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 in order to evaporate the water according to the principle well known to those skilled in the art. The powder obtained is driven by the heat flow to a cyclone or a bag filter that will separate the air from the powder. Preferably, in the case where said drying step d) is carried out by atomization, the atomization is carried out according to the operating protocol described in the Asep Bayu Dani Nandiyanto publication, Kikuo Okuyama, Advanced Powder Technology, 22, 1 In accordance with the invention, the powder obtained at the end of step d) of drying is shaped in a step e) 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 e) is carried out by extrusion kneading, by pelletizing, by the method of drop coagulation (oil-drop), by rotating plate granulation or by any other well-known method of the method. skilled person. In a very preferred manner, said shaping step e) is carried out by extrusion kneading.
[0050] Step f) of heat treatment According to the invention, the green material obtained at the end of the shaping step e) is then subjected to a heat treatment step f) at a temperature of between 500 and 1000 ° C. , for a period of between 2 and 10 h, in the presence or absence of air flow containing up to 60% water volume.
[0051] Preferably, said heat treating step f) operates at a temperature of between 540 ° C and 850 ° C. Preferably, said heat treatment step f) operates for a duration of between 2 h and 10 h.
[0052] Said heat treatment step f) allows the transition from boehmite to final alumina. The method for preparing the alumina used as a catalyst support used in the process according to the invention makes it possible to obtain an amorphous mesoporous alumina having a connectivity of greater than 2.7 and a controlled mesoporosity, said alumina exhibiting good thermal and chemical stability, having a centered, uniform and controlled mesopore size distribution, and a specific surface and a pore volume and in particular mesoporous calibrated.
[0053] The catalyst used in the hydrotreatment process according to the invention is then advantageously obtained by adding the elements constituting the active phase. The elements of group VIB and / or group VIII and optionally at least one doping element chosen from boron, silicon, fluorine and phosphorus and optionally the elements of groups IVB, or IB in the case where the active phase contains reduced nickel, and optionally at least one organic additive may be optionally introduced, in whole or in part, at any stage of the preparation, during the synthesis of the support, preferably during the shaping of the support, or very preferred after forming the support by any method known to those skilled in the art. They can be introduced after the shaping of the support and after or before the drying and calcination of the support and preferably after the calcination step of the shaped support. According to a preferred embodiment of the present invention, all or part of the elements of group VIB and / or of group VIII, and optionally at least one doping element chosen from boron, silicon and phosphorus and possibly elements of groups IVB, or IB in the case where the active phase contains reduced nickel, and optionally at least one organic additive, can be introduced during the shaping of the support, for example, during the kneading step extrusion of the dried powder obtained.
[0054] According to another preferred embodiment of the present invention, all or part of the elements of group VIB and / or group VIII and optionally at least one doping element chosen from boron, silicon and phosphorus and optionally the elements of groups IVB, or IB, in the case where the active phase contains reduced nickel, and possibly at least one organic additive, can be introduced by one or more impregnation operations of the shaped and calcined support by a solution containing the precursors of said elements. . In a preferred manner, the support is impregnated with an aqueous solution. The impregnation of the support is preferably carried out by the so-called "dry" impregnation method well known to those skilled in the art in which the quantity of desired elements in the form of soluble salts in the chosen solvent is introduced just by demineralised water, so as to fill as accurately as possible the porosity of the support. In the case where the catalyst used in the hydrotreatment process according to the present invention contains a non-noble group VIII metal, the Group VIII metals are preferably introduced by one or more impregnation operations of the shaped support and calcined, after those in group VIB or at the same time as these.
[0055] According to another preferred embodiment of the present invention, the deposition of Group IVB or Group IB elements can also be carried out simultaneously using, for example, a solution containing a tin salt or a copper salt.
[0056] According to another preferred embodiment of the present invention, the deposition of boron and silicon can also be carried out simultaneously using, for example, a solution containing a boron salt and a silicon-type silicon compound.
[0057] When at least one doping element, P and / or B and / or Si, is introduced, its distribution and location can be determined by techniques such as the Castaing microprobe (distribution profile of the various elements), microscopy transmission electron coupled to an EDX analysis (energy dispersive analysis) of the catalyst components, or even by establishing a mapping of the distribution of the elements present in the catalyst by electron microprobe. For example, among the sources of molybdenum and tungsten, it is possible to use oxides and hydroxides, molybdic and tungstic acids and their salts, in particular ammonium salts such as ammonium molybdate, ammonium heptamolybdate, ammonium tungstate, phosphomolybdic acid, phosphotungstic acid and their salts, silicomolybdic acid, silicotungstic acid and their salts. Oxides and ammonium salts such as ammonium molybdate, ammonium heptamolybdate and ammonium tungstate are preferably used.
[0058] Sources of non-noble group VIII elements that can be used are well known to those skilled in the art. For example, for non-noble metals, use will be made of nitrates, sulphates, hydroxides, phosphates, halides, for example chlorides, bromides and fluorides, carboxylates, for example acetates and carbonates.
[0059] The element (s) promoter (s) chosen (s) in the group formed by silicon, boron and phosphorus can advantageously be introduced by one or more impregnation operations with excess of solution on the calcined precursor. The boron source may advantageously be boric acid, preferably orthoboric acid H3B03, ammonium biborate or pentaborate, boron oxide, boric esters. Boron may for example be introduced in the form of a mixture of boric acid, hydrogen peroxide and a basic organic compound containing nitrogen such as ammonia, primary and secondary amines, cyclic amines. compounds of the family of pyridine and quinolines and compounds of the pyrrole family. Boron may be introduced for example by a boric acid solution in a water / alcohol mixture.
[0060] The preferred phosphorus source is orthophosphoric acid H 3 PO 4, but its salts and esters such as ammonium phosphates are also suitable. The phosphorus may for example be introduced in the form of a mixture of phosphoric acid and a basic organic compound containing nitrogen such as ammonia, primary and secondary amines, cyclic amines, compounds of the family of pyridine and quinolines and compounds of the pyrrole family. Many sources of silicon can advantageously be employed. Thus, it is possible to use ethyl orthosilicate Si (OEt) 4, siloxanes, polysiloxanes, silicones, silicone emulsions, halide silicates, such as ammonium fluorosilicate (NH4) 2SiF6 or fluorosilicate. sodium Na2SiF6. Silicomolybdic acid and its salts, silicotungstic acid and its salts can also be advantageously employed. Silicon may advantageously be added for example by impregnation of ethyl silicate in solution in a water / alcohol mixture. Silicon can be added, for example, by impregnating a silicon-type silicon compound or silicic acid suspended in water.
[0061] Group IB source materials that can be used are well known to those skilled in the art. For example, among copper sources, Cu (NO 3) 2 copper nitrate can be used. Sources of Group IVB elements that can be used are well known to those skilled in the art. For example, among tin sources tin chloride SnCl 2 can be used. The catalyst used in the hydrotreatment process according to the invention may advantageously be additive. In this case, at least one organic additive is added as defined above and preferably introduced into the impregnating solution containing the precursors of the active phase or in a subsequent impregnation step. The invention is illustrated by the following examples, which in no way present a limiting character.
[0062] Examples: Example 1: (Comparative) Preparation of a support AL-1 (non-conforming) according to US Pat. No. 7,790,562. First of all, the synthesis of a non-compliant alumina gel is carried out. in that Example 2 is carried out according to the preparation process described in U57790562. In particular, the process for preparing the alumina gel according to Example 2 does not include a heat treatment step of the suspension obtained at the end of the precipitation steps and in that the first precipitation step a) does not produce an amount of alumina greater than 40% equivalent A1203 relative to the total amount of alumina 10 formed at the end of the second precipitation step. 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 3868 ml. The final alumina concentration is 30g / L.
[0063] A first step of co-precipitating Al2 (504) aluminum sulphate and NaA100 sodium aluminate 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.
[0064] A solution of aluminum sulphate Al2 (504) is added continuously for 8 minutes at a flow rate of 19.6 ml / min to a sodium aluminate solution NaA100 in a mass 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.
[0065] 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 / ml. min and 23.3 ml / min. These flow rates of aluminum-containing acidic and basic precursors make it possible to obtain at the end of the first precipitation step an advancement rate 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 Al2 (504) at a concentration of 102 g / l in Al2O3 and sodium aluminate 32 Na2O3 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. sodium NaA100 in a mass basis / acid ratio = 1.68 to adjust the pH to 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. As the final concentration of alumina is 30 g / l, the flow rate of aluminum sulphate precursors Al 2 (SO 4) and aluminum aluminate NaAl 100 containing aluminum introduced in the second precipitation stage are respectively 12.8 ml / 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. The suspension thus obtained does not undergo a heat treatment or ripening step.
[0066] The suspension obtained is then filtered by displacement of water on a sintered Buchner type tool and the resulting alumina gel is washed 3 times with 5 L of distilled water at 70 ° C. Filtration time and washes are 4 hours.
[0067] The characteristics of the alumina gel thus obtained are summarized in Table 1. Table 1: Characteristics of the alumina gel obtained according to Example 1. Alumina gel according to Example 1 Dispersibility index Ta = 10 ° / 0 (° / 0) 60 Size (020) (nm) 2.9 Size (120) (nm) 4.1 Sodium Na (ppm) 0.011 S sulfur (ppm) 0.057 Filtration time 4 h 25 Alumina gel is then spray-dried with an inlet temperature of 250 ° C and an exit temperature of 130 ° C. 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 5 minutes, during mixing at 20 ° C. revolutions / min. The acid mixing is continued for 15 minutes. A neutralization step is then carried out by adding an ammoniacal solution in the kneader, at a neutralization rate of 50%, expressed by weight of ammonia relative to the amount of nitric acid introduced into the kneader for the first time. acidification step. The kneading is continued for 3 minutes.
[0068] 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. The characteristics of the alumina formed are reported in Table 2: Table 2: Characteristics of alumina AL-1 obtained according to Example 1.
[0069] AL-1 SBET (M21g) 230 VDEL = N2 (ml / g) 0.91 VPT (Hg) (ml / g) 0.78 Vmacro (Hg) (ml / g) 0.01Masos (Hg) (ml) g) 0.81V (d <6nm)% 43V (6 <d <15nm)% 55V (15 <d <50nm)% 1 2.5 Dp (Hg) (nm) 11.9 Example 2 ( according to the invention): Preparation of supports AL-2 and AL-3 (compliant). Firstly, the synthesis of two alumina supports AL-2 and AL-3 according to a preparation method according to the invention in a 7L reactor and a final suspension of 5L in 3 steps, two precipitation steps followed. a stage of ripening. The final alumina concentration is 45g / L. The amount of water added to the reactor is 3267 ml. The agitation is 350 rpm throughout the synthesis.
[0070] A first co-precipitation step in water, aluminum sulphate Al2 (SO4) and sodium aluminate NaA100 is carried out at 30 ° C and pH = 9.5 for a period of 8 minutes. The concentrations of the aluminum precursors used are as follows: Al 2 (SO 4) = 102 g / l in Al 2 O 3 and Naa 100 to 155 g / l in Al 2 O 3 A solution of aluminum sulphate Al 2 (SO 4) is added continuously for 8 minutes at a flow rate of 69.6 ml / min to a solution of sodium aluminate NaA100 at a flow rate of 84.5 ml / min in a basis / acid mass ratio = 1.84 so as to adjust the pH to a value of 9.5. The temperature of the reaction medium is maintained at 30 ° C. A suspension containing a precipitate of alumina is obtained.
[0071] The final concentration of alumina targeted being 45 g / l, the flow rate of aluminum sulphate precursors Al 2 (SO 4) and aluminum aluminate NaA 100 containing aluminum introduced in the first precipitation stage are respectively 69.6 ml. / min and 84.5 ml / min. These flow rates of aluminum-containing basic and basic precursors make it possible to obtain at the end of the first precipitation step an advancement rate of 72%. The resulting suspension is then subjected to a temperature rise of 30 to 68 ° C. A second step of co-precipitation of the suspension obtained is then carried out by adding aluminum sulphate Al 2 (SO 4) at a concentration of 102 g / l in Al 2 O 3 and sodium aluminate NaA 100 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 7.2 ml / min to an aluminate solution. of sodium NaA100 in a mass basis / acid ratio = 1.86 so as to adjust the pH to a value of 9. The temperature of the reaction medium in the second step is maintained at 68 ° C. A suspension containing a precipitate of alumina is obtained. As the final concentration of alumina is 45 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 7.2 ml / min. and 8.8 ml / min. These flow rates of acid and basic precursors containing aluminum make it possible to obtain at the end of the second precipitation stage a progress rate of 28%. The resulting suspension is then subjected to a temperature rise of 68 to 90 ° C.
[0072] The slurry then undergoes a heat treatment step in which it is held at 90 ° C for 60 minutes. 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. Filtration time 30 and washes is 3h. The characteristics of the alumina gel thus obtained are summarized in Table 3.
[0073] TABLE 3 Characteristics of the Alumina Gel Obtained According to Example 2. Alumina Gel According to Example 2 Dispersibility Index Ta = 10 ° / 0 (° / 0) 100 Size (020) (nm) 2 , 8 Size (120) (nm) 3.5 Sodium Na (° / 0) 0.074 S sulfur (° / 0) 0.0364 Filtration time 3h A gel having a dispersibility index of 100% is thus obtained.
[0074] The resulting alumina gel is then spray-dried with an inlet temperature of 250 ° C and an exit temperature of 130 ° C. The gel dried by atorreation is called Gel No. 1. The alumina gel obtained according to Example 3 was also dried in a ventilated study at 35 ° C. for 4 days. The dried gel in an oven is called Gel No. 2.
[0075] Dried alumina gels Nos. 1 and 2 are then respectively introduced into a Brabender-type kneader. 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 5 minutes during a 20-minute mixing. / min. The acid kneading is continued for 15 minutes. A neutralization step is then carried out by adding an ammoniacal solution in the kneader, at a neutralization rate of 50%, 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 resulting extrudates are dried at 100 ° C overnight and then calcined for 2 hours at 600 ° C. The characteristics of the aluminas AL-2 and AL-3 formed are shown in Table 4: Table 4: Characteristics of alumina AL-2 and AL-3 obtained according to Example 2. AL-2 AL-3 Type SBET drying (m2 / g) VPT (Hg) (ml / g) Vmacro (50-7000nm) (Hg) (ml / g) VmSo (Hg) (ml / g) V (2 <d <8nm)% V (8 <d <20nm) ") / 0 V (20 <d <50nm)% V (50 <d <7000nm)% Dp (nm) (Hg) Atomization 35 ° C 289 292 0.68 0.69 20 / 0 3% 0.71 0.73 26 21 61 64 3 4 2 3 6,5 6 9,7 9,8 5 Example 3: Preparation of catalysts Cl (non-compliant), C2 (compliant) and C3 (compliant) with AL-1, AL-2, and AL-3 alumina supports are respectively started from alumina supports AL-1, AL-2, AL-3, and which are in the form of extrudates. respectively the catalysts C1, C2, C3 by adding nickel, molybdenum and phosphorus The impregnating solution is prepared by hot dissolving molybdenum oxide (21.5 g) and nickel hydroxide (5 , 4g) in the phosphonic acid solution orique (8.2 g) in aqueous solution. After dry impregnation of the supports AL-1, AL-2, AL-3 the extrudates are allowed to mature in an atmosphere saturated with water for 12 hours, then they are dried overnight at 90 ° C. Calcination of the catalytic precursor at 450 ° C. for 2 h respectively leads to calcined catalysts C1, C2 and C3. The final composition of catalysts C1, C2, and C3 expressed as oxides is then: MoO3 = 21.5 +/- 0.2 (wt%), NiO = 4.3 +/- 0.1 (w / w%) and P205 = 5.0 +/- 0.1 (w / w). The porous distribution of the catalysts is shown in Table 5.
[0076] Table 5: Porous Distribution of Catalysts Cl, 02 and 03 Cl 02 03 Porous Distribution (° / oVPT) (° / oVPT) (° / oVPT) d <8 nm 44 29 24 8 <d <21 nm 54 58 61 21 <d <50 nm 1 3 4 50 <d <7000 nm 1 2 3 VmSo (mL / g) 0.38 0.39 0.40 Vmacro (mL / g) 0.01 0.02 0.02 Dp at Vmso / 2 (nm) (Hg) 11.3 9.6 9.7 Z 2.5 6.5 6.0 Example 4: Preparation of Catalysts Cl '(non-compliant), 02' (compliant) and 03 5 (compliant) respectively from the alumina supports AL-1, AL-2, and AL-3. Starting from the alumina supports AL-1, AL-2, and AL-3, which are in the form of extrudates, the catalysts Cl ', 02' and 03 'are respectively prepared by adding nickel, cobalt, molybdenum and phosphorus. The impregnating solution is prepared by hot dissolving molybdenum oxide (18.0 g), cobalt carbonate (4.95 g) and nickel hydroxide (1.3 g) in the acid solution. phosphoric acid (8.1 g) in aqueous solution. After dry impregnation of the supports AL-1, AL-2, and AL-3 the extrudates are allowed to mature in an atmosphere saturated with water for 12 hours, then they are dried overnight at 90 ° C. The calcination of the catalytic precursor at 450 ° C. for 2 hours respectively leads to the calcined catalysts Cl ', O 2' and O 3 "The final composition of the catalysts Cl ', O 2' and O 3 'expressed in the form of oxides is then the following Mo03 = 18.0 +/- 0.2 (wt%), NiO = 1.0 +/- 0.1 (wt%), Co ° = 3.1 +/- 0, 1 (wt%) and P205 = 4.9 +/- 0.1 (wt%) The porous distribution of the catalysts is shown in Table 6. Table 6: Porous distribution of catalysts Cl ', O 2' and 03 'Cl' 02 '03' Porous distribution (° / oVPT) (° / oVPT) (° / oVPT) d <8 nm 44 28 23 8 <d <21 nm 54 59 62 21 <d <50 nm 1 3 4 50 <d <7000 nm 1 2 3 Vmeso (mL / g) 0.46 0.43 0.42 Vmacro (mL / g) 0.01 0.02 0.02 Dp (nm) (Hg) 11.3 9.6 9.7 Z 2.5 6.5 6.0 20 38 3022255 Example 5: Evaluation of the Catalytic Performance of Catalysts Cl, 02 and 03 in Live Load Tests in the Case of a Hydrotreatment Process a vacuum distillate charge (DSV) placed upstream of a The catalysts Cl (non-compliant), O2 (compliant), and O3 (compliant) previously described were compared in hydrotreating of a vacuum distillate cut. Catalysts C1, O2 and O3 are previously sulphurized, using a straight run diesel filler (density 0.863 g / cm3, 1200 ppm organic sulfur, 140 ppm nitrogen), with a 4% additive. of DMDS evolution®. The flow rate of said feedstock at the reactor inlet is 18 cm3 / h (at 15 ° C.), the flow rate of hydrogen at the reactor inlet is 19.8 NL / h, and the pressure is 140 bar (14 MPa). ) output. The reactor is also subjected to a rise in temperature under liquid and gas flow from ambient temperature to 350 ° C. at a rate of 12 ° C./h (6 hour stage at 350 ° C.).
[0077] Test conditions The feed used is a vacuum distillate and has a TMP of 474 ° C (T 5% = 389 ° C, T 50% = 468 ° C, T 70% = 498 ° C), density 0.9355 g mL at 15 ° C containing 2.23% sulfur, 1750 ppm nitrogen including 500 ppm basic nitrogen, and refractive index 1.5004. The boiling temperatures of 5% of the feed is 370 ° C and 550 ° C for 95% of the feed. The catalyst test is carried out at reaction temperatures of 370 ° C., 380 ° C. and 390 ° C. after the catalysts are sulphurized. The feedstock flow at the reactor inlet is 18 cm3 / h (at 15 ° C.), the flow rate of hydrogen at the reactor inlet is 19.8 NL / h and the pressure is 140 bar (14 MPa) in exit. The test is carried out in a pilot reactor of 9 ml of catalyst. After stabilizing the reactor for about 150 hours at 370 ° C., the activity measurements are carried out at 380 ° C. and 390 ° C. in a steady state (for 100 hours). The effluents are analyzed in terms of organic nitrogen contents, density, refractive index and simulated distillation. The aromatic carbon values are obtained with the ASTM method 3238-95 called n-d-M.
[0078] Table 7: Catalytic Test Results Organic Nitrogen (ppm) Aromatic Carbon (°) / 0) 370 ° C 380 ° C 390 ° C 370 ° C 380 ° C 390 ° C Cl no 304 145 50 10.2 9 , 8.3.3 compliant 220 87 22 10.0 8.9 7.8 C2 compliant C3 232 91 27 10.1 9.0 7.9 compliant Table 7 shows that, surprisingly, catalysts C2 and C3 comply with the invention are more active than the catalyst C1 (non-compliant). The table shows that with the use of the catalyst C2 or the catalyst C3, at the same test temperature, the amount of organic nitrogen in the effluents is lower than when using the catalyst Cl, and therefore that the catalysts C2 and C3 are more active in vacuum distillate hydrodenitrogenation than the catalyst C1. The table also shows that at the same test temperature the effluents from the catalyst C2 or catalyst C3 test contain a lower proportion of aromatic carbon than when using catalyst C1, and therefore that catalysts C2 and C3 are more active in vacuum distillate hydrogenation than catalyst C1. EXAMPLE 6 Evaluation of the Catalytic Performance of Cl ', C2' and C3 'Catalysts 15 tests on real charges in the case of a process for hydrotreating a vacuum distillate feedstock (DSV) placed upstream of a fluidized catalytic cracking unit. Catalysts Cl '(non-compliant), C2' (compliant), and C3 '(compliant) previously described were compared in hydrotreating of a vacuum distillate cut. Catalysts C1, C2 and C3 are previously sulphurized, using a straight run diesel filler (density 0.863 g / cm3, 1200 ppm organic sulfur, 140 ppm nitrogen), additive of 4% of DMDS evolution®. The feed rate at the inlet of the reactor is 9 cm3 / h (at 15 ° C.), the flow rate of hydrogen at the reactor inlet is 2.25 NL / h, and the pressure is 65 bar (6.5 MPa) at the output. The reactor is also subjected to a temperature rise in liquid and gas flow from ambient temperature to 350 ° C. at a rate of 12 ° C./h (6 hour stage at 350 ° C.).
[0079] 3022255 Test conditions The feed used is a vacuum distillate and has a TMP of 474 ° C (T5% = 389 ° C, T50% = 468 ° C, T70 ° / 0 = 498 ° C), density 0.9355. g / mL at 15 ° C containing 2.23% sulfur, 1750 ppm nitrogen including 500 ppm basic nitrogen, and refractive index 1.5004. The boiling temperatures of 5% of the feed is 370 ° C and 550 ° C for 95% of the feed. The catalysts are tested at reaction temperatures of 360 ° C., 375 ° C. and 390 ° C. after the catalysts are sulphurized. Flow rate cb reactor inlet charge of 9 cm3 / h (at 15 ° C), hydrogen flow rate at the reactant inlet of 2.25 NL / h, pressure of 65 bars (6.5 MPa) at the outlet. The test is carried out in a pilot reactor of 9 ml of catalyst. After stabilization of the reactor for about 150 hours at 360 ° C., the activity measurements are carried out at 375 ° C. and 390 ° C. under steady state conditions (for 100 hours). The effluents are analyzed in terms of sulfur and nitrogen contents. residual organic compounds in the effluents. Table 8: Results of catalytic tests Organic sulfur (ppm) Organic nitrogen (ppm) 360 ° C 375 ° C 390 ° C 360 ° C 375 ° C 390 ° C Cl no 990 374 120 809 575 360 compliant 820 294 91 743 515 302 According to Table 8, surprisingly, the catalyst C2 '(in accordance with the invention) and the catalyst C3' (in accordance with the invention) are more active than the Catalyst Cl '(non-compliant). The table shows that at the same test temperature, the amount of organic sulfur in the effluents of the C2 'and C3' catalyst test is lower than when using the catalyst Cl ', and therefore that the catalysts C2' and C3 are more active in vacuum distillate hydrodesulphurization than the catalyst Cl '. The table also shows that at the same test temperature, the effluents from the C2 'catalyst test or the C3' catalyst test contain a lower proportion of organic nitrogen than when the catalyst Cl 'is used, and therefore that the catalysts C2 'and C3' are more active in vacuum distillate hydrodenitrogenation than the catalyst Cl '. 25 41

权利要求:
Claims (14)
[0001]
REVENDICATIONS1. Process for the hydrotreatment of at least one hydrocarbon feedstock having a weighted average temperature (TMP) greater than 380 ° C using at least one catalyst comprising at least one Group VIB metal and / or at least one Group VIII metal and a support comprising an amorphous mesoporous alumina having a connectivity (Z) greater than 2.7, the connectivity being determined from the nitrogen adsorption / desorption isotherms, said hydrotreatment process operating at a temperature of between 250 C. and 430 ° C., at a total pressure of between 4 MPa and 20 MPa, with a ratio of volume of hydrogen per volume of hydrocarbon feedstock of between 200 and 2000 liters per liter and at a fixed hourly volume velocity (VVH) defined by the ratio of the volume flow rate of the liquid hydrocarbon feedstock by the volume of catalyst charged to the reactor between 0.5 and 5 h -1.
[0002]
2. Method according to claim 1 wherein said hydrocarbon feedstock is selected from vacuum distillates, effluents from a catalytic cracking unit FOC, light gas oils from a catalytic cracking unit, heavy cutting oils, paraffinic effluents from Fischer-Tropsch synthesis, effluents from vacuum distillation, effluents from the coal liquefaction process, biomass feedstocks or effluents from the conversion of feedstock from biomass, and aromatic extracts and fillers from aromatics extraction units, alone or in admixture.
[0003]
3. Method according to one of claims 1 or 2 wherein the group VIII elements are selected from cobalt and nickel, alone or in mixture.
[0004]
4. Method according to one of claims 1 to 3 wherein the Group VIB elements are selected from tungsten and molybdenum, alone or in mixture.
[0005]
5. Method according to one of claims 1 to 4 wherein the catalyst support comprises an amorphous mesoporous alumina having a connectivity (Z) between 3 and 7. 42 3022255
[0006]
6. Method according to one of claims 1 to 5 wherein said hydrotreatment process according to the invention is carried out upstream of a hydrocracking unit of said hydrocarbon feedstock. 5
[0007]
7. The method of claim 6 wherein said hydrotreatment process operates at a temperature between 350 and 430 ° C, at a total preoeion of between 8 MPa and 20 MPa with a volume ratio of hydrogen per volume of hydrocarbon feedstock included between 200 and 2000 liters per liter and at a Time Volumetric Velocity (VVH) defined by the ratio of the volume flow rate of liquid hydrocarbon feedstock by the volume of catalyst loaded in the reactor between 0.5 and 5 h-1.
[0008]
8. Method according to one of claims 1 to 5 wherein said hydrotreatment process according to the invention is carried out upstream of a fluidized catalytic cracking unit fluidized bed of said hydrocarbon feedstock. 15
[0009]
9. The method of claim 8 wherein said hydrotreating process operates at a temperature between 250 and 420 ° C, at a total preoeion of between 4 MPa and 15 MPa with a volume ratio of hydrogen per volume of hydrocarbon feedstock included between 200 and 2000 liters per liter and at a Hourly Volumetric Velocity (VVH) defined by the ratio of the volume flow rate of the liquid hydrocarbon feedstock to the volume of catalyst charged to the reactor between 0.5 and 5 h -1.
[0010]
10. Process according to one of claims 1 to 9 wherein the support used in the catalyst has the following porous distribution, measured by mercury porosimetry, the percentage of volume included in the pores of size between 2 and 8 nm relative to at the total pore volume, is between 20 and 40%, the percentage of volume included in the pores with a size of between 8 and 20 nm relative to the total pore volume is between 50 and 65%, the percentage of volume included in the pores of size between 20 and 50 nm relative to the total pore volume, is less than 10%, the percentage of volume included in the pore size between 50 and 7000 nm relative to the total pore volume, is less than 10%, and preferably less than 6%. 43 3022255
[0011]
11. Method according to one of claims 1 to 10 wherein said alumina has a mesoporous volume measured by mercury porosimetry, between 0.6 and 0.8 ml / g.
[0012]
12. A method according to one of claims 1 to 11 wherein said catalyst has the following porous distribution determined by mercury prosimeter: the percentage of volume included in the pores less than 8 nm in size relative to the total pore volume, is between 20 and 40%, the percentage of volume included in the pores between 8 and 20 nm in size relative to the total pore volume is between 40 and 65%, the percentage of volume included in the pores of size between 20 and 50 nm relative to the total pore volume, is less than 10%, the percentage of volume included in the pore size between 50 and 7000 nm relative to the total pore volume, is less than 10%, and preferably less than 5%. 15
[0013]
13. Method according to one of claims 1 to 12 wherein said catalyst has a mesoporous volume measured by mercury porosimetry between 0.1 and 0.6 ml / g.
[0014]
14. Process for the hydrotreatment of at least one hydrocarbon feed having a weighted average temperature (TMP) greater than 380 ° C., operating at a temperature of between 250 ° C. and 430 ° C., at a total pressure of between 4 MPa and 20 MPa with a ratio volume of hydrogen per volume of hydrocarbon feedstock of between 200 and 2000 liters per liter and at a Hourly Volumetric Velocity (VVH) defined by the ratio of the volume flow rate of liquid hydrocarbon feedstock by the volume of catalyst charged in the reactor is between 0.5 and 5 h -1, said process using at least one catalyst comprising at least one Group VIB metal and / or at least one Group VIII metal of the Periodic Table and a carrier comprising a mesoporous alumina amorphous, said alumina being prepared according to at least the following steps: a) at least a first step a) of precipitation of alumina, in an aqueous reaction medium, of at least one precursor alkali metal selected from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide and at least one acidic precursor selected from aluminum sulfate, sodium chloride, aluminum, 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 44 3022255 precursors acid and basic is selected 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 degree of progress of the first step being between 40 and 100%, the advancement rate being defined as the proportion of alumina formed in Al 2 O 3 equivalent during said step a) of precipitation with respect to the total amount of alumina formed in after the precipitation stage (s), ladi step a) operating at a temperature between 10 and 50 ° C, and for a period of between 2 minutes and 30 minutes, b) a heat treatment step of the suspension obtained at the end of step a) to a temperature of between 50 and 200 ° C. for a duration of between 30 minutes and 5 hours; and c) a filtration step of the suspension obtained at the end of the heat treatment step b), followed by at least one washing step of the gel obtained, d) a step of drying the alumina gel obtained at the end of step c) to obtain a powder, e) a step of shaping the powder obtained at the from step d) to obtain the raw material, f) a step of heat treatment of the green material obtained at the end of step e) at a temperature of between 500 and 1000 ° C., in the presence or absence of a stream of air containing up to 60% by volume of water.

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US10392570B2|2019-08-27|

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EP3155073B1|2018-10-10|

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RU2017100963A3|2018-12-11|

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CN107155331B|2019-04-02|

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FR3022255B1|2016-07-29|

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JP2017523264A|2017-08-17|

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WO2015189200A1|2015-12-17|

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DK3155073T3|2019-02-04|

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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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FR1455425A|FR3022255B1|2014-06-13|2014-06-13|PROCESS FOR HYDROPROCESSING DISTILLATE CUTTINGS USING A CATALYST BASED ON AMORPHOUS AMORPHOUS ALUMINA HAVING HIGH CONNECTIVITY|FR1455425A| FR3022255B1|2014-06-13|2014-06-13|PROCESS FOR HYDROPROCESSING DISTILLATE CUTTINGS USING A CATALYST BASED ON AMORPHOUS AMORPHOUS ALUMINA HAVING HIGH CONNECTIVITY|

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US15/318,598| US10392570B2|2014-06-13|2015-06-09|Method for the hydrotreatment of distillate cuts using a catalyst made from an amorphous mesoporous alumina having high connectivity|

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CN201580043461.XA| CN107155331B|2014-06-13|2015-06-09|Carry out the method for hydrotreating distillate fraction using the catalyst containing the amorphous mesoporous aluminas substrate with high connectivity|

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BR112016028805A| BR112016028805A2|2014-06-13|2015-06-09|hydrotreating process of distilled cuts using a catalyst based on an amorphous mesoporous alumina having high connectivity|

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EP15726640.4A| EP3155073B1|2014-06-13|2015-06-09|Method for the hydrotreatment of distillate cuts using a catalyst made from an amorphous mesoporous alumina having high connectivity|

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JP2016572404A| JP6643261B2|2014-06-13|2015-06-09|Hydrotreating process of distillation fraction using catalyst produced from amorphous mesoporous alumina with high connectivity|

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PCT/EP2015/062826| WO2015189200A1|2014-06-13|2015-06-09|Method for the hydrotreatment of distillate cuts using a catalyst made from an amorphous mesoporous alumina having high connectivity|

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RU2017100963A| RU2690843C2|2014-06-13|2015-06-09|Method for hydrotreatment of distillate fractions using catalyst based on amorphous mesoporous aluminium oxide having high coherence of structure|

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DK15726640.4T| DK3155073T3|2014-06-13|2015-06-09|METHOD FOR HYDROGEN TREATMENT OF DISTILLATION FRACTIONS USING A CATALYST BASED ON A HIGH CONNECTIVITY OF AMORFT MESOPOROUS ALUMINA|

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SA516380453A| SA516380453B1|2014-06-13|2016-12-08|Method for the Hydrotreatment of Distillate Cuts|