METHOD OF HYDROPROCESSING GAS CUTTINGS USING A CATALYST BASED ON AMORPHOUS AMORPHOUS ALUMINA HAVING

专利摘要:
A process for the hydrotreatment of at least one gas oil fraction having a weighted average temperature (TMP) of between 240 ° C and 350 ° C using a catalyst comprising at least one Group VIB metal and / or at least one metal of the same is described. group VIII 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 400 ° C, at a total pressure of between 2 MPa and 10 MPa with a ratio of volume of hydrogen per volume of hydrocarbon feedstock of between 100 and 800 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 loaded into the reactor between 1 and 10 h -1.
公开号:FR3022254A1
申请号:FR1455424
申请日:2014-06-13
公开日:2015-12-18
发明作者:Malika Boualleg；Elodie Devers；Bertrand Guichard
申请人:IFP Energies Nouvelles IFPEN；
IPC主号:

专利说明:

[0001] FIELD OF THE INVENTION The present invention relates to the field of hydrotreatments of hydrocarbon feedstocks of the diesel type.
[0002] It mainly relates to the use of a catalyst based on a specific alumina in processes for the hydrotreatment of diesel type feeds. In particular, the present invention relates to the use in a hydrotreatment process of at least one gas oil fraction having a weighted average temperature (TMP) of between 240 ° C. and 350 ° 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 aluminas 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 A1203 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 The tightening of automobile pollution standards in 2009 in the European community forces refiners to very strongly reduce the sulfur content in gas oils and gasolines, to a maximum of 10 parts per million weight (ppm) of sulfur in the European Community. diesel fuel as of January 1, 2009, compared to 50 ppm as of January 1, 2005 (measured by the ASTM D-4294 method). These constraints result in a need for new refining units or a sharp increase in the iso-volume activity of the hydrotreatment catalysts. These new constraints will also lead to an increased need for hydrogen in the refinery, necessary for the hydrodesulphurization, hydrodenitrogenation and hydrodearomatization reactions. On the other hand, these new standards are also accompanied by constraints in terms of product quality. Thus, the gas oils must have a good cetane number. The hydrotreatment reactions of gas oils 5 also result in the hydrogenation of aromatic rings contained in said diesel fuel cuts, which has the consequence of improving the cetane number of said final diesel fuel cut. The increase in the hydrotreating performance of the gas oil cuts may be partly due to the choice of the process, but in all cases the use of an inherently more active catalyst system is very often a key factor. Thus, new techniques for preparing hydrotreatment catalysts need to be developed to further improve the performance of these catalysts and meet future legislation.
[0003] In general, it is accepted that a hydrotreatment catalyst having a high catalytic potential is characterized by an optimized hydrogenating function, that is to say an active phase which is perfectly dispersed on the surface of the support and has 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 constraints. specific 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 BS Clausen article. , HT Topsoe, FE 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 can be in mass form or in the supported state then 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 of the 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, this is called in-situ sulphurization, or prior to the loading of the catalyst into the unit, this is called ex-situ sulphurization. The usual methods leading to the formation of the active phase of the hydrotreatment catalysts consist of a deposition of 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 steps of maturation, drying and possibly calcination leading to the formation of the so-called oxidized form of the said metal (s) used (s). Then comes the final stage of sulfuration generating the active phase as mentioned above.
[0004] 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 than 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 greater than 343 ° C. In particular, the heavy-lift hydroconversion process according to US Pat. No. 7,790,652 makes it possible to obtain a conversion of hydrocarbon compounds boiling at a temperature above 524 ° C. which is greatly improved compared to conversions obtained with conventional catalysts of the invention. prior art.
[0005] 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 which make it possible to obtain a dispersion containing the desired amount of water. 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 methods known to those skilled in the art, without prior heat treatment step, to produce an alumina powder which is then shaped according to the known methods of the invention. 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.
[0006] The Applicant has therefore demonstrated that 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 specific porous distribution as well as a very high connectivity, had an improved catalytic activity compared to conventional hydrotreating gas oil catalysts, said catalyst being sulfurized and then used in a process for hydrotreating at least one gas oil cut according to the invention.
[0007] In particular, the process according to the invention allows a better activity in hydrodesulphurization that is to say a lower processing temperature than the catalysts of the prior art for a given level of sulfur in the effluent. . In practice, the use of the catalyst according to the invention may also allow refiners to desulphurize a greater proportion of diesel fuel resulting from conversion processes (LCO for light cycle oil according to the English terminology, coker ...). The object of the present invention is to provide a process for the hydrotreatment of at least one diesel fuel cut using a catalyst having improved catalytic performance, especially in terms of hydrodesulfurization and hydrodenitrogenation of the treated sections. Another object of the present invention is to provide a process for the hydrotreatment of at least one gas oil cut using a catalyst having improved catalytic performance, said method making it possible to obtain an increased hydrodesulphurizing activity. SUMMARY AND INTEREST OF THE INVENTION The present invention relates to a process for the hydrotreatment of at least one gas oil fraction having a weighted average temperature (TMP) of between 240 ° C. and 350 ° C., using a catalyst comprising at least a 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 connectivity (Z) greater than 2.7, the connectivity being determined from the adsorption isotherms nitrogen desorption, said hydrotreatment process operating at a temperature of between 250 ° C. and 400 ° C., at a total pressure of between 2 MPa and 10 MPa, with a ratio by volume of hydrogen per volume of hydrocarbon feedstock included, between 100 and 800 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 catalyst charged in the reaction ur between 1 and 10 h-1.
[0008] One of the advantages of the present invention lies in the implementation, in a process for the hydrotreatment of at least one gas oil cut, of a catalyst based on a support comprising an alumina whose porosity is very closely connected, that is, having a very large number of adjacent pores. High connectivity represents an important advantage for the diffusion of the molecules of the gas oil fraction to be treated during the implementation of the hydrotreatment process according to the invention using this material and during the preparation of the catalyst, in particular during the preparation of the catalyst. impregnation of metal solutions with high metal concentrations.
[0009] An advantage of the present invention is therefore to provide a process using a catalyst comprising a specific support for obtaining an improved hydrodesulfurization activity compared to the catalysts of the prior art. Another subject of the invention is also a process for the hydrotreatment of at least one gas oil fraction having a weighted average temperature (TMP) of between 240 ° C. and 350 ° C., operating at a temperature of between 250 ° C. and At 400 ° C., at a total pressure of between 2 MPa and 10 MPa with a ratio of volume of hydrogen per volume of hydrocarbon feedstock of between 100 and 800 liters per liter and at a rate per hour volume (VVH) defined by the ratio of the flow rate volume of liquid hydrocarbon feedstock by the volume of catalyst charged to the reactor between 1 and 10 h -1, said process using at least one catalyst comprising at least one Group VIB metal and / or at least one Group VIII metal the periodic 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 precipitation of alumina, in a 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 the group consisting of 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 to obtain a forwarding rate of the first step of between 40 and 100%, the rate of progress being defined as the proportion of alumina formed in A1203 equivalent during said step a) of precipitation with respect to the total quantity of alumina formed at the end of 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, 7 3022254 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 a gel of alumina, 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 gel of alumina obtained at the end 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 raw material obtained at the end of step e) at a temperature of 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 new 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 even prepared from a precipitation step in which at least 40% by weight of alumina equivalent A1203 with respect to the total amount of alumina formed at the end of said process for preparing the gel, are formed from the first stage precipitation. This process is carried out by virtue of the implementation of a heat treatment step and in particular a calcination step making 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 (%).
[0010] 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.
[0011] "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.
[0012] 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 intruder porosimeter intrusion. mercury measured on the same sample for a pressure corresponding to 30 psi (about 0.2 MPa).
[0013] 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. The mesoporous volume of the catalyst is defined as the cumulative volume of mercury introduced at a pressure of between 30 MPa and 400 MPa, corresponding to the volume contained in the pores with an apparent diameter of between 2 and 50 nm. The micropore volume is measured by nitrogen porosimetry. The quantitative analysis of the microporosity is carried out using the "t" method (Lippens-De Boer method, 1965) which corresponds to a transformation of the starting adsorption isotherm as described in the book "Adsorption". by powders and porous solids. Principles, methodology and applications "written by F. Rouquerol, J. Rouquerol and K. Sing, Academic Press, 1999. The median diameter of the mesopores (Dp in nm) is also defined as a diameter such that all size pores less than this diameter constitute 50% of the mesoporous volume, measured by mercury porosimetry. 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, the volume measured for P / Po = 0.99, pressure for which it is assumed that nitrogen has filled all the pores.
[0014] In the following description of the invention, the term "specific surface" means the specific surface area B.E.T. determined by nitrogen adsorption according to ASTM D 3663-78 established from the BRUNAUER-EMMETT-TELLER method described in the journal "The Journal of the American Society", 60, 309, (1938).
[0015] In the following, groups of chemical elements are given according to the CAS classification (CRC Handbook of Chemistry and Physics, publisher CRC Press, editor-in-chief D. R. Lide, 81st edition, 2000-2001). For example, group VIII according to the CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IUPAC classification.
[0016] DESCRIPTION OF THE INVENTION The invention relates to a hydrotreatment process and in particular to the hydrodesulfurization of at least one diesel fuel cut having a weighted average temperature (TMP) of between 240 ° C. and 350 ° C. The TMP is defined from the temperature at which 5%, 50% and 70% of the volume of the batch 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 treated hydrocarbon feedstock generally has a distillation range between 150 ° C and 500 ° C, preferably between 180 and 450 ° C. In the remainder of the text, we will conventionally call this diesel charge, but this designation has no restrictive character. Any sulfur-containing hydrocarbon feedstock and nitrogen compounds that inhibit hydrotreatment, and a TMP similar to that of a diesel fuel cut may be concerned by the process that is the subject of the present invention. The hydrocarbon feed may be of any chemical nature, that is to say have any distribution between the different chemical families including paraffins, olefins, naphthenes and aromatics. Charges The feedstock used in the hydrotreatment process according to the invention is a diesel fuel cutter containing sulfur. The sulfur content in the filler is generally less than 5% by weight, preferably between 0.2 and 4% by weight and even more preferably between 0.25 and 3% by weight.
[0017] The total (neutral and basic) nitrogen content in the feed is greater than or equal to 50 ppm, preferably it is between 200 and 6000 ppm by weight, more preferably between 300 and 4000 ppm by weight and even more so. preferred between 400 and 4000 ppm. The basic nitrogen content has at least one third of the overall nitrogen content.
[0018] The basic nitrogen content is generally greater than or equal to 10 ppm, more preferably between 65 and 2000 ppm by weight and even more preferably between 100 and 2000 ppm. The treated filler generally contains very few resins, the resin content is generally less than 1 wt%.
[0019] The gasoil cuts used in the process according to the invention are advantageously chosen from diesel fuel cuts resulting from straight-run distillation (or straight run gas oil according to the English terminology) alone or in admixture with at least one cut resulting from a coking unit (coking according to the Anglo-Saxon terminology), or at least one cut resulting from catalytic cracking (Fluid Catalytic Cracking according to the English terminology) or at least one diesel cut from other conversion processes such as as mild hydrocracking or hydrotreating of residues. The gasoil cuts used in the process according to the invention are cuts in which at least 90% of the compounds advantageously have a boiling point of between 250 ° C. and 400 ° C. According to the invention, the process for hydrotreatment or hydrodesulphurization of at least one gas oil cut according to the invention is carried out at a temperature of between 250 ° C. and 400 ° C., preferably between 320 ° C. and 380 ° C a total pressure of between 2 MPa and 10 MPa and preferably between 3 MPa and 9 MPa with a volume ratio of hydrogen per volume of hydrocarbon feedstock of between 100 and 800 liters per liter and preferably between 200 and 400 liters per liter and at a Time Volumetric 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 of between 1 and 10 h -1, and preferably between 2 and 8 h -1.
[0020] In accordance with the invention, the catalyst used in said hydrotreatment or hydrodesulphurization process comprises at least one Group VIB metal and / or at least one Group VIII metal of the Periodic Table and a support comprising and preferably 3022254 consisting of an amorphous mesoporous alumina having a connectivity (Z) greater than 2.7, the connectivity of said alumina being determined from the nitrogen adsorption / desorption isotherms.
[0021] The catalyst used in the present invention also has a connectivity (Z), determined from nitrogen adsorption / desorption isotherms, preferably greater than 2.7 and preferably from 2.7 to 10, most 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 of said catalyst being determined from the isotherms adsorption / desorption of nitrogen. Preferably, the group VIII elements are chosen 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 mixed. 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, nickel, iron, and preferably from cobalt and nickel, taken alone or in mixture. Preferably, Group VIB elements are selected from tungsten and molybdenum, alone or in admixture. 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 sulfurized form. The metal contents to be followed are expressed in their oxide equivalent form in the case where the dosage would not be X-ray fluorescence on the solid which would have been calcined, although the catalyst could be calcined or not before sulphurization. In the case where said 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 10 and 35% by weight of oxide relative to the total mass of said catalyst, preferably between 15 and 30% by weight of oxide and very preferably between 18 and 25% by weight of oxide and the non-noble metal content of group VIII is advantageously between 1 and 10% by weight of oxide based on the total weight of said catalyst, preferably between 1.5 and 8% by weight of oxide and very preferably between 2 and 6% by weight of oxide. The molar ratio of the metals (ux) of the group VIII relative to the metal (ux) of the group VIB in the oxide catalyst is preferably between 0.1: 1.0 and 0.8: 1.0, very preferably between 0 , 2: 1.0 and 0.6: 1.0, and even more preferably between 0.3: 1.0 and 0.5: 1.0.
[0022] 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 or boron. When the catalyst contains phosphorus, the phosphorus content in said oxide catalyst is preferably 0.5 to 15% by weight of P205, more preferably 1 to 10% by weight of P205, very preferably Preferably, the amount of phosphorus is also advantageously chosen so that the molar ratio of phosphorus to molybdenum is between 0.1: 1.0 and 0.8: 1, And most preferably between 0.2: 1.0 and 0.6: 1.0.
[0023] When the catalyst contains boron, the boron content in said oxide catalyst is preferably between 0.2 and 8 weight percent B 2 O 3, more preferably between 0.5 and 5 weight percent. B203, very preferably between 1 and 4 (3/0 weight of B203.) The boron content is also advantageously chosen so that the molar ratio of boron to molybdenum is between 0.1: 1.0 and 0. , 8: 1.0, and most preferably between 0.2: 1.0 and 0.6: 1.0. When the catalyst contains silicon, the silicon content in said oxide catalyst is preferably in the range from 0 to 1.0. , 5 and 30 (3/0 weight of SiO 2, more preferably 3 to 10 (3/0 weight of SiO 2.) When the catalyst contains fluorine, the fluorine content in said oxide catalyst is preferably in the range from 0 to 10 weight percent. , 5 and 5 (3/0 weight, more preferably between 1 and 3 (3/0 weight.) Preferably, the catalyst used in the process according to the invention comprises nd a support comprising and is preferably constituted by an amorphous mesoporous alumina, said alumina being prepared according to the invention.
[0024] Preferably, the catalyst support used in the present invention comprises and is preferably composed of an amorphous mesoporous alumina having a connectivity (Z) of between 2.7 and 10, preferably of 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 alumina used as support in the catalyst used according to the present invention is an alumina controlled mesoporous mesoporous having good thermal and chemical stability, having a centric, uniform and controlled mesopore size distribution. Said alumina 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 the hydrotreatment of at least one diesel fuel cut.
[0025] Said alumina used as support in the catalyst used in the process according to the present invention and the support of the catalyst advantageously have a specific porous distribution. Preferably, the mesoporous alumina is devoid of micropores. Preferably, the mesoporous support comprising said alumina is devoid of 20 micropores. Preferably, said alumina and said support comprising said alumina have the following porous distribution, measured by mercury porosimetry, the percentage of volume comprised in the pores between 2 and 6 nm in size, relative to the total pore volume, is between 1 and 25%, the percent of volume included in the pores of sizes greater than 6 nm and less than 15 nm represents between 60 and 95% of the total pore volume, the percentage of volume included in the pores of size between 15 and 50 nm represents 0 to 8 (3/0 of the total pore volume and the percentage of volume included in the pore size between 50 and 7000 nm which corresponds to the macroporous volume represents 0 to 5 (3/0, preferably 0 to 2% of the total pore volume.
[0026] 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 7 and 12.5 nm.
[0027] Preferably, the total pore volume of said alumina and said medium measured by mercury porosimetry is between 0.5 and 0.85 ml / g. Preferably, the volume of the mesopores of said alumina and of said support, measured by mercury porosimetry, is between 0.5 and 0.8 ml / g, preferably between 0.55 and 0.75 and very preferably between 0.60 and 0.75 ml / g.
[0028] Preferably, the volume of the macropores of said alumina and said support, measured by mercury porosimetry, is between 0 and 0.04 ml / g, preferably between 0 and 0.02 ml / g. Preferably, the alumina and said support advantageously have a specific surface area greater than 180 m 2 / g, preferably greater than 220 m 2 / g. Preferably, the alumina used in the invention and said support comprising said alumina are non-mesostructured.
[0029] 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, aluminum chloride, aluminum nitrate, sulfuric acid, hydrochloric acid, and nitric acid, wherein at least one of the basic precursors or acid 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 obtaining a progress rate of said first step of between 40 and 100%, the advancement rate being defined as the proportion of alumina formed in Al 2 O 3 equivalent during said first precipitation step relative to the total amount of alumina formed at the end of the precipitation step (s), 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 heated to a temperature between 50 and 200 ° C for a period of time between 30 minutes and 5 hours to obtain an alumina gel, c) a filtration stage of the suspension obtained at the outcome 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, 10 e) a step 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 step e) at a temperature between 500 and 1000 ° C, with or without air flow containing up to 60% by volume of water.
[0030] In general, the "rate of progress" of the nth precipitation stage is understood to mean 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.
[0031] 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 / L, preferably between 20 and 80 g / l, preferably between 20 and 50 g / l.
[0032] 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.
[0033] Preferably, the basic precursor (s) and acid (s) are added in said first precipitation step a) in aqueous solution containing said precursor (s). Preferably, the basic precursor (s) and acid (s) are added in said first precipitation step a) in aqueous solutions.
[0034] 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.
[0035] 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. 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.
[0036] 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 equivalent Al 2 O 3 based on the total amount of alumina formed at the end of the precipitation stage (s) and more generally at room temperature. from the 30 steps of preparing 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%.
[0037] 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 rate of progress obtained at the end of the precipitation step a) is less than 100%, a second precipitation step is necessary so as 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.
[0038] Thus, depending on the concentration of alumina targeted 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 according to the concentration of said added aluminum precursors, the amount of water added to the reaction medium and the rate of progress required for the precipitation step (s). The flow rates of the acidic and / or basic precursor (s) containing aluminum depend on the size of the reactor used and thus on the amount of water added to the reaction medium.
[0039] Preferably, said precipitation step a) is carried out at a temperature between 10 and 45 ° C, preferably between 15 and 45 ° C, more preferably between 20 and 45 ° C and most preferably between 20 and 45 ° C. and 40 ° C. 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. 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) Heat Treatment According to the invention, said preparation process comprises a step b) of heat treatment of the suspension obtained at the end of the precipitation step a), said heat treatment stage operating at a temperature of a 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.
[0040] Second optional 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.
[0041] 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). In the case where a second precipitation step is carried out, a heating step of the suspension obtained at the end of the precipitation step a) is advantageously carried out between the two precipitation stages 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.
[0042] 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 precipitating the suspension obtained at the end of the heating step, said second step operating by adding to said suspension 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 acidic and basic precursor (s) containing aluminum is adjusted so as to obtain a progress rate of the second stage comp between 0 and 60%, the feed rate being defined as the proportion of alumina formed in Al 2 O 3 equivalent during said second precipitation step relative to the total amount of alumina formed at the end of 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 that at least the basic precursor or the acidic precursor comprises aluminum, that the two basic and acidic precursors comprise aluminum. Basic precursors comprising aluminum are sodium aluminate and potassium aluminate. The preferred basic precursor is sodium aluminate. Acidic precursors comprising aluminum are aluminum sulphate, aluminum chloride and aluminum nitrate. The preferred acidic precursor is aluminum sulphate.
[0043] Preferably, the basic precursor (s) and acid (s) are added in said second precipitation step (a) in aqueous solutions. Preferably, said second precipitation step operates with stirring. Preferably, said second step is carried out in the absence of organic additive.
[0044] 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.
[0045] 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 comprised 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. For the other basic and acidic precursors, whether they contain aluminum or not, the base / acid mass ratio is established by a curve of neutralization of the base by the acid. Such a curve is easily obtained by those skilled in the art.
[0046] 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. 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 0 to 60% by weight of alumina in Al 2 O 3 equivalent relative to the total amount of alumina formed at the end of the two precipitation stages. As in step a) of precipitation, it is the flow rate of the aluminum-containing acidic and basic precursor (s) which is adjusted so as to obtain a progress rate of the second stage of between 0 and 60%. Preferably, the rate of progress of said precipitation step a) is between 10 and 55 (3/0 and preferably between 15 and 55%.
[0047] 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 basic are calculated and the flow rate of the precursors is adjusted according to the concentration of said added aluminum precursors, the amount of water added to the reaction medium and the rate of progress required for each of the precipitation steps. As in step a) of precipitation, the flow rate of the acid-containing precursor (s) and / or base (s) containing aluminum depending on the size of the reactor used and thus the amount of water added to the reaction medium.
[0048] By way of example, if one works in a reactor of 3 liters and is aimed at slurry of alumina with a final concentration of Al 2 O 3 of 50 g / l, the target rate of advancement is 50%. in equivalent A1203 for the first precipitation stage. Thus, 50% of the total alumina must be provided during step a) of precipitation. The alumina precursors are sodium aluminate at a concentration of 155 g / l in Al 2 O 3 and aluminum sulphate at a concentration of 102 g / l in Al 2 O 3. The precipitation pH of the first stage is set at 9. And the second to 9. The amount of water added to the reactor is 622 ml. 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 of sodium aluminate is 13.2 10 ml / min. The mass ratio of sodium aluminate to aluminum sulfate is therefore 1.91. For the second precipitation stage, operating at 70 ° C., for 30 minutes, the aluminum sulfate flow rate should be 2.9 ml / min and the sodium aluminate flow rate is 3.5 ml / min. The mass ratio of sodium aluminate to aluminum sulfate is therefore 1.84.
[0049] 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.
[0050] 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. / I.
[0051] 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.
[0052] Filtration step c) According to the invention, the process for preparing alumina according to the invention also comprises a step c) of filtering the suspension obtained at the end of step b) of heat treatment. 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 Productivity of the preparation process as well as extrapolation of the process to 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.
[0053] 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 index 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 / The weight percentages are expressed relative to the total weight of alumina gel The alumina gel thus obtained, also known as boehmite, has a dispersibility index of between 70 and 100%, preferably between 80 and 100% by weight. and 100%, most preferably between 85 and 100% and even more preferably between 90 and 100%, Preferably the alumina gel thus obtained has a crystallite size of from 2 to 35 nm. the alumina gel thus obtained comprises a sulfur content of from 0.001 to 0.40% by weight, more preferably from 0.003 to 0.33% by weight, and more preferably from 0.003 to 0.3% by weight. between 0.005 and 0.25 (3/0 weight).
[0054] 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% by weight, very preferably between 0.001% and 0.1% by weight). , 0015 and 0.10% by weight, and 0.002 and 0.040% by weight.
[0055] In particular, the alumina gel or the boehmite in powder form according to the invention is composed of crystallites whose size, obtained by the Scherrer formula in X-ray diffraction according to the crystallographic directions (020) and (120) are respectively between 2 and 20 nm and between 2 and 35 nm. Preferably, the alumina gel according to the invention has a crystallite size in the crystallographic direction (020) of between 2 to 15 nm and a crystallite size in the crystallographic direction (120) of between 2 to 35 nm. X-ray diffraction on alumina or boehmite gels was performed using the conventional powder method using a diffractometer.
[0056] The Scherrer 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.
[0057] The alumina gel thus prepared and having a high degree of dispersibility makes it possible to facilitate the shaping step of 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.
[0058] Drying step d) According to the invention, the alumina gel obtained at the end of the filtration step c) 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 spraying. 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 can advantageously be carried out in an oven. closed 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.
[0059] In the case where said drying step d) is carried out by spraying, 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 to evaporate the water according to the principle well known to those skilled in the art. The resulting powder is driven by the heat flow to a cyclone or bag filter which 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 publication Asep Bayu Dani Nandiyanto, Kikuo Okuyama, Advanced Powder Technology, 22, 1-19 , 2011.
[0060] Step e) Shaping In accordance with the invention, the powder obtained at the end of the drying step d) is shaped in a step e) to obtain a green material. By raw material is meant the shaped material which has not undergone any heat treatment steps. Preferably, said shaping step e) is carried out by extrusion kneading, by pelletization, by the method of dropwise coagulation (oil-drop), by rotary plate granulation or by any other method well known to man. of career. Very preferably, said forming step e) is carried out by extrusion kneading. Step f) 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. Preferably, said heat treatment step f) operates at a temperature of between 540 ° C. and 850 ° C.
[0061] Preferably, said heat treatment step f) operates for a duration of between 2 h and 10 h. Said f) heat treatment step allows the transition of the boehmite to the final alumina.
[0062] The process for preparing the alumina used as 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 pore volume and in particular mesoporous calibrated and has the specific porous distribution as described below. The catalyst used in the hydrotreatment process according to the invention is then advantageously obtained by adding the elements constituting the active phase. The catalyst according to the invention may be prepared using any technique known to those skilled in the art, and in particular by impregnation of the elements of groups VIII and / or VIB on the selected support. The addition of dopant such as phosphorus can be done at the same time as the addition of metal salts. This impregnation may, for example, be carried out according to the method known to those skilled in the art in the dry-impregnation terminology, in which the quantity of desired elements is introduced in the form of soluble salts in the chosen solvent, for example demineralised water, so as to fill the porosity of the support as exactly as possible. The impregnation can also be carried out in excess if the person skilled in the art deems it necessary. The support thus filled with the solution according to one or the other of the above methods is preferably dried. This step is preferably preceded by a maturation step whose duration will be less than 72 hours and preferably between 0 and 24 hours, very preferably between 1 and 12 hours. The drying step which follows is preferably carried out in air or under inert at a temperature of between 50 and 200 ° C., very preferably between 65 and 180 ° C. and even more preferably between 75 and 160 ° C. This drying step is optionally followed by a calcination step, generally between 200 ° C. and 550 ° C., preferably between 300 ° C. and 500 ° C. Calciation is then conducted in the presence of air or an inert gas.
[0063] In some cases it may be advantageous to carry out the impregnation in at least two stages. When this solution is preferred, steps of maturation and drying or even intermediate calcination are possible. The precursors of the group VIII metal (s) are advantageously chosen from oxides, citrates, oxalates, carbonates, hydroxycarbonates, hydroxides, phosphates, sulphates, aluminates, molybdates, tungstates, nitrates and halides, for example chlorides. fluorides, bromides, acetates, or any mixture of the compounds set forth herein. Nickel hydroxycarbonate, cobalt or nickel nitrate, cobalt carbonate or cobalt or nickel hydroxide are preferably used.
[0064] The molybdenum precursors used are well known to those skilled in the art. For example, among the sources of molybdenum, it is possible to use oxides and hydroxides, molybdic acids and their salts, in particular ammonium salts such as ammonium molybdate, ammonium heptamolybdate, phosphomolybdic acid ( H3PM012040) and their salts, and optionally silicomolybdic acid (H4SiM012040) and the corresponding salts. Molybdenum sources can also be any heteropolycomposed Keggin type, Keggin lacunary, Keggin substituted, Dawson, Anderson, Strandberg, for example. Molybdenum trioxide and heteropolyanions of the Strandberg, Keggin, Keggin lacunary or substituted Keggin type known to those skilled in the art are preferably used. The tungsten precursors used are well known to those skilled in the art. For example, among the sources of tungsten, it is possible to use oxides and hydroxides, tungstic acids and their salts, in particular ammonium salts such as ammonium tungstate, ammonium metatungstate and phosphotungstic acid (H3PW012040). ) and their salts, and optionally silicotungstic acid (H4SiW12040) and its salts. The sources of tungsten may also be any heteropolycomposed Keggin type, Keggin lacunary, Keggin substituted, Dawson, for example. Oxides and ammonium salts such as ammonium metatungstate or heteropolyanions of the Keggin, Keggin lacunary or substituted Keggin type known to those skilled in the art are preferably used. A chelating agent of organic nature may advantageously be introduced into the metal solution (es) which are used if the person skilled in the art deems it necessary. Whether or not the catalyst undergoes a calcination step, it may then be impregnated with one or more organic agents alone or in admixture in an organic or aqueous solvent. In this case, the skilled person will rely on the abundant literature that exists. Said catalyst thus obtained and used in the process according to the present invention advantageously has the following porous distribution determined by mercury porosimeter: the percentage of volume comprised in the pores of size between 2 and 6 nm, relative to the total pore volume, is between 1 and 25 (3/0, the percentage of volume included in the pores of sizes greater than 6 nm and less than 15 nm represents between 60 and 95% of the total pore volume, the percentage of volume included in the pores of size between 15 and 50 nm represents 0 to 15 (3/0 of the total pore volume and, the percentage of volume included in the pore size between 50 and 7000 nm which corresponds to the macroporous volume represents 0 to 5 (3/0 total pore volume and is preferably between 0 and 3%.
[0065] Finally, the median diameter of the mesopores of said catalyst determined by volume (Dp in nm) measured by mercury porosimetry is advantageously between 8 and 14 nm. The catalyst also advantageously has a specific surface area greater than 130 m2 / g, preferably greater than 150 m2 / g. Preferably, said catalyst also has a total pore volume measured by mercury porosimetry greater than or equal to 0.35 ml / g, preferably greater than or equal to 0.40 ml / g. Preferably, the catalyst used in the present invention has 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 process for preparing the catalyst according to the invention advantageously comprises at least one sulphidation step so that the active phase of the catalyst is in sulphide form. view of the implementation of said catalyst in a hydrotreatment process as described in the present description. This activation treatment by sulphurisation is well known to those skilled in the art and can be carried out by any method known to those skilled in the art. Said sulphurization step is carried out by bringing said catalyst used in the process according to the invention into contact with at least one decomposable sulfur-containing organic compound and generating H 2 S or by placing said catalyst in direct contact with a gaseous stream of H 2 S , for example diluted in hydrogen. Said sulfur-containing organic compound is advantageously chosen from alkyldisulphides such as dimethyl disulphide (DMDS), alkyl sulphides such as dimethyl sulphide, mercaptans such as n-butyl mercaptan, polysulfide compounds of tertiononyl polysulfide type such as TPS- 37 or TPS-54 marketed by ARKEMA, or any other compound known to those skilled in the art to obtain good sulfuration of the catalyst.
[0066] Said sulphurization step can be carried out in situ (that is to say after loading the catalyst in the reaction unit of the hydrotreating process according to the invention) or ex situ (that is to say before loading catalyst in the reaction unit of the hydrotreatment process according to the invention) at a temperature between 200 and 600 ° C and more preferably between 300 and 500 ° C. When the extrusion is carried out ex situ, it will be possible to introduce an organic additive or a solvent or any mixture thereof. This alternative may either lead to a better activity or facilitate the loading and the implementation of the catalyst. The invention is illustrated by the following examples, which are in no way limiting in nature. Examples: Example 1 (Comparative): Preparation of a support AL-1 (non-conforming) according to the patent US7790562.
[0067] In a first step, the synthesis of a non-compliant alumina gel is carried out in that Example 1 is carried out according to the preparation process described in US Pat. No. 7,785,562. In particular, the process for preparing the alumina gel according to Example 1 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 with respect to the total amount of alumina 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.
[0068] A first step of co-precipitating aluminum sulphate Al2 (SO4) and sodium aluminate NaA100 is carried out at 30 ° C and pH = 9.3 for a period of 8 minutes. The concentrations of the aluminum precursors used are as follows: Al 2 (SO 4) = 102 g / l for Al 2 O 3 and Naa 100 for 155 g / l for Al 2 O 3. The agitation is 350 rpm throughout the synthesis. A solution of aluminum sulphate Al2 (SO4) is added continuously for 8 minutes at a flow rate of 19.6 ml / min to a solution of sodium aluminate NaA100 in a weight ratio base / acid = 1.80 to adjust the pH to a value of 9.3. The temperature of the reaction medium is maintained at 30 ° C. A suspension containing a precipitate of alumina is obtained. The final alumina concentration targeted at 30 g / l, the flow rate of aluminum sulphate precursors Al 2 (SO 4) and aluminum aluminate Na 3 100 containing aluminum introduced in the first precipitation stage are respectively 19.6 ml / min. and 23.3 ml / min. These flow rates of acid and basic precursors containing aluminum make it possible to obtain at the end of the first precipitation step a degree of progress of 30%. The suspension obtained is then subjected to a temperature rise of 30 to 57 ° C.
[0069] A second step of co-precipitation of the suspension obtained is then carried out by adding Al 2 (SO 4) aluminum sulphate at a concentration of 102 g / l of Al 2 O 3 and of sodium aluminate NaAl 3 at a concentration of 155 g / l. 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 a solution of sodium aluminate NaA100 in a weight ratio base / acid = 1.68 so as to adjust the pH to a value of 8.7. The temperature of the reaction medium in the second step is maintained at 57 ° C. A suspension containing a precipitate of alumina is obtained. As the final concentration of alumina is 30 g / l, the flow rate of aluminum sulphate precursors Al 2 (SO 4) and aluminum aluminate Na 3 100 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.
[0070] The suspension thus obtained does not undergo a heat treatment step. The suspension obtained is then filtered by displacement of water on a sintered Buchner type tool and the alumina gel obtained is washed 3 times with 5 L of distilled water at 70 ° C. Filtration time and washes are 4 hours. 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. 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 The alumina gel is then spray-dried with a temperature of 250 ° C inlet and 130 ° C outlet. 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 20-minute mixing. / 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 stage. acidification. The kneading is continued for 3 minutes. The paste obtained is then extruded through a 2 mm trilobal die. The extrudates obtained are dried at 100 ° C. overnight and then calcined for 2 hours at 600 ° C. The characteristics of the alumina formed are reported in Table 2: Table 2: Characteristics of alumina AL-1 obtained according to Example 1. AL-1 SBET (m2 / g) 230 VD N (MI / g) ) 0.91 VPT (Hg) (ml / g) 0.78 Vmacro (Hg) (ml / g) 0.01 VmSo (Hg) (ml / g) 0.81 V (d <6nm) 43 V (6) <d <15nm) "(15 <d <50 nm)% Dp (Hg) (nm) Example 2 (according to the invention): Preparation of AL-2 and AL-3 supports (compliant) In a first step, the synthesis of two alumina supports AL-2 and AL-3 is carried out according to a preparation method according to the invention in a 7L reactor and a final suspension of 5L in 3 steps, two precipitation stages. The final concentration of alumina is 45 g / L. The amount of water added to the reactor is 3267 ml.The agitation is 350 rpm throughout the synthesis. step of co-precipitation in water, aluminum sulphate Al2 (SO4) and sodium aluminate NaA1 00 is performed 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 weight 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. 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 first precipitation stage are respectively 69.6 ml / ml. min and 84.5 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 72%. The resulting suspension is then subjected to a temperature rise of 30 to 68 ° C.
[0071] A second step of co-precipitation of the suspension obtained is then carried out by adding Al 2 (SO 4) aluminum sulphate at a concentration of 10 2 / 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 a solution of sodium aluminate NaA100 in a weight ratio base / acid = 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. 1 2.5 11.5 33 3022254 The final concentration of alumina target being 45g / L, the flow rate of aluminum sulphate precursors Al2 (SO4) and aluminum aluminate NaA100 containing aluminum introduced in the second stage of precipitation are respectively 7.2 ml / min and 8.8 ml / min.
[0072] These flow rates of aluminum-containing acidic and basic precursors 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.
[0073] 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 and washes is 3h.
[0074] The characteristics of the alumina gel thus obtained are summarized in Table 3. Table 3: Characteristics of the alumina gel obtained 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 with a dispersibility index of 100% is thus obtained.
[0075] 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 2 was also dried in a ventilated study at 35 ° C. for 4 days. The dried gel in an oven is called Gel No. 2.
[0076] The dried alumina gels Nos. 1 and 2 are then respectively 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 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 first time. acidification step. The kneading is continued for 3 minutes. The paste obtained is then extruded through a 2 mm trilobal die. The extrudates obtained are dried at 100 ° C. overnight and then calcined for 2 hours at 600 ° C.
[0077] The characteristics of the alumina 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 of drying Atomization 35 ° C SBET (M2 / g) 289,292 VD 'N2 (ml / g) 0.83 0.84 VPT (Hg) (ml / g) 0.68 0.69 Vmacro (50-7000nm) (Hg) ( ml / g) 0.01 (2%) 0.01 (2%) VmSo (Hg) (ml / g) 0.71 (99%) 0.73 (99%) V (d <6 nm)% 3 2 V (6 <d <15 nm)% 82 84 V (15 <d <50 nm)% 6.56 6 Dp at Vmso / 2 (nm) (Hg) 9.7 9.8 Example 3: Preparation of catalysts C1 and O2 (non-compliant), from alumina AL-1 and catalysts 03 and 04 (compliant) respectively from alumina supports AL-2, and AL-3. The catalysts C1 and 02 are obtained by dry impregnation of the Al-1 alumina support in the form of extrudates, prepared according to Example 1, with an impregnation solution prepared by hot-dissolving molybdenum oxide and of cobalt hydroxycarbonate in a solution of phosphoric acid in aqueous solution, the volume of said impregnating solution being strictly equal to the pore volume of the alumina support mass. The precursor concentrations in the impregnating solution are adjusted so as to deposit on the alumina support the desired Mo, Co and P weight contents. After the dry impregnation step, the extrudates are allowed to mature in a saturated water atmosphere for 12 h, then they are dried overnight at 90 ° C and calcined at 450 ° C for 2 hours. The final composition of the catalyst Cl, expressed in the form of oxides and determined by X-ray fluorescence, is then as follows: MoO 3 = 20.4 ± 0.2 (w / w%), Co ° = 3.6 25 ± 0 , 1 (% by weight) and P205 = 5.9 ± 0.1 (% by weight), which corresponds to Co / Mo = 0.34 mol / mol and P / Mo = 0.59 mol / mol.
[0078] The final composition of the catalyst O 2 expressed as oxides and determined by X-ray fluorescence is then as follows: MoO 3 = 25.6 ± 0.2 (w / w%), Co ° = 3.9. ± 0.1 (wt%) and P205 = 2.8 ± 0.1 (wt%), which corresponds to Co / Mo = 0.29 mol / mol and P / Mo = 0, 22 mol / mol.
[0079] For catalysts C1 and O2, the Z parameter remains close to that of alumina AL-1 with 2.4 and 2.3, respectively. Catalyst 03 is prepared analogously to catalyst C1, but from support AL-2. It retains a Z value greater than that of Cl catalyst with 6.4.
[0080] The final composition of the catalyst, expressed in the form of oxides and determined by X-ray fluorescence, is then as follows: MoO 3 = 20.1 ± 0.2 (w / w%), Co ° = 3.4 ± 0.1 (w / w%) and P205 = 6.0 ± 0.1 (wt / wt), which corresponds to Co / Mo = 0.33 mol / mol and P / Mo = 0 60 mol / mol. Catalyst 04 is prepared analogously to catalyst C1, but from support AL-3. It also retains a Z value greater than that of catalyst 02, with 6.1. The final composition of the catalyst 04 expressed in the form of oxides is then the following: Mo03 = 25.1 ± 0.2 (`) / 0 by weight), Co ° = 3.6 ± 0.1 (`) / 0 by weight and P205 = 2.9 ± 0.1 (wt%), which corresponds to Co / Mo = 0.28 mol / mol and P / Mo = 0.23 mol / mol.
[0081] EXAMPLE 4 Evaluation of the Catalytic Performance of Catalysts Cl and O2 (Non-Conforming) and 03 and 04 (Compliant) in Test Molecule Model Hydrogenation of Toluene in Clohexane Under Pressure and H 2 S Resistance In applications such as hydrotreatment or to reach the sulfur targets in force, it is necessary to desulphurize mainly refractory compounds such as DMDBT 4.6, the hydro-dehydrogenating function plays a critical role. The hydrogenation test of toluene was therefore used to know the interest of catalysts for the hydrotreatment of such fillers. Catalysts C1 to 04 previously described are in-situ sulphurized dynamically in a fixed bed tubular reactor through a Microcat pilot unit (manufacturer: Vinci), the fluids flowing from top to bottom. The measurements of hydrogenating activity are carried out immediately after sulphurization under pressure and without re-airing with the hydrocarbon feedstock which was used to sulphurize the catalysts.
[0082] The sulfurization and test load is composed of 5.8% (3% dimethyldisulphide (DMDS), 20% toluene and 74.12% cyclohexane (by weight). by decomposition into methane and H2S to maintain the catalyst in its sulphurized form The sulphurization is carried out from room temperature up to 350 ° C, with a temperature ramp of 2 ° C / min, a VVH = 4h1 and H2 / HC = 450 N1 / 1. The catalytic test is carried out at 350 ° C at VVH = 2h1 and H2 / HC equivalent to that of the sulfurization, with online analysis on at least 4 samples / effluents to determine its composition. thus the stabilized catalytic activities of equal volumes of the catalysts in the hydrogenation reaction of toluene.
[0083] The detailed activity measurement conditions are as follows: Total pressure: 6.0 MPa 0.37 MPa 1.42 MPa 0.22 MPa 3.68 MPa 0.22 MPa Toluene pressure: Cyclohexane pressure: Pressure of methane Hydrogen pressure: H2S pressure: A volume of catalyst equal to 4 cm 3 (extruded length of between 2 and 4 mm) is loaded by weighing via the density of the catalytic bed. The determination of unconverted toluene (T) molar concentrations and hydrogenation product concentrations (methylcyclohexane (M006), ethylcyclopentane (Et005) and dimethylcyclopentanes (DM005)) make it possible to calculate a hydrogenation rate of toluene. XHyD defined by: MCC6 + EtCC5 + DMCC5 X HyD (%) = 100X T + MCC6 + EtCC5 + DMCC5 The hydrogenation reaction of toluene being of order 1 under the test conditions used and the reactor behaving like a piston reactor ideally, the hydrogenating activity AHYD of the catalysts is calculated by applying the formula: AHyD = 1n (100 100 - X HyD 20 Table 5 below compares the relative hydrogenating activities of catalysts C1 to of the impregnated active phase and the connectivity parameter Z.
[0084] Table 5: Relative Activity Relative to Catalyst C1 (Non-Conforming) in Toluene Hydrogenation of Catalysts 03 and 04 (Compliant) and Catalyst 02 (Non-Conform) Catalyst AHyD Relative to Cl (`) / O) Cl ( non-compliant) 20 ° / 0Mo03 Z = 2.4 AL-1 100 03 (compliant) 20`) 0Mo03 Z = 6.4 AL-2 122 02 (non-compliant) 25 ° / 0Mo03 Z = 2.3 AL-1 118 04 (in conformity) 25`) 0Mo03 Z = 6.1 AL-3 153 The results in Table 5 demonstrate that the catalytic performances, in terms of hydrogenating activity, of the catalyst 03 prepared according to the invention from AL-2 support and whose Z parameter is 6.4 is significantly higher than the non-compliant catalyst C1 which was obtained from the support AL-1 and which therefore has a Z parameter of 2.4. This increase in hydrogenating activity is particularly advantageous since it makes it possible in particular to reach a level of activity close to that of the non-compliant catalyst O 2, but with only 20 μMo0 3 as against 25 μMOD 3 on the catalyst O 2. at this molybdenum content, the catalyst prepared according to the invention from support AL-3 has an even higher hydrogenating activity. In the absence of diffusional limitation of the reaction charge, the test taking place in the gas phase, this result demonstrates the interest of the impregnation of the metal phase on a support with high connectivity. The quality of the deposited active phase seems improved. EXAMPLE 5 Evaluation of the Catalytic Performance of Catalysts C1 and O2 (Non-Conforming) and Catalysts 03 and 04 (Conforming) in Hydrotreating of Direct Diesel Fuel With a view to their evaluation in hydrodesulfurization (HDS) of gas oil, catalysts C1 to C4 undergo an in-situ sulphurization step in a crossed-bed type reactor (30 cm3 of catalyst in the form of extrudates mixed with 10 cm3 of SiC with a particle size of 0.8 mm). The sulphurization is carried out at 30 bar (3 MPa), at VVH = 2 11-1, with a ratio (of volume flow) H2 / HC entry = 250 Std 1/1. The sulphurization charge (gas oil additive of 2% (3/0) of DMDS Evolution® from Arkema) is introduced into the reactor at a flow rate of H2 as soon as it reaches 150 ° C. After one hour at 150 ° C. , the temperature is increased with a ramp of 25 ° C / hour up to 220 ° C, then with a ramp of 12 ° C / hour until reaching a plateau of 350 ° C, maintained 12 hours.
[0085] After sulfurization, the temperature is lowered to 330 ° C and the test load is injected (without DMDS). The catalytic test is carried out at a total pressure of 3 MPa, with hydrogen lost (without recycling), at VVH = 2 11-1, with a volume ratio H2 / HC at the inlet of 250 Std 1/1 (flow rate H2 = 24 Std 1.h-1, flow rate = 60 cm3.h-1), and at three different temperatures 330 ° C then 340 ° C and 350 ° C, observing between each point a sufficient time for the sulfur content 10 be stabilized. In order to be able to evaluate the performance of the catalysts in HDS, and to avoid the presence of H2S in the effluents, the pot containing the effluents is stripped with nitrogen at a rate of 10 L.11-1. The diesel fuel used here comes from a heavy Arab crude. It contains 0.89% sulfur, 150 ppm nitrogen, a density of 0.848 g / cm3 and a weighted average temperature (TMP), defined from the temperature at which 5%, 50% is distilled. % and 70% of the charge volume according to the following formula: TMP = (15 + 2150 + 4195) / 7, is 324 ° C. The catalytic performances of the catalysts are given in Table 6. They are expressed as activity relative, assuming that that of the catalyst Cl is equal to 100 and considering that they are of apparent order 1.25 with respect to the sulfur (one indicates an average activity calculated at the three points of temperature) Another way to quantify the gain is to raise the temperature for which the effluent contains 50 ppm of sulfur, in the same way the catalyst C1 is placed as a base.
[0086] Table 6: Relative activity (with catalyst iso-volume) of direct catalytic diesel HDS catalysts C1 to C4 Ahds relative catalyst, relative to T5Oppm Cl ('Y ()) Cl (non-compliant) 20 ° / 0Mo03 Z = 2.4 AL-1 100 Base C3 (compliant) 20`) 0Mo03 Z = 6.4 AL-2 105 Base - 2.3 ° C C2 (non compliant) 25% Mo03 Z = 2.3 AL-1 117 Base - 5.1 ° C C4 (compliant) 25`) 0Mo03 Z = 6.1 AL-3 127 Base - 6.9 ° C a lower temperature indicates a gain in activity 39 3022254 The results in the table 6 demonstrate the significant activity gain obtained on the catalyst 03 prepared according to the process of the invention by impregnating a support having a high Z parameter (6.4) relative to the catalyst C1 prepared with a support whose Z parameter is low (2.4). ).
[0087] The effect is confirmed at higher metal content (catalyst O2 according to a process of the prior art compared to catalyst O4 prepared according to the invention). More generally, the results obtained demonstrate that the catalyst prepared according to the invention makes it possible to reduce the operating temperature of the unit by about 2 ° C. for the same sulfur content in the effluent compared with the catalysts of the invention. the prior art. This gain may also allow the refiner to treat charges which would be more refractory and which would not be compatible with the operating temperatures required by the catalysts of the prior art, but which become so if the catalysts according to the invention are used. . 1540

权利要求:
Claims (15)
[0001]
REVENDICATIONS1. Process for the hydrotreatment of at least one gas oil fraction having a weighted average temperature (TMP) of between 240 ° C and 350 ° C using 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 connectivity (Z) greater than 2.7, the connectivity being determined from the nitrogen adsorption / desorption isotherms, said hydrotreatment process operating at a temperature between 250 ° C. and 400 ° C., at a total pressure of between 2 MPa and 10 MPa with a ratio of volume of hydrogen per volume of hydrocarbon feedstock of between 100 and 800 liters per liter and at a fixed 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 of between 1 and 10 h -1.
[0002]
2. Process according to claim 1, in which the gasoil fraction used is chosen from diesel fuel cuts resulting from the direct distillation alone or mixed with at least one cut from a coking unit, or at least one cut resulting from catalytic cracking. or at least one diesel cut from other conversion processes such as mild hydrocracking or hydrotreating residues.
[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 in the case where the catalyst comprises at least one metal of group VIB in combination with at least one non-noble metal of group VIII, the metal content of group VIB is included between 10 and 35% by weight of oxide relative to the total mass of said catalyst, and the non-noble metal content of group VIII is between 1 and 10% by weight of oxide relative to the total mass of said catalyst.
[0006]
6. Method according to one of claims 1 to 5 wherein the catalyst contains at least one doping element selected from phosphorus, boron, fluorine or silicon, alone or in admixture. 41 3022254
[0007]
7. The process according to claim 6 wherein the phosphorus content in said catalyst is 0.5 to 15% by weight of P205.
[0008]
8. Method according to one of claims 1 to 7 wherein the catalyst support comprises an amorphous mesoporous alumina having a connectivity (Z) of between 3 and 7.
[0009]
9. Method according to one of claims 1 to 8 wherein the catalyst has a connectivity (Z) of between 3 and 7.
[0010]
10. Process according to one of claims 1 to 9 wherein the catalyst support has the following porous distribution, measured by mercury porosimetry: the percentage of volume included in the size of the pores and 2 and 6 nm, in relation to at the total pore volume, is between 1 and 25%, the percentage of volume included in the pores of sizes greater than 6 nm and less than 15 nm represents between 60 and 95% of the total pore volume, the percentage of volume included in the Pores of size between 15 and 50 nm represent 0 to 8% of the total pore volume and the percentage of volume included in the pore size between 50 and 7000 nm which corresponds to the macroporous volume represents 0 to 5%.
[0011]
11. Method according to one of claims 1 to 10 wherein said support has a median diameter of the mesopores measured by mercury porosimetry determined by volume between 7 and 12.5 nm.
[0012]
12. Method according to one of claims 1 to 11 wherein said support has a mesopore volume measured by mercury porosimetry, between 0.5 and 0.8 ml / g. 30
[0013]
13. Method according to one of claims 1 to 12 wherein said catalyst has the following porous distribution determined by mercury prosimeter: the percentage of volume in the pore size of between 2 and 6 nm, relative to the total pore volume. is between 1 and 25%, the percentage of volume comprised in the pores of sizes greater than 6 nm and less than 15 nm represents between 60 and 95% of the total pore volume, the percentage of volume included in the pores with a size of between 15 and 50 nm represent 0 to 15% of the total pore volume and the percentage of volume included in the pore size between 50 and 7000 nm which corresponds to the macroporous volume represents 0 to 5% of the pore volume 5 total.
[0014]
14. Method according to one of claims 1 to 13 wherein said catalyst has a total pore volume measured by mercury porosimetry greater than or equal to 0.35 ml / g. 10
[0015]
15. Process for the hydrotreatment of at least one diesel fuel cut having a weighted average temperature (TMP) of between 240 ° C. and 350 ° C., operating at a temperature of between 250 ° C. and 400 ° C., at a total pressure comprised between between 2 MPa and 10 MPa with a ratio of volume of hydrogen per volume of hydrocarbon feedstock of between 100 and 800 liters per liter and at a Time Volumetric Speed (VVH) defined by the ratio of volume flow rate of liquid hydrocarbon feedstock by volume of a catalyst charged in the reactor of between 1 and 10 hl, 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 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 precipitation of alumina, in an aqueous reaction medium, of at least one basic precursor e 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 of acid precursors and basic is chosen so as to obtain a pH of the reaction medium of between 8.5 and 10.5 and the flow rate of the aluminum-containing acidic and basic precursor (s) is adjusted so as to obtain a progress rate of the first a step of between 40 and 100%, the rate of progress 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 at the end of the precipitation stage or steps, said step a) performed at a temperature 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 period of between 30 minutes and 5 hours to obtain an alumina gel, c) a filtering step of the suspension obtained at the end of step b ) of heat treatment, 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 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 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. 10

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优先权:

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申请号 | 申请日 | 专利标题

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FR1455424A|FR3022254B1|2014-06-13|2014-06-13|METHOD OF HYDROPROCESSING GAS CUTTINGS USING A CATALYST BASED ON AMORPHOUS AMORPHOUS ALUMINA HAVING HIGH CONNECTIVITY|FR1455424A| FR3022254B1|2014-06-13|2014-06-13|METHOD OF HYDROPROCESSING GAS CUTTINGS USING A CATALYST BASED ON AMORPHOUS AMORPHOUS ALUMINA HAVING HIGH CONNECTIVITY|

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CN201580043444.6A| CN107155314A|2014-06-13|2015-06-09|Using the catalyst being made up of the amorphous mesoporous aluminas with high connectivity come the method for hydroprocessed diesel cut|

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US15/318,587| US10626337B2|2014-06-13|2015-06-09|Method for the hydrotreatment of diesel cuts using a catalyst made from an amorphous mesoporous alumina having high connectivity|

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BR112016028971A| BR112016028971A2|2014-06-13|2015-06-09|hydrotreating process of fuel oil cuts using an amorphous mesoporous alumina-based catalyst having high connectivity|

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RU2017100965A| RU2689116C2|2014-06-13|2015-06-09|Method for hydrotreatment of gas-oil fractions using catalyst based on amorphous mesoporous aluminium oxide having high coherence of structure|

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ES15730989.9T| ES2677523T3|2014-06-13|2015-06-09|Hydrotreatment method of diesel cuts using a catalyst based on an amorphous mesoporous alumina that has high connectivity|

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PCT/EP2015/062827| WO2015189201A1|2014-06-13|2015-06-09|Method for the hydrotreatment of diesel cuts using a catalyst made from an amorphous mesoporous alumina having high connectivity|

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EP15730989.9A| EP3155074B1|2014-06-13|2015-06-09|Method for the hydrotreatment of diesel cuts using a catalyst made from an amorphous mesoporous alumina having high connectivity|

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JP2016572434A| JP6703956B2|2014-06-13|2015-06-09|Hydrotreating process of diesel fraction using catalyst made from amorphous mesoporous alumina with high connectivity|

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