Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
  • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/88—Molybdenum
  • B01J23/883—Molybdenum and nickel
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/14—Phosphorus; Compounds thereof
  • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/14—Phosphorus; Compounds thereof
  • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
  • B01J27/19—Molybdenum
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
  • B01J37/0213—Preparation of the impregnating solution
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/08—Heat treatment
  • B01J37/082—Decomposition and pyrolysis
  • B01J37/084—Decomposition of carbon-containing compounds into carbon
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/20—Sulfiding
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/44—Hydrogenation of the aromatic hydrocarbons
  • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/44—Hydrogenation of the aromatic hydrocarbons
  • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
  • C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
  • C10G45/50—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metal, or compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/44—Hydrogenation of the aromatic hydrocarbons
  • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
  • C10G45/54—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/18—Carbon
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
  • B01J27/04—Sulfides
  • B01J27/043—Sulfides with iron group metals or platinum group metals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
  • B01J27/04—Sulfides
  • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
  • B01J27/04—Sulfides
  • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
  • B01J27/049—Sulfides with chromium, molybdenum, tungsten or polonium with iron group metals or platinum group metals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
  • B01J27/04—Sulfides
  • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
  • B01J27/051—Molybdenum
  • B01J27/0515—Molybdenum with iron group metals or platinum group metals
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/70—Catalyst aspects

Definitions

• the present invention relates to the field of hydrotreating processes of hydrocarbon feeds operated in the presence of a catalyst comprising composite materials comprising a compound based on at least one crystalline aluminum solid and carbon.
• a hydrotreating catalyst for hydrocarbon cuts is intended to eliminate the sulfur or nitrogen compounds contained therein or to hydrogenate the aromatic molecules, for example to bring a petroleum product to the required specifications (sulfur content, aromatic content, etc.) for a given application (automotive fuel, gasoline or diesel, heating oil, jet fuel). It may also be pretreat this load in order to remove impurities or hydrogenate before subjecting it to various transformation processes to modify the physicochemical properties, such as for example reforming processes, hydrocracking vacuum distillates, catalytic cracking, hydroconversion of atmospheric residues or under vacuum.
• the composition and use of hydrotreatment catalysts are particularly well described in the book Catalysis By Transition Metal Sulfides, From Molecular Theory To Industrial Application by H. Toulhoat and P. Raybaud, published by Technip (2013).
• refractory fillers require catalysts having hydrodesulphurizing and hydrogenating functions which are greatly improved over traditional catalysts.
• conversion processes such as catalytic cracking or hydrocracking use catalysts having an acid function, which makes them particularly sensitive to the presence of nitrogen impurities, including basic nitrogen compounds. It is therefore necessary to use pretreatment catalysts of these fillers so as to remove these compounds.
• Conventional hydrotreatment catalysts generally comprise an oxide-based support (s) and an active phase based on Group VIB and VIII metals.
• the preparation of these catalysts generally comprises a step of impregnating the metals on the support, followed by drying and optionally calcination to obtain the elements in their oxide forms.
• these catalysts are generally subjected to sulphidation in order to form the active phase.
• US2013 / 267409 discloses the use of an organic compound of formula R1COCH2COR2 wherein R1 and R2 are the same or different and are selected from a group consisting of C1 to C12 alkyl, C6 to C12 allyl, alkoxy C1 to C12 and hydroxy. Whatever the organic compounds chosen, the induced modifications do not always make it possible to increase sufficiently the performances of the catalyst to meet the specifications relating to the sulfur and / or nitrogen contents of the fuels.
• CVD Chemical Vapor Deposition
• a carbon precursor methane, ethylene, benzene
• CVD Chemical Vapor Deposition
• a third, more recent, possible option is to adsorb a sugar or polyol-type carbon precursor on the surface of a crystalline aluminum solid under "hydrothermal” (HT) operating conditions, to pyrolyze said precursor and to reproduce as many cycles. "Adsorption / pyrolysis” as necessary until the deposit of the desired carbon content (see application FR 17 / 57.841).
• the composite C / Al2O3 thus obtained is characterized by a relatively low carbon content (1 to 15% by weight relative to the total mass of the final solid) and by a specific localization of the carbon on the surface of the aluminum support, which results in by an inhibition of the reactive surface sites at the origin of the rehydration of the aluminum support under specific conditions, for example HT conditions.
• the weight content of carbon deposited is different according to the proposed synthesis methodologies, which implies that the latter have an impact on the nature and the intrinsic properties of the carbon deposit produced and on the potential interactions [oxide-based support ( s) with carbon / precursors of the sulphide phase], in the case of the synthesis of a hydrotreatment and / or hydrocracking catalyst.
• Another possible strategy, intended to cover the surface OHs of aluminum solids, is not to synthesize solid C / Al2O3 composites but to use the adsorption capacity of the aluminum surface with respect to specific organic molecules, such as polyols for example (Ravenelle et al., Top Catal., 2012, 55, 3, 162).
• This method nevertheless has several major disadvantages such as the impossibility of protecting the aluminum support before the deposition of the active metal phase, the need to achieve and control this protection "in situ" during the implementation of the catalyst (or during pretreatment of the latter) and the difficulty of regenerating said catalyst during a possible implementation in cyclic processes.
• a composite material comprising a compound based on at least one crystalline aluminum solid and carbon allows the catalysts prepared from this support to significantly increase the hydrotreatment reactions (hydrodesulfurization). , hydrogenation and hydrodenitrogenation) compared to conventionally used hydrotreatment catalysts.
• the invention relates to a process for the hydrotreatment of a hydrocarbon feedstock, carried out at a temperature of between 180 ° C. and 450 ° C., at a pressure of between 0.5 MPa and 30 MPa, in the presence of a catalyst comprising ) a composite material comprising at least one compound based on at least one crystalline aluminum solid and carbon, the deposited carbon content being between 1 and 25% by weight of the total mass of the composite material, and ii) at least one Group VIB element and at least one group VIII element, in their sulphide form, said catalyst being prepared by a process comprising at least:
• step c) depositing at least one element of group VI and at least one element of group VIII on the surface of the composite material obtained at the end of step c);
• step d a solid sulphidation step obtained in step d).
• the hydrotreatment process according to the invention using this type of catalyst, has improved catalytic performance compared to the processes of the prior art using catalysts not comprising the specific material according to the invention. More particularly, the process according to the invention has an improved activity compared to the methods of the prior art.
• the hydrotreating process of a hydrocarbon feedstock according to the invention is especially used in the hydrodesulfurization, hydrodenitrogenation, hydrodemetallation, hydrogenation and aromatic hydrogenation (or hydrodearomatization) reactions of said hydrocarbon feedstock.
• it makes it possible to obtain a hydrogenation of the aromatics of the feedstock which is higher than that obtained by conventional processes using, for example, catalysts based on non-carbonated alumina.
• hydrocarbon feed normally treated in hydrotreatment processes such as, for example, gasolines, gas oils, vacuum gas oils, atmospheric residues, vacuum residues, atmospheric distillates, distillates vacuum, heavy fuels, oils, waxes and paraffins, used oils, residues or deasphalted crudes, fillers from thermal or catalytic conversion processes, alone or in mixtures.
• the treated fillers, and in particular those mentioned above generally contain heteroatoms such as sulfur, oxygen and nitrogen and, for heavy loads, they most often also contain metals.
• the composite material as described in the present invention is in particular described using the following characterization techniques: nitrogen adsorption / desorption volumetry and elementary analysis known as "CHNS".
• Specific surface area is understood to mean the BET specific surface area (SBET in m 2 / g) determined by nitrogen adsorption according to the ASTM D 3663-78 standard established from the BRUNAUER-EMMETT-TELLER method described in the "The Journal of the American Society, 1938, 60, 309.
• the representative porous distribution of a mesopore population centered in a range of 2 to 50 nm is determined by the Barrett-Joyner-Halenda model (BJH).
• BJH Barrett-Joyner-Halenda model
• the nitrogen adsorption-desorption isotherm according to the BJH model thus obtained is described in the periodical "The Journal of the American Society", 1951, 73, 373, written by E. P. Barrett, L. G. Joyner and P. Halenda.
• the diameter of the mesopores f of the composite material according to the invention corresponds to the maximum diameter obtained on the curve of the porous distribution to desorption.
• the pore volume (Vp) corresponds to the volume obtained at the maximum value of R / R0.
• the shape of the nitrogen adsorption isotherm and the hysteresis loop can provide information on the nature of the mesoporosity.
• the CHNS Elemental Analyzer allows the rapid determination of carbon (C), hydrogen (H), nitrogen (N), sulfur (S) content in organic matter and other types of materials, based on on the total combustion of the analytical sample at 1000 ° C under oxygen flow and under pressure.
• the carbon, hydrogen, nitrogen and sulfur of the samples are respectively transformed into carbon dioxide, water, nitrogen dioxide and sulfur dioxide. These products are separated on a chromatographic column and quantified on a thermal conductivity detector, a katharometer.
• crystalline aluminum solid is meant, according to the invention, any aluminum compound belonging to the family of transition aluminas as well as alpha alumina (or corundum) and their derivatives which result from the dehydration of aluminum precursor materials.
• aluminum trihydroxide type (gibbsite, bayerite, norstandite, doyleite) or aluminum oxy (hydroxyl) (boehmite, diaspore)
• gamma-alumina delta, theta, eta, rho, chi, kappa.
• transition aluminas and alpha alumina any transition alumina or alpha alumina which would include one or more additional elements, such as beta alumina which is stabilized by alkaline ions.
• compound based on at least one crystalline aluminum solid is meant any compound having at least one crystalline aluminum solids content such that the latter is detected by analysis by X-ray diffraction (XRD), that is to say say that the latter represents at least 10% by weight, preferably at least 20% by weight and even more preferably at least 50% by weight relative to the total weight of said compound.
• XRD X-ray diffraction
• the compound based on at least one crystalline aluminum solid may contain up to 100% crystalline aluminum solids.
• the process according to the invention is a process for hydrotreating a hydrocarbon feedstock operated at a temperature of between 180 ° C. and 450 ° C. and at a pressure of between 0.5 MPa and 30 MPa in the presence of a catalyst comprising i) a composite material comprising at least one compound based on at least one crystalline aluminum solid and carbon, the deposited carbon content being between 1 and 25% by weight of the total mass of the composite material, and ii) at least a group VIB element and at least one group VIII element, in their sulphide form, said catalyst being prepared by a process comprising at least:
• step c) depositing at least one element of group VI and at least one element of group VIII on the surface of the composite material obtained at the end of step c);
• step d a solid sulphidation step obtained in step d).
• the process according to the invention preferably involves a catalyst prepared according to a process consisting of the above steps a) to e).
• the process according to the invention is advantageously applied to the hydrotreatment reactions of hydrocarbon feeds and more particularly to the hydrogenation reactions, hydrodenitrogenation, hydrodearomatization, hydrodesulfurization, hydrodemetallation or hydroconversion of hydrocarbon feedstocks. It can also be applied during pre-treatment of catalytic cracking feeds or hydrodesulfurization of residues or the deep hydrodesulfurization of gas oils (ULSD Ultra Low Sulfur Diesel).
• the hydrocarbon feedstocks treated by the hydrotreatment process according to the invention are chosen in particular from petroleum cuts, cuts resulting from the liquefaction of coal or hydrocarbons produced from natural gas. These are, for example, gasolines, gas oils, vacuum gas oils, atmospheric residues, vacuum residues, atmospheric distillates, vacuum distillates, heavy fuels, oils, waxes and the like. paraffins, used oils, residues or deasphalted crudes, fillers derived from thermal or catalytic conversion processes, alone or in mixtures.
• the treated fillers, and in particular those mentioned above generally contain heteroatoms such as sulfur, oxygen and nitrogen and, for heavy loads, they most often also contain metals.
• the hydrotreatment process according to the invention is advantageously carried out at a temperature of between 180 and 450 ° C., preferably between 250 and 440 ° C., at a pressure of between 0.5 and 30 MPa, preferably between 1 and 20. MPa and more preferably between 1 and 18 MPa, at an hourly volume velocity (WH) between 0.1 and 20 h 1 and preferably between 0.2 and 5 h 1 , and with a hydrogen / charge ratio, expressed in volume of hydrogen, measured under normal conditions of temperature and pressure, by volume of liquid charge, ranging from 50 1/1 to 2000 1/1.
• WH hourly volume velocity
• the catalyst used in the process according to the invention has a carbon content deposited between 1 and 25% by weight relative to the total mass of the catalyst, preferably between 1 and 15% by weight and even more preferably between 3 and 15% by weight relative to the total mass of the catalyst.
• the composite material comprises at least one compound based on at least one crystalline aluminum solid and carbon.
• said composite material consists of at least one compound based on at least one crystalline aluminum solid and carbon.
• the carbon content deposited is between 1 and 25% by weight relative to the total mass of said composite material, preferably between 1 and 15% by weight and even more preferably between 3 and 15% by weight relative to the total mass of the composite material. catalyst.
• the catalyst used in the process according to the invention comprises at least one element of group VIB and at least one element of group VIII according to the IUPAC classification.
• Group VIB elements are preferably selected from Mo and W alone or in admixture.
• the Group VIII elements are preferably selected from Co, Ni and Fe, alone or in admixture.
• the term "catalyst” means a solid comprising a composite material comprising a compound based on at least one crystalline aluminum solid and carbon, and also comprising at least one group VIB element and at least one Group VIII element in their active form for hydrotreatment reactions, that is, in their sulphide form.
• Said active phase is a sulphurized form of Group VIB and Group VIII elements, which results from bringing said Group VIB and Group VIII elements into contact with TELS or any other compound capable of generating TELS by decomposition.
• non-activated catalyst the solid comprising the material comprising a compound based on at least one crystalline aluminum solid and carbon, and also comprising at least one element of group VIB and at least one element Group VIII in their non-sulphured form.
• the total content of elements of groups VIB and VIII of the periodic table according to the IUPAC classification is advantageously between 0.1% and 35% by weight and preferably between 0.1 and 25% by weight relative to total weight of said catalyst.
• the element of group VIB is advantageously between 0.1 and 25% by weight relative to the total weight of said catalyst and the element of group VIII is advantageously between 0.1% and 10% by weight relative to the total weight of said catalyst .
• the molar ratio of Group VIII element to Group VI element is advantageously between 0.1 and 0.8, and preferably between 0.15 and 0.6.
• the catalyst used in the process according to the invention is prepared by a process comprising a step a) of contacting a mixture comprising at least one carbon precursor with at least one compound based on at least one aluminum solid crystalline at a temperature between 50 and 300 ° C at a pressure corresponding at least to the autogenous pressure.
• Said step a) is carried out under hydrothermal conditions. That is to say that the placing in contact is carried out in an autoclave, the whole of the reaction medium then being brought to a temperature of between 50 and 300 ° C., preferably between 100 and 250 ° C. and still more preferred between 140 and 210 ° C, the pressure corresponding to at least the autogenous pressure associated with the chosen temperature.
• the placing in contact can be carried out under oxidizing atmosphere (air), neutral (Inert gas: dinitrogen, argon, etc.) or reducing, that is to say composed partially or totally of hydrogen. In a preferred manner, the atmosphere is air.
• Said carbon precursor is an organic molecule, advantageously of the sugar (glucose, fructose, sucrose, etc.) or polyol type.
• said carbon precursor is a polyol
• said polyol preferably contains at least 3 carbon atoms and even more preferably at least 5 carbon atoms and also preferably has at least 3 vicinal hydroxyl groups (excluding terminal hydroxyl groups) and Even more preferably, there are vicinal hydroxyl groups in the threo configuration.
• Useful polyols may for example be selected from the following list: xylitol, sorbitol, dulcitol.
• the carbon precursor is an organic molecule of the polyol type.
• the mixture comprising the carbon precursor is advantageously aqueous. It can be neutral, acidic or basic. It is preferably neutral.
• the pH of the mixture can be adjusted by the addition of compounds to regulate the pH, so as to lead to an acidic mixture, basic or neutral. These compounds may belong to the following non-exhaustive list: nitric acid, hydrochloric acid, sulfuric acid, carboxylic acids, ammonia, tetraethylammonium hydroxide, urea.
• the concentration of carbon precursor of the mixture is between 2 and 100 g / l, preferably between 5 and 50 g / l and more preferably between 5 and 35 g / l.
• the suspension has a composition such that the mass ratio of carbon precursor relative to the compound based on at least one aluminum solid in the suspension is between 0.1 and 2, preferably between 0.3 and 1, and more preferably preferred between 0.3 and 0.6.
• Said suspension is advantageously autoclaved with stirring in any autoclave for imposing a specific temperature at a pressure at least equal to the autogenous pressure with stirring, at a temperature between 50 and 300 ° C, preferably between 100 and 250 ° C and even more preferably between 140 and 210 ° C.
• the catalyst used in the process according to the invention is prepared by a process comprising a step b) of heat treatment of the solid obtained at the end of step a).
• Step b) of heat treatment of the solid obtained after step a) is advantageously constituted by a first drying step at a temperature of between 50 and 150 ° C., for example in an oven, and then a second pyrolysis step carried out in a through-bed tubular furnace under a stream of inert gas (dinitrogen, argon, etc.) with a flow rate of between 1 and 30 ml / min / g and preferably between 5 and 15 ml / min / gsoiide and at a temperature between 300 and 1000 ° C, preferably between 400 and 700 ° C, for a period of 0.5 to 24 hours, preferably for a period of 0.5 to 12 hours and even more preferred for a period of 0.5 to 5 hours.
• inert gas dinitrogen, argon, etc.
• Step c) repeating steps a) and b)
• the catalyst used in the process according to the invention is prepared by a process comprising a step c) of repeating steps a) and b) until the desired deposited carbon content is obtained, namely up to obtaining a carbon content deposited between 1 and 25% by weight relative to the total mass of the composite material, preferably between 1 and 15% by weight and even more preferably between 3 and 15% by weight.
• Step c) is advantageously carried out at least once, preferably at least twice and even more preferably at least 5 times.
• the catalyst used in the process according to the invention is prepared by a process advantageously comprising a step d) of depositing at least one element of group VIB and at least one element of group VIII of the periodic table according to the classification of IUPAC on the composite material obtained at the end of step c).
• the deposition of at least one element of group VIB and at least one element of group VIII according to step d) can advantageously be carried out by any technique known to those skilled in the art, such as, for example, ion exchange, dry impregnation, excess impregnation, vapor deposition, etc.
• the deposit can take place in one stage or in several successive stages.
• said depositing step (s) is (are) carried out by the so-called “dry” impregnation method well known to those skilled in the art.
• the deposition of at least one element of group VIB and at least one element of group VIII advantageously involves a precursor of said metals.
• Group VIII precursors that can be used are well known to those skilled in the art.
• the precursors of the non-noble metal (s) of the group VIII are advantageously chosen from oxides, hydroxides, hydroxycarbonates, carbonates and nitrates. Nickel hydroxycarbonate, nickel nitrate, cobalt nitrate, nickel carbonate or nickel hydroxide, cobalt carbonate or cobalt hydroxide are preferably used.
• Group VIB precursors that can be used are well known to those skilled in the art.
• the sources of molybdenum it is possible to use oxides and hydroxides, organometallic complexes, molybdic acids and their salts, in particular ammonium salts such as ammonium molybdate, ammonium heptamolybdate phosphomolybdic acid (H3PM012O40) and their salts, and optionally silicomolybdic acid (H4S1M012O40) and the corresponding salts.
• Molybdenum sources may also be any polyoxometalate of Keggin type, Keggin lacunary, Keggin substituted, Dawson, Anderson, Strandberg, for example.
• Molybdenum trioxide and heteropolyanions of the Strandberg (P2M05O23 6 ), Keggin (PM012O40 3 ), lacunated Keggin or substituted Keggin type known to those skilled in the art are preferably used.
• tungsten precursors 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 (H3PW12O40). ) and their salts, and optionally silicotungstic acid (H4S1W12O40) and its salts.
• Tungsten sources may also be any Keggin type polyoxometalate, 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.
• the solutions used in the different stages of successive impregnation or impregnation may optionally contain at least one precursor of a doping element chosen from boron, phosphorus and silicon, and / or at least one organic compound.
• the precursors of said doping element and / or the organic compound may also advantageously be added in impregnating solutions which do not contain the precursors of at least one group VIB element and at least one group VIII element, taken alone or in mixture.
• Said organic compound, when it is added, is advantageously deposited by impregnation, before the impregnation of the metal precursors, by co-impregnation with the metal precursors or post-impregnation after impregnation of the metal precursors.
• Said organic compound may be chosen from chelating agents, non-chelating agents and reducing agents. It may also be chosen from optionally etherified mono-, di- or polyalcohols, carboxylic acids, sugars, non-cyclic mono, di or polysaccharides such as glucose, fructose, maltose, lactose or sucrose, esters, ethers, crown ethers, cyclodextrins and compounds containing sulfur or nitrogen such as nitriloacetic acid, ethylenediaminetetraacetic acid, or diethylenetriamine alone or in admixture.
• said group VIII metal precursors and Group VIB metals, the precursors of the doping elements and the organic compounds are advantageously introduced into the impregnation solution (s) in a corresponding amount:
• group VIII element (s) group VIII element (s) to group VIB element (s) of between 0.1 and 0.8, and preferably between 0.15 and 0.6,
• dopant element (s) for example B, Si, P
• element (s) of group VIB between 0 and 1, and preferably between 0.08 and 0.7
• the impregnation or the successive impregnations is (are) followed (s) of a maturation step.
• This maturation allows the diffusion of the precursors within the porosity of the support. It is advantageously carried out at atmospheric pressure and at a temperature of between 17 ° C. and 50 ° C.
• a ripening time of from ten minutes to forty-eight hours and preferably from thirty minutes to five hours is generally sufficient. Longer durations are not excluded.
• a drying step at a temperature of less than or equal to 120 ° C may further be carried out following the maturation step.
• This drying makes it possible to eliminate all or part of the solvent used during the impregnation. It is advantageously carried out according to any technique known to those skilled in the art.
• the drying step is advantageously carried out at atmospheric pressure under air or under inert gas (dinitrogen or argon) or under reduced pressure. In a preferred manner, this step is carried out under reduced pressure. It is advantageously carried out at a temperature of between 50 and less than 120 ° C., preferably of between 60 and 120 ° C. and very preferably of between 80 and 120 ° C.
• this drying step has a duration of between 30 minutes and 4 hours and preferably between 1 hour and 3 hours.
• step d) of depositing at least one element of group VIB and at least one element of group VIII consists of an impregnation step, followed by a maturation step carried out at atmospheric pressure, at a temperature between 17 ° C and 50 ° C, for a period of between 10 minutes and 48 hours, then a drying step at a temperature of less than or equal to 120 ° C.
• the catalyst used in the process according to the invention is prepared according to a process comprising a step of sulphurizing the solid obtained at the end of step d).
• This sulphurization step may be advantageously carried out ex situ or in situ, that is to say respectively outside or inside the hydrotreatment reactor.
• the solid obtained at the end of step d) is ex-situ sulphurated using a H2S / H2 or H2S / N2 gas mixture containing at least 5% by volume of EDS, a temperature equal to or greater than the ambient temperature, under a total pressure equal to or greater than 1 bar for at least 2 hours.
• the sulfurization temperature is greater than or equal to 250 ° C.
• the sulphurization temperature is greater than or equal to 350 ° C.
• the sulphurization step may also be carried out in situ, prior to the implementation of the method according to the invention, by any sulphurization process well known to those skilled in the art.
• the sulphurization step is, in particular, carried out using the feedstock to be treated in the presence of hydrogen (H2) and hydrogen sulphide (H2S) introduced as such or via at least one compound organic sulfur which, when decomposing, forms hydrogen sulphide (H2S).
• the organic sulfur compound may be chosen from dimethyldisulphide (DMDS), dimethylsulfide, n-butylmercaptan and polysulfide compounds. This sulphurization is carried out at a temperature of between 200 and 600 ° C.
• the composite material according to the invention, or the catalyst, or the non-activated catalyst, comprising said composite material may be in the form of powder, beads, pellets, granules, or extrusions, the shaping operations being carried out by conventional techniques known to those skilled in the art.
• the sample is then recovered and the entire process is repeated identically 7 consecutive times.
• the sorbitol concentration in the sorbitol / water mixture remains the same (10 g / l), the weight ratio of sorbitol relative to the composite is maintained at 0.5 and the volume of distilled water is maintained at 100 ml for each repetition.
• the final sample is characterized by nitrogen adsorption / desorption volumetry.
• the data are shown in Table 1.
• the corresponding sample is called C / Al2O3 ads.
• the unactivated catalysts C1 (compliant) and C2 (non-compliant) are prepared by impregnating respectively 10 g of "C / Al2O3 ads” and "calcined Al2O3 600 ° C” supports with an aqueous solution in which the following precursors were solubilized at reflux: Ni (OH) 2 and MoO 3 with H 3 PO 4.
• the volumes of solution prepared are respectively 4.1 ml and 3.8 ml.
• the concentrations of elements are adjusted so that the mass content of metal Mo is 17% by weight relative to the weight of the non-activated catalyst.
• the solids undergo a maturation step at room temperature in air for 12 h before being dried under vacuum for 4 h at 100 ° C.
• the aim of the toluene hydrogenation test is to evaluate the hydrogenating activity of the supported or bulk sulfurized catalysts in the presence of SLE and under hydrogen pressure.
• Catalysts C1 and C2 are tested on the same test unit and under the same operating conditions.
• the test is carried out in the gas phase, in a reactor in fixed fixed cross.
• the test is broken down into two distinct phases, sulphidation and catalytic testing.
• the test load is composed of dimethyl disulphide (DMDS), toluene and cyclohexane. It is also the charge that is used during the sulphidation.
• DMDS dimethyl disulphide
• the sulfurization or activation phase is carried out in situ, inside the catalytic reactor.
• the unactivated catalysts undergo a rise in temperature from room temperature to 350 ° C, in the presence of the load described above with a temperature ramp of 2 ° C / min in a fixed bed tubular reactor through a unit Flowrence type pilot (Avantium manufacturer), flowing fluids from top to bottom.
• the activation phase is maintained for 2 hours before starting the test phase.
• Stabilized catalytic activities are measured for equal volumes of catalysts (450 m ⁇ ) and at a temperature of 350 ° C.
• the measurements of hydrogenating activity are carried out 2 hours after reaching 350 ° C.
• the effluent samples are analyzed by gas chromatography.
• the catalytic performances of the catalysts are expressed using the hydrogenating activity which corresponds, following a kinetic law of order 1, to:
• % HYDoluene is the percentage of hydrogenated toluene.
• the catalytic performances are collated in Table 2. They are expressed in relative activity, while that of catalyst C2 is equal to 100.
• Table 2 shows a significant hydrogen power gain obtained with the catalyst C1 compliant with respect to the non-compliant catalyst C2.
• the catalyst C1 according to the invention, is more active in hydrogenation than the catalyst C2 which is its homologous formulation, but prepared conventionally on the non-carbonaceous alumina.

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