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
  • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
  • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
  • C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
• • 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
  • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
  • B01J21/04—Alumina
• • 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
  • B01J23/882—Molybdenum and cobalt
• • 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
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/613—10-100 m2/g
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/615—100-500 m2/g
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/63—Pore volume
  • B01J35/635—0.5-1.0 ml/g
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/63—Pore volume
  • B01J35/638—Pore volume more than 1.0 ml/g
• • 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
• • 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
  • C10G45/02—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
  • C10G45/06—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 containing nickel or cobalt metal, or compounds thereof
  • C10G45/08—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 containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, 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
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/02—Gasoline

Definitions

• the present invention relates to the field of the hydrotreating of gasoline cuts, in particular gasoline cuts from fluidized bed catalytic cracking units. More particularly, the present invention relates to a catalyst and its use in a process for the hydrodesulfurization of an olefinic gasoline cut containing sulfur, such as gasolines from catalytic cracking, for which it is sought to reduce the content of sulfur compounds. , without hydrogenating olefins and aromatics.
• Petroleum refining and petrochemicals are now subject to new constraints. Indeed, all countries are gradually adopting strict sulfur specifications, the objective being to achieve, for example, 10 ppm (weight) of sulfur in commercial gasoline in Europe and Japan.
• the problem of reducing sulfur content essentially focuses on gasolines obtained by cracking, whether catalytic (FCC Fluid Catalytic Cracking according to Anglo-Saxon terminology) or non-catalytic (coking, visbreaking, steam cracking), the main precursors of sulfur in gasoline pools.
• a solution, well known to those skilled in the art, for reducing the sulfur content consists in carrying out a hydrotreatment (or hydrodesulphurization) of the hydrocarbon cuts (and in particular gasolines from catalytic cracking) in the presence of hydrogen and a heterogeneous catalyst.
• this process has the major drawback of causing a very significant drop in the octane number if the catalyst used is not selective enough. This decrease in the octane number is in particular linked to the hydrogenation of the olefins present in this type of gasoline concomitantly with the hydrodesulphurization.
• the hydrodesulphurization of gasolines must therefore make it possible to respond to a double antagonistic constraint: to ensure deep hydrodesulphurization of gasolines and to limit the hydrogenation of the unsaturated compounds present.
• document US2010/219102 discloses a process for the production of a gasoline base catalyst containing one or more metals from cobalt, molybdenum, nickel and tungsten, on an oxide support based on alumina and containing besides another metal chosen from alkali metals, iron, chromium, cobalt, nickel, copper, zinc, yttrium, scandium and lanthanides.
• the alkali metal is preferably potassium.
• this document does not disclose the presence of phosphorus in the catalyst.
• document US2006/213814 discloses a process for the hydrodesulphurization of a naphtha fraction in the presence of a catalyst comprising an active phase based on a metal from group VIB, preferably molybdenum, a metal from group VIII , preferably cobalt, and a metal from group IA or MA, preferably calcium or sodium, more preferably calcium, at a content of between 0.01 and 2% by weight relative to the total weight of the catalyst and an alumina-based support.
• a metal from group VIB preferably molybdenum
• a metal from group VIII preferably cobalt
• a metal from group IA or MA preferably calcium or sodium, more preferably calcium
• one of the objectives of the present invention is to provide a catalyst and its use, a process for the hydrodesulfurization of an olefinic gasoline cut containing sulfur, exhibiting performance in terms of activity and selectivity, at least as good, or even better, than the catalysts known from the state of the art.
• the subject of the present invention is a catalyst comprising at least one element from group VIB, at least one element from group VIII, phosphorus, sodium and a support comprising alumina, the sodium content being between 50 and 2000 ppm weight in Na20 form relative to the total weight of said catalyst, and the molar ratio between phosphorus and sodium being between 1.5 and 300.
• a catalyst comprising at least one element from group VIB, at least one element from group VIII, phosphorus, sodium and a support comprising alumina, with a specific sodium and a specific molar ratio between sodium and phosphorus makes it possible, by synergistic effect, to improve the performance in a process for the hydrodesulfurization of an olefinic gasoline cut containing sulfur, and more particularly in terms of selectivity.
• the presence of sodium in a well-determined quantity added to a specific relative composition between sodium and phosphorus within the catalyst induces a modification of the interactions between the surface of the alumina support and the active phase of the catalyst and thus makes it possible to improve performance in a gasoline hydrodesulphurization process, in particular in terms of selectivity and activity.
• the total content of group VIII element is between 0.5 and 10% by weight of oxide of said group VIII element relative to the total weight of the catalyst.
• the content of group VIB element is between 1 and 30% by weight of oxide of said group VIB element relative to the total weight of the catalyst.
• the phosphorus content is between 0.1 and 10% by weight of P2O5 relative to the total weight of catalyst.
• the molar ratio between the element of group VIII and the element of group VI B is between 0.1 and 0.8.
• the molar ratio between the group VIII element and the sodium, calculated on the basis of the content of the group VIII element and the sodium content with respect to the total weight of the catalyst is comprised between 2 and 400.
• the molar ratio between the element of group VI B and sodium, calculated on the basis of the content of element of group VI B and the sodium content relative to the total weight of the catalyst is between 5 and 500.
• the molar ratio between phosphorus and the element of group VI B is between 0.2 and 0.35.
• the phosphorus content is between 0.3 and 5% by weight of P2O5 relative to the total weight of catalyst.
• the molar ratio between phosphorus and sodium calculated on the basis of the phosphorus element content and the sodium element content relative to the total weight of the catalyst, is between 2 and 100.
• the group VIII element is cobalt and the group VI B element is molybdenum.
• the specific surface of said catalyst is between 50 and 200 m 2 /g.
• the pore volume of said catalyst is between 0.5 cm 3 /g and 1.3 cm 3 /g.
• Another object according to the invention relates to a process for the hydrodesulphurization of an olefinic gasoline cut containing sulfur in which said gasoline cut is brought into contact with hydrogen and said catalyst according to the invention, said hydrodesulphurization process being carried out at a temperature of between 200 and 400° C., a total pressure of between 1 and 3 MPa, an hourly volume rate, defined as being the volume flow rate of charge relative to the volume of the catalyst, of between 1 and 10 h 1 , and a hydrogen/gasoline cut volume ratio of between 100 and 600 NL/L.
• the gasoline is a gasoline from a catalytic cracking unit.
• group VIII according to the CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IUPAC classification.
• the BET specific surface is measured by physisorption with nitrogen according to standard ASTM D3663-03, method described in the work Rouquerol F.; Rouquerol J.; Singh K. “Adsorption by Powders & Porous Solids: Principle, methodology and applications”, Academy Press, 1999.
• the total porous volume is measured by mercury porosimetry according to the ASTM D4284-92 standard with a wetting angle of 140°, for example by means of an Autopore® III model device from the Microméritics® brand.
• the catalyst according to the invention comprises at least one element from group VIB, at least one element from group VIII, phosphorus, sodium and a support comprising alumina, the sodium content being between 50 and 2000 ppm by weight, measured in Na 2 0 oxide form, relative to the total weight of said catalyst and the molar ratio between phosphorus and sodium calculated on the basis of the phosphorus content and the sodium content relative to the total weight of the catalyst being between 1.5 and 300.
• the catalyst according to the invention comprises between 50 and 2000 ppm by weight of sodium, measured in Na 2 0 oxide form, relative to the total weight of the catalyst, preferably between 100 and 1500 ppm by weight, and even more preferably between 100 and 1000 ppm weight, and even more preferably between 150 and 950 ppm weight.
• the element from group VIB is preferably chosen from molybdenum and tungsten, more preferably molybdenum.
• the group VIII element is preferably chosen from cobalt, nickel and the mixture of these two elements, more preferably cobalt.
• the total content of group VIII element is generally between 0.5 and 10% by weight of oxide of the group VIII element relative to the total weight of the catalyst, preferably between 0.8 and 9% by weight, of very preferably between 0.9 and 6% by weight of oxide of the element from group VIII relative to the total weight of the catalyst.
• the element content is expressed as CoO or NiO respectively.
• the content of group VI B element is generally between 1 and 30% by weight of oxide of the group VI B element relative to the total weight of the catalyst, preferably between 2 and 20% by weight, very preferably between 4 and 15% by weight of oxide of the element from group VI B relative to the total weight of the catalyst.
• the element is molybdenum or tungsten, the metal content is expressed as M0O 3 or WO 3 respectively.
• group VIB element, group VIII element, phosphorus and sodium in the catalyst are expressed in oxides after correction of the loss on ignition of the catalyst sample at 550°C for two hours in a muffle furnace . Loss on ignition is due to moisture loss. It is determined according to ASTM D7348.
• the phosphorus content is preferably between 0.1 and 10% by weight of P2O5 relative to the total weight of catalyst, preferably between 0.3 and 5% by weight, and even more preferably between 0.5 and 3% by weight of P2O5 relative to total catalyst weight.
• the molar ratio between phosphorus and sodium in the catalyst is between 1.5 and 300, preferably between 2 and 100, very preferably between 3 and 80, more preferably between 4 and 60.
• the molar ratio between the element of group VIII and the sodium in the catalyst is advantageously between 2 and 400, preferably between 2 and 300, very preferably between 3 and 250.
• the molar ratio is calculated on the basis the group VIII element content and the Na content relative to the total weight of the catalyst.
• the molar ratio between the element of group VIB and the sodium in the catalyst is advantageously between 5 and 500, preferably between 5 and 400, very preferably between 5 and 250.
• the molar ratio is calculated on the basis the group VIB element content and the Na content relative to the total weight of the catalyst.
• the molar ratio between the element of group VIII and the element of group VIB of the catalyst is between 0.1 and 0.8, preferably between 0.2 and 0.6, preferably between 0 .3 and 0.5 and even more preferably between 0.35 and 0.45.
• the molar ratio between phosphorus and the element of group VIB is between 0.2 and 0.35, preferably between 0.23 and 0.35 and even more preferably between 0.25 and 0.35.
• the catalyst generally comprises a specific surface comprised between 50 and 200 m 2 /g, preferably comprised between 60 and 190 m 2 /g, and preferably comprised between 60 and 170 m 2 /g.
• the pore volume of the catalyst is generally between 0.5 cm 3 /g and 1.3 cm 3 /g, preferably between 0.6 cm 3 /g and 1.1 cm 3 /g.
• the catalyst support according to the invention comprises alumina.
• the support is made of alumina.
• the presence of sodium in the catalyst comes from the presence of sodium in the support.
• the sodium content is preferably between 50 and 2500 ppm by weight of sodium, measured in its Na 2 0 oxide form, relative to the total weight of the support, preferably between 50 and 2000 ppm by weight, and again more preferably between 100 and 1500 ppm by weight.
• the pore volume of the support is generally between 0.5 cm 3 /g and 1.3 cm 3 /g, preferably between 0.65 cm 3 /g and 1.2 cm 3 /g.
• the support generally comprises a specific surface of between 50 and 200 m 2 /g, preferably between 60 and 190 m 2 /g.
• the support can be in the form of balls, extrudates of any geometry, powder, platelets, pellets, compressed cylinder, crushed solids or any other formatting.
• the support is in the form of balls of 0.5 to 6 mm in diameter or in the form of cylindrical, trilobed or quadrilobed extrudates of 0.8 to 3 mm in circumscribed diameter.
• the catalyst support according to the invention can be synthesized by various methods known to those skilled in the art, for example by rapid dehydration of a precursor of aluminum trihydroxide (Al(OH)3) type (otherwise called hydrargillite or gibbsite ) by example from the process commonly called “Bayer”. Then a shaping is carried out, for example by granulation, then a hydrothermal treatment and finally a calcination which leads to obtaining alumina.
• Al(OH)3 aluminum trihydroxide
• a hydrothermal treatment e.g. alumina
• This method is detailed in particular in the document P. Euzen, P. Raybaud, X. Krokidis, H. Toulhoat, JL Le Loarer, JP Jolivet, C. Froidefond, Alumina, in Handbook of Porous Solids, Eds F. Schüth, KSW Sing , J. Weitkamp, Wiley-VCH, Weinheim, Germany, 2002, pp. 1591-1677.
• the sodium is generally introduced during or after the synthesis of the alumina. More particularly, the sodium present in the support may already be present in the aluminum precursors, for example in the precursor of aluminum hydroxide type.
• the sodium present in the alumina support can also be introduced in the desired quantity into the support either during the shaping of the support, for example during the granulation step in the synthesis of a flash alumina or even by impregnation aluminum precursor.
• the introduction of the active phase on the support can be carried out according to any method of preparation known to those skilled in the art.
• the addition of the active phase to the support consists of bringing at least one component of a group VI B element, at least one component of a group VIII element, phosphorus and optionally sodium into contact with the support, so as to obtain a catalyst precursor.
• each co-impregnation step is preferably followed by an intermediate drying step generally at a temperature below 200° C., advantageously between 50° C. and 180°C, preferably between 60°C and 150°C, very preferably between 75°C and 140°C, generally for a period of 0.5 to 24 hours, preferably 0.5 to 12 hours .
• the impregnation solution is preferably an aqueous solution.
• the aqueous impregnation solution when it contains cobalt, molybdenum and phosphorus is prepared under pH conditions favoring the formation of heteropolyanions in solution.
• the pH of such an aqueous solution is between 1 and 5.
• the catalyst precursor is prepared by carrying out the successive depositions and in any order of a component of an element of group VIB, of a component of an element of group VIII and of the phosphorus and optionally sodium on said support.
• the deposits can be made by dry impregnation, by excess impregnation or else by precipitation-deposition according to methods well known to those skilled in the art.
• the deposition of the metal components of groups VIB and VIII, phosphorus and possibly sodium can be carried out by several impregnations with an intermediate drying step between two successive impregnations generally at a temperature below 200°C. , advantageously between 50°C and 180°C, preferably between 60°C and 150°C, very preferably between 75°C and 140°C, generally for a period of 0.5 to 24 hours, preferably from 0.5 to 12 hours.
• the solvent which enters into the composition of the impregnation solutions is chosen so as to solubilize the metallic precursors of the active phase, such as water or an organic solvent (for example an alcohol).
• the sources of molybdenum use may be made of oxides and hydroxides, 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 its salts.
• the sources of molybdenum can also be any heteropolycompound of Keggin, lacunary Keggin, substituted Keggin, Dawson, Anderson, Strandberg type, for example.
• molybdenum trioxide and the heteropolycompounds of Keggin, lacunary Keggin, substituted Keggin and Strandberg type are used.
• the tungsten precursors which can be used are also well known to those skilled in the art.
• the sources of tungsten use may be made of oxides and hydroxides, tungstic acids and their salts, in particular ammonium salts such as ammonium tungstate, ammonium metatungstate, phosphotungstic acid and their salts, and optionally silicotungstic acid (H4S1W12O40) and its salts.
• the tungsten sources can also be any heteropolycompound of Keggin, lacunary Keggin, substituted Keggin, Dawson type, for example.
• oxides and ammonium salts such as ammonium metatungstate or heteropolyanions of Keggin, lacunary Keggin or substituted Keggin type.
• cobalt precursors which can be used are advantageously chosen from oxides, hydroxides, hydroxycarbonates, carbonates and nitrates, for example. Cobalt hydroxide and cobalt carbonate are preferably used.
• the nickel precursors which can be used are advantageously chosen from oxides, hydroxides, hydroxycarbonates, carbonates and nitrates, for example. Nickel hydroxide and nickel hydroxycarbonate are preferably used.
• the phosphorus can advantageously be introduced into the catalyst at various stages of its preparation and in various ways.
• the phosphorus can be introduced during the shaping of said alumina support, or preferably after this shaping. It can advantageously be introduced alone or as a mixture with at least one of the metals from group VI B and VIII.
• the phosphorus is preferably introduced as a mixture with the precursors of the metals of group VI B and of group VIII, in whole or in part on the shaped alumina support, by dry impregnation of said alumina support with using a solution containing the metal precursors and the phosphorus precursor.
• the preferred source of phosphorus is orthophosphoric acid H 3 PO 4 , but its salts and esters such as ammonium phosphates or mixtures thereof are also suitable.
• the phosphorus can also be introduced at the same time as the element(s) of group VI B in the form, for example, of heteropolyanions of Keggin, lacunary Keggin, substituted Keggin or of the Strand
• the sodium in which sodium is added during the introduction of the active phase on the support, the sodium can advantageously be introduced into the catalyst at various stages of its preparation and in various ways. It can advantageously be introduced alone or as a mixture with at least one of the elements of group VIB and VIII and phosphorus.
• Any source of sodium known to those skilled in the art can be used.
• the source of sodium is sodium nitrate, sodium chloride, sodium hydroxide, or even sodium sulphate.
• the precursor of the catalyst is subjected to a drying step carried out by any technique known to those skilled in the art. It is advantageously carried out at atmospheric pressure or at reduced pressure. Preferably, this step is carried out at atmospheric pressure. This step is carried out at a temperature below 200° C., preferably between between 50°C and 180°C, preferably between 60°C and 150°C and very preferably between 75°C and 140°C.
• the drying step is advantageously carried out in a traversed bed using air or any other hot gas.
• the gas used is either air or an inert gas such as argon or nitrogen.
• the drying is carried out in a traversed bed in the presence of air.
• this drying step lasts between 30 minutes and 24 hours, and preferably between 1 hour and 12 hours.
• a dried catalyst is obtained which can be used as a hydrotreating catalyst after an activation phase (sulphidation step).
• the dried catalyst can be subjected to a subsequent calcination step, for example in air, at a temperature greater than or equal to 200°C.
• the calcination is generally carried out at a temperature less than or equal to 600°C, and preferably between 200°C and 600°C, and in a particularly preferred manner between 250°C and 500°C.
• the calcining time is generally between 0.5 hour and 16 hours, preferably between 1 hour and 6 hours. It is generally carried out under air. Calcination makes it possible in particular to transform the precursors of the elements of group VI B and VIII into oxides.
• activation phase Before its use as a hydrotreating catalyst, it is advantageous to subject the dried or optionally calcined catalyst to a sulfurization step (activation phase).
• This activation phase is carried out by methods well known to those skilled in the art, and advantageously under a sulfo-reducing atmosphere in the presence of hydrogen and hydrogen sulfide.
• Hydrogen sulfide can be used directly or generated by a sulfide agent (such as dimethyl disulfide).
• the hydrotreating process consists of bringing the olefinic gasoline cut containing sulfur into contact with a catalyst as described above and hydrogen under the following conditions:
• VVH hourly volume velocity
• the method according to the invention makes it possible to treat any type of olefinic gasoline cut containing sulfur, such as for example a cut from a coking unit (coking according to the Anglo-Saxon terminology), visbreaking (visbreaking according to the Anglo-Saxon terminology), steam cracking (steam cracking according to the Anglo-Saxon terminology) or catalytic cracking (FCC, Fluid Catalytic Cracking according to the Anglo-Saxon terminology).
• This gasoline may optionally be composed of a significant fraction of gasoline from other production processes such as atmospheric distillation (gasoline from direct distillation (or straight run gasoline according to Anglo-Saxon terminology) or from conversion (gasoline from coking or steam cracking)
• Said feed preferably consists of a gasoline cut from a catalytic cracking unit.
• the feed is advantageously a gasoline cut containing sulfur compounds and olefins and has a boiling point of between 30° C. and less than 250° C., preferably between 35° C. and 240° C., and preferably between 40° C. °C and 220°C.
• the sulfur content of gasoline cuts produced by catalytic cracking depends on the sulfur content of the FCC-treated feedstock, the presence or not of a pretreatment of the FCC feedstock, as well as the end point of the chopped off.
• the sulfur contents of an entire gasoline cut, in particular those coming from the FCC are above 100 ppm by weight and most of the time above 500 ppm by weight.
• the sulfur contents are often higher than 1000 ppm by weight, they can even in certain cases reach values of the order of 4000 to 5000 ppm by weight.
• gasolines from catalytic cracking units contain, on average, between 0.5% and 5% by weight of diolefins, between 20% and 50% by weight of olefins, between 10 ppm and 0.5% weight of sulfur of which generally less than 300 ppm of mercaptans.
• Mercaptans are generally concentrated in the light fractions of gasoline and more specifically in the fraction whose boiling point is below 120°C.
• the sulfur compounds present in gasoline can also comprise heterocyclic sulfur compounds, such as for example thiophenes, alkylthiophenes or benzothiophenes. These heterocyclic compounds, unlike mercaptans, cannot be eliminated by extractive processes. These sulfur compounds are therefore removed by hydrotreating, which leads to their transformation into hydrocarbons and H 2 S.
• the gasoline treated by the process according to the invention is a heavy gasoline (or HCN for Heavy Cracked Naphtha according to the Anglo-Saxon terminology) resulting from a distillation step aimed at separating a large cut from the gasoline resulting a cracking process (or FRCN for Full Range Cracked Naphtha according to the Anglo-Saxon terminology) into a light gasoline (LCN for Light Cracked Naphtha according to the Anglo-Saxon terminology) and a heavy gasoline HCN.
• the cut point of light gasoline and heavy gasoline is determined in order to limit the sulfur content of light gasoline and to allow its use in the gasoline pool preferably without additional post-treatment.
• the large FRCN cut is subjected to a selective hydrogenation step described below before the distillation step.
• Example 1 Catalyst A (not in accordance with the invention)
• TH200® alumina marketed by Sasol® 100 grams are calcined in a fixed bed traversed at 750° C. for 4 hours under an air flow of 1 L/h/g.
• the support S1 thus obtained has a specific surface area of 90 m 2 /g, a porous volume measured by mercury porosimetry of 0.60 ml/g and a loss on ignition of 2.6% by weight.
• the impregnation solution is prepared by dissolving at 90°C molybdenum oxide (2.25 g, purity 3 99.5%, Sigma-Aldrich TM), cobalt hydroxide (0.61 g, purity 99.9%, Alfa Aesar®), 85% weight phosphoric acid (0.51 g, 99.99% purity, Sigma-AldrichTM) in 15.6 mL of water. After dry impregnation of 20 grams of S1 support, the impregnated alumina is left to mature in a water-saturated atmosphere for 24 hours at room temperature, then dried at 120°C for 16 hours. The dried catalyst thus obtained is denoted A.
• the Co/Mo and P/Mo molar ratios are 0.40 and 0.28 respectively.
• the P/Na molar ratio of catalyst A is 306.
• the Co/Na and Mo/Na molar ratios are 436 and 1082 respectively.
• Example 2 Catalyst B (not in accordance with the invention)
• the support S2 is obtained from the support S1 to which sodium is then added.
• the impregnation solution is prepared by dissolving sodium nitrate (0.3 g) at 90°C in 18.6 mL of water. After dry impregnation of 20 grams of support S1, the impregnated alumina is left to mature in an atmosphere saturated with water for 24 hours at room temperature, then dried at 120° C. for 16 hours and calcined in a fixed bed traversed at 450° C. for 4 hours under an air flow of 1 L/h/g.
• the support S2 thus obtained has a pore volume measured by mercury porosimetry of 0.60 ml/g and a loss on ignition of 1.4% by weight.
• the impregnation solution is prepared by dissolving at 90°C molybdenum oxide (2.28 g, purity 399.5%, Sigma-AldrichTM), cobalt hydroxide (0.62 g, purity 99 .9%, Alfa Aesar®), 85% weight phosphoric acid (0.52 g, 99.99% purity, Sigma-AldrichTM) in 15.6 mL of water. After dry impregnation of 20 grams of S2 support, the impregnated alumina is left to mature in a water-saturated atmosphere for 24 hours at room temperature, then dried at 120°C for 16 hours. The dried catalyst thus obtained is denoted B.
• the Co/Mo and P/Mo molar ratios are 0.40 and 0.28 respectively.
• the P/Na molar ratio of catalyst B is 1.4.
• the Co/Na and Mo/Na molar ratios are 1.9 and 4.8 respectively.
• Example 3 Catalyst C (not in accordance with the invention)
• the S3 alumina support supplied by Axens® has a specific surface area of 95 m 2 /g, a pore volume measured by mercury porosimetry of 0.76 ml/g and a loss on ignition of 5.0% by weight.
• the impregnation solution is prepared by dissolving at 90°C ammonium heptamolybdate tetrahydrate (2.71 g, purity 99.98%, Sigma-AldrichTM) and cobalt nitrate hexahydrate (1.80 g, 98% purity, Sigma-AldrichTM), in 15.0 ml of water. After dry impregnation of 20 grams of S3 support, the impregnated alumina is left to mature in an atmosphere saturated with water for 24 hours at room temperature, then dried at 120° C. for 16 hours. The dried catalyst thus obtained is denoted C.
• the Co/Mo and P/Mo molar ratios are respectively 0.40 and 0.
• the P/Na molar ratio of the catalyst is 0.
• the Co/Na and Mo/Na molar ratios are 10 and 25 respectively.
• the catalyst support D is also the support S3. Cobalt, molybdenum and phosphorus are then added.
• the impregnation solution is prepared by dissolving at 90°C molybdenum oxide (2.2 g, purity 399.5%, Sigma-AldrichTM), cobalt hydroxide (0.60 g, purity 99 .9%, Alfa Aesar®), 85% weight phosphoric acid (0.48 g, 99.99% purity, Sigma-AldrichTM) in 14.9 mL of water. After dry impregnation of 20 grams of S3 support, the impregnated alumina is left to mature in a water-saturated atmosphere for 24 hours at room temperature, then dried at 120°C for 16 hours. The dried catalyst thus obtained is denoted D.
• the Co/Mo and P/Mo molar ratios are 0.40 and 0.28 respectively.
• the P/Na molar ratio of the catalyst is 7.3.
• the Co/Na and Mo/Na molar ratios are 10 and 26 respectively.
• Example 5 Assessment of catalysts A to D used in a hydrodesulfurization reactor
• the performances of catalysts A to D are evaluated in the hydrodesulphurization of a gasoline from catalytic cracking.
• a representative model charge of a catalytic cracked gasoline (FCC) containing 10% by weight of 2,3-dimethylbut-2-ene and 0.33% by weight of 3-methylthiophene (i.e. 1000 ppm by weight of sulfur in the charge) is used for the evaluation of the catalytic performances of the various catalysts.
• the solvent used is heptane.
• the catalyst Prior to the HDS reaction, the catalyst is sulfurized in-situ at 350° C. for 2 hours under a stream of hydrogen containing 15 mol% of H 2 S at atmospheric pressure.
• Each of the catalysts is successively placed in said reactor. Samples are taken at different time intervals and are analyzed by gas phase chromatography in order to observe the disappearance of the reagents and the formation of the products.
• the catalytic performances of the catalysts are evaluated in terms of catalytic activity and selectivity.
• the hydrodesulphurization (HDS) activity is expressed from the rate constant for the HDS reaction of 3-methylthiophene (kHDS), normalized by the volume of catalyst introduced and assuming first-order kinetics with respect to to the sulfur compound.
• the hydrogenation activity of olefins (HydO) is expressed from the rate constant of the hydrogenation reaction of 2,3-dimethylbut-2-ene, normalized by the volume of catalyst introduced and assuming a kinetics of order 1 with respect to the olefin.
• the selectivity of the catalyst is expressed by the normalized rate constant ratio kHDS/kHydO.
• the kHDS/kHydO ratio will be higher the more selective the catalyst.
• the values obtained are normalized by taking catalyst A as reference (relative HDS activity and relative selectivity equal to 100). The performances are therefore the relative H DS activity and the relative selectivity.
• Table 1 Table 1
• catalyst D has better performance in terms of activity and selectivity compared to non-compliant catalysts A, B and C and therefore underlines the importance of an adjusted Na 2 0 content in the catalyst and the specific and optimized P/Na molar ratio to obtain improved performance in a gasoline hydrodesulphurization process.
• This improvement in the selectivity of the catalysts is particularly advantageous in the case of an implementation in a process for the hydrodesulphurization of gasoline containing olefins for which it is sought to limit as much as possible the loss of octane due to the hydrogenation of the olefins.

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