Classifications

• • 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
  • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
  • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or 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
  • 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
  • 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
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
  • B01J31/0255—Phosphorus containing compounds
  • B01J31/0257—Phosphorus acids or phosphorus acid esters
  • B01J31/0258—Phosphoric acid mono-, di- or triesters ((RO)(R'O)2P=O), i.e. R= C, R'= C, H
• • 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
  • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
• • 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
  • B01J37/0205—Impregnation in several steps
• • 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
  • B01J37/28—Phosphorising
• • 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
  • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
  • C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
  • C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
• • 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
  • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1081—Alkanes
• • 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
  • C10G2300/10—Feedstock materials
  • C10G2300/1088—Olefins
• • 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
  • C10G2300/10—Feedstock materials
  • C10G2300/1096—Aromatics or polyaromatics
• • 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
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/44—Solvents

Definitions

• the invention relates to the field of hydrotreatments.
• a hydrotreating catalyst for hydrocarbon cuts is intended to eliminate the sulfur or nitrogen compounds contained therein in order, for example, to bring a petroleum product to the required specifications (sulfur content, aromatic content, etc.) for a given application (motor fuel, gasoline or diesel, heating oil, jet fuel). It may also be to pre-treat this load in order to remove impurities before subjecting it to various transformation processes to modify the physico-chemical properties, such as for example reforming processes, hydrocracking vacuum distillates, hydroconversion of atmospheric residues or vacuum.
• the composition and use of the hydrotreatment catalysts are particularly well described in the article by B. S Clausen, HT Tops0e, and FE Massoth, from Catalysis Science and Technology, Volume 11 (1996), Springer- Verlag.
• Anderson heteropolyanions is detected by Raman spectrometry at the surface of the aluminum support, and at high molybdenum contents.
• sulphurization refractory phases can be formed by sintering on the catalyst surface, such as the CoMoO 4 or Co 3 O 4 phases (B. S Clausen, HT Tops ⁇ e, and FE Massoth, from Catalysis Science and Technology, volume 11 (1996), Springer-Verlag).
• a solution to avoid the formation of [Al (OH) 6 Mo 6 Ois] 3 may be the use of phosphomolybdic heteropolyanions. These are traditionally obtained by introducing phosphoric acid co-impregnation with the precursors of the active phase. Molybdenum is protected by formation of more stable phosphomolybdic heteropolyanions than the heteropolyanion [Al (OH) 6 Mo 6 O 18 ] 3 -
• US Patent 4743574 Intevep proposes a solution of previously introducing all the phosphorus into the support.
• the patent describes a method for preparing a catalyst for hydrodesulfurization and hydrodenitrogenation containing an aluminophosphate or aluminoborate support and allowing the implementation of a reduced cobalt content.
• a support based on aluminophosphate that is by adding small amounts of phosphorus in P 2 O 5 form (or boron form B 2 Cb) to alumina before the deposition of the metals constituting the active phase on the support, the interactions between said metals and alumina are reduced, which makes it possible to reduce the amount of metal constituting the active phase involved, in particular the amount of cobalt, without loss of catalytic activity.
• the shaping of such supports is difficult because of the drying properties of phosphorus pentoxide (P 2 O 5 ) and does not allow the improvement of the BET surface of the final catalyst, which leads to a reduction in the dispersion. precursors of the active phase on the surface of the support.
• An advantage of the invention is to provide a process for preparing a hydrotreatment catalyst for introducing phosphorus in the form of a phosphorus compound by a step of impregnating a dried and / or calcined catalytic precursor. containing at least one member of the group VHI and / or at least one element of the group VIB and an amorphous support, said hydrotreatment catalyst obtained having a better catalytic activity compared to the catalysts of the prior art.
• Another advantage of the present invention is to provide a process for preparing a hydrotreatment catalyst allowing the introduction of a significant amount of phosphorus in the form of a phosphorus compound by a stage of impregnation of a precursor dried and / or calcined catalyst containing at least one group VIII element and / or at least one group VIB element and an amorphous support, while maintaining the specific surface area, calculated in m 2 per gram of alumina, between the catalytic precursor dried and / or calcined starting and the final catalyst obtained by the process according to the invention. It has now been found in the context of the invention a method of remedying the problems mentioned above and which, unlike the prior art, make it possible to moderate the possible reduction of the BET surface.
• the present invention describes a process for preparing a hydrotreatment catalyst comprising the following steps:
• step b) a step of maturation of said impregnated catalytic precursor resulting from step a),
• the process according to the invention because of its step a), allowing at least one impregnation of a catalytic precursor previously containing at least one element of group VIII and / or VIB and an amorphous support, preferably alumina, with an impregnation solution consisting of at least one phosphorus compound in solution in at least one polar solvent with a dielectric constant of greater than 20, makes it possible to prevent direct contact of the support amorphous, preferably alumina with said phosphorus compound.
• the process according to the invention thus makes it possible to avoid the phenomenon of dissolution of the amorphous support, preferably alumina, in the presence of the phosphorus compound, thus avoiding a decrease in the BET surface area.
• the dried and / or calcined catalytic precursor containing at least one element of the YJE group and / or at least one element of group VIB and an amorphous support, used in step a) of the process according to the invention, as well as its mode of preparation are described below.
• Said catalytic precursor used in step a) of the process according to the invention can be prepared for the most part by all methods well known to those skilled in the art.
• Said catalytic precursor contains a hydro-dehydrogenating function consisting of at least one element of the VHI group and / or of at least one element of the group VEB and optionally contains phosphorus and / or silicon as dopant and an amorphous support.
• the amorphous support of said catalytic precursor generally used is chosen from the group formed by alumina and silica-alumina.
• amorphous support is silica-alumina
• said amorphous support preferably contains at least 40% by weight of alumina.
• said amorphous support consists of alumina and very preferably of gamma-alumina.
• said amorphous support is advantageously shaped in the following manner: a matrix consisting of a wet alumina gel, such as, for example, hydrated aluminum oxyhydroxide is mixed with an acidic aqueous solution such as for example a nitric acid solution, and then kneaded. This is peptisation. After mixing, the paste obtained is passed through a die to form extrudates of diameter preferably between 0.4 and 4 mm. The extrudates then undergo a drying step at a drying temperature of between 80 and 150 ° C. The shaping of said amorphous support is then advantageously followed by a calcination step, operating at a calcination temperature of between 300 and 600 ° C. 0 C.
• a calcination step operating at a calcination temperature of between 300 and 600 ° C. 0 C.
• the hydro-dehydrogenating function of said catalytic precursor is ensured by at least one metal of group VIB of the periodic table chosen from molybdenum and tungsten, taken alone or as a mixture and / or by at least one metal of the HIV group of the periodic table. chosen from cobalt and nickel, taken alone or as a mixture.
• the total content of hydro-dehydrogenating elements of groups VIB and / or VIII is advantageously greater than 2.5% by weight oxide relative to the total weight of the catalyst.
• the metals of the hydro-dehydrogenating function advantageously consist of the combination of cobalt and molybdenum; if a high hydrodenitrogenation activity is desired, a combination of nickel and molybdenum or tungsten is preferred.
• the precursors of Group VIB elements that can be used are well known to those skilled in the art.
• oxides and hydroxides molybdic and tungstic acids and their salts, in particular ammonium salts such as ammonium molybdate, ammonium heptamolybdate, ammonium tungstate, acid phosph.omolybd.ic acid, phosphotungstic acid and their salts.
• molybdenum trioxide or phosphotungstic acid is preferably used.
• the amounts of the precursors of the group VIB elements are advantageously between 5 and 35% by weight of oxides relative to the total mass of the catalytic precursor, preferably between 15 and 30% by weight and very preferably between 16 and 29%. weight.
• the precursors of the elements of the group VIII that can be used are advantageously chosen from the oxides, hydroxides, hydroxycarbonates, carbonates and nitrates of the elements of the group VH1.
• the element of the VDI group used is cobalt
• cobalt hydroxide and cobalt carbonate are preferably used.
• nickel hydroxycarbonate is preferably used.
• the amounts of the precursors of the group VIII elements are advantageously between 1 and 10% by weight of oxides with respect to the total mass of the catalytic precursor, preferably between 1.5 and 9% by weight and very preferably between 2 and 8% weight
• the hydro-dehydrogenating function of said catalytic precursor can advantageously be introduced into the catalyst at various levels of the preparation and in various ways.
• Said hydro-dehydrogenating function can advantageously be introduced at least partly during the shaping of said amorphous support or preferably after this shaping.
• the hydro-dehydrogenating function is introduced at least in part during the shaping of said amorphous support, it can advantageously be introduced in part only at the time of mixing with an oxide gel chosen as a matrix, the rest of the hydrogenating element (s) being then introduced after kneading, and preferably after calcination of the preformed support.
• Said hydro-dehydrogenating function may also be advantageously introduced in full at the moment of mixing with the oxide gel chosen as a matrix.
• the Group VIB metal is introduced at the same time or just after the group VIII metal, regardless of the mode of introduction.
• the introduction of said hydro-dehydrogenating function on the amorphous support can advantageously be carried out by one or several impregnation in excess of solution on the support shaped and calcined, or preferably by one or several dry impregnation and very preferably by dry impregnation of said shaped and calcined support, using solutions containing metal precursor salts.
• the hydro-dehydrogenating function is introduced completely after shaping of said amorphous material, by dry impregnation of said support with an impregnating solution containing the precursor salts of the metals.
• the introduction of said hydro-dehydrogenating function can also be advantageously carried out by one or more impregnations of the shaped and calcined support, with a solution of the precursor (s) of the metal oxide of the VHI group when the (or) the precursor (s) of the Group VIB metal oxides was (were) previously introduced (s) at the time of mixing the support.
• a step of intermediate calcination of the catalyst is generally carried out at a temperature between 250 and 500 0 C.
• a dopant of the catalyst chosen from phosphorus, boron, fluorine and silicon, taken alone or as a mixture, and preferably said dopant being phosphorus, can also advantageously be introduced.
• Said dopant may advantageously be introduced alone or as a mixture with the metal or the metals of group VIB and / or the group VU1. It may advantageously be introduced just before or just after peptization of the chosen matrix, such as, for example, and preferably aluminum oxyhydroxide (boehmite) precursor of alumina.
• Said dopant may also advantageously be introduced in admixture with the Group VIB metal or the Group VIII metal, in whole or in part on the shaped amorphous support, preferably extruded alumina, by dry impregnation of said dopant.
• amorphous support using a solution containing the metal precursor salts and the dopant precursor.
• ethyl orthosilicate Si (OEt) 4 silanes, polysilanes, siloxanes, polysiloxanes, halide silicates, such as ammonium fluorosilicate (NEL t ) 2 SiFe or fluorosilicate.
• NNL t ammonium fluorosilicate
• sodium Na 2 SiF 6 - Silicomolybdic acid and its salts, silicotungstic acid and its salts can also be advantageously used.
• the silicon may be added, for example, by impregnation of ethyl silicate in solution in a water / alcohol mixture.
• the silicon may also be added, for example, by impregnating a polyalkyl siloxane silicon compound suspended in water.
• the source of boron may be boric acid, preferably orthoboric acid H 3 BO 3 , biborate or ammonium pentaborate, boron oxide, boric esters. Boron may be introduced for example by a boric acid solution in a water / alcohol mixture or in a water / ethanolamine mixture.
• the preferred phosphorus source is orthophosphoric acid H 3 PO 4 , but its salts and esters as ammonium phosphates are also suitable.
• Fluoride sources that can be used are well known to those skilled in the art.
• the fluoride anions can be introduced in the form of hydrofluoric acid or its salts. These salts are formed with alkali metals, ammonium or an organic compound.
• the salt is advantageously formed in the reaction mixture by reaction between the organic compound and the hydrofluoric acid.
• hydrolysable compounds that can release fluoride anions in water such as ammonium fluorosilicate (MHU) 2 SiFg or sodium Na 2 SiFo, silicon tetrafluoride SiF 4 .
• the fluorine may be introduced for example by impregnation with an aqueous solution of hydrofluoric acid, or ammonium fluoride or ammonium bifluoride.
• the dopant is advantageously introduced into the catalytic precursor in an amount of oxide of said dopant of between 0.1 to 40%, preferably from 0.1 to 30% and even more preferably from 0.1 to 20% when said Dopant is chosen from boron and silicon, (the% being expressed in% by weight of oxides).
• the dopant may also be advantageously introduced into the catalytic precursor in an amount of oxide of said dopant of between 0 to 20%, preferably from 0.1 to 15% and even more preferably from 0.1 to 10%, when said dopant is phosphorus, (the% being expressed in% by weight of oxides).
• the dopant may also be advantageously introduced into the catalytic precursor in an amount of oxide of said dopant of between 0 to 20%, preferably from 0.1 to 15% and even more preferably from 0.1 to 10%, when said dopant is fluorine (the% being expressed in% of oxides).
• the introduction of said hydro-dehydrogenating function and optionally a dopant of the catalyst into or onto the shaped and calcined support is then advantageously followed by a drying step during which the solvent of the metal salts precursors of ( or metal oxides (with) (usually water) is removed at a temperature between 50 and 150 0 C.
• the step of drying the catalytic precursor thus obtained is then optionally followed by a step of calcination under air, at a temperature of between 200 and 500 ° C., said step of calcination being intended to structure the oxide phase of the catalytic precursor obtained and to increase the stability of said catalytic precursor and thus its lifetime in the unit.
• said catalytic precursor is obtained by impregnation with a solution of the precursor (s) of the Group VIII metal oxide and / or Group VIB metal oxide precursor (s) on a shaped and calcined support, followed by drying at a drying temperature of between 50 and 150 ° C. C.
• the catalytic precursor thus obtained is therefore a dried catalyst precursor.
• the above impregnating solution also contains at least one dopant chosen from phosphorus and silicon, taken alone or mixed.
• said catalytic precursor is obtained by impregnation of a solution of the precursor (s) of the metal oxide of the group HIV and / or the precursor (s) of the metal oxides of group VTB on a shaped and calcined support, followed by drying at a drying temperature of between 50 and 150 0 C and calcination in air, at a temperature between 200 and 500 0 C.
• the catalytic precursor thus obtained is therefore a calcined catalytic precursor.
• the above impregnating solution also contains at least one dopant chosen from phosphorus and silicon. , taken alone or in a mixture.
• step a) of the process according to the invention The dried and / or calcined catalytic precursor thus obtained is then used in step a) of the process according to the invention.
• the dried and / or calcined catalytic precursor contains at least one element of the VDI group and / or at least one element of group VIB and an amorphous support.
• said dried and / or calcined catalytic precursor contains at least one element of group VTIT 1 chosen from cobalt and nickel, taken alone or in mixture and / or at least one element of group VIB chosen from molybdenum and tungsten, taken alone or as a mixture, at least one dopant selected from the group formed by phosphorus and silicon, taken alone or as a mixture and an amorphous support selected from alumina and silica alumina.
• said dried and / or calcined catalytic precursor contains at least one element of group VTJI, said element of group VIJI being cobalt and at least a group VIB element, said group VIB element being molybdenum, phosphorus as a dopant and an amorphous alumina support.
• said dried and / or calcined catalytic precursor contains at least one element of the VHJ group, said member of the VTJI group being nickel and at least one least one group VIB element, said group VIB element being molybdenum, phosphorus as a dopant and an amorphous alumina support.
• said dried and / or calcined catalytic precursor contains at least one element of the group VTJI, said element of the group VUI being nickel and at least one least one group VIB element, said group VIB element being tungsten, phosphorus as a dopant and an amorphous alumina support.
• step a) of the process according to the invention said dried and / or calcined catalytic precursor is impregnated with an impregnation solution consisting of at least one phosphorus compound in solution in at least one polar solvent of higher dielectric constant at 20.
• the phosphorus compound of the impregnating solution of step a) of the process according to the invention is advantageously chosen from the group formed by orthophosphoric acid H 3 PO 4, metaphosphoric acid and phosphorus pentoxide or phosphoric anhydride P 2 O 5 or P 4 O] 0 , taken alone or as a mixture, and preferably, said phosphorus compound is orthophosphoric acid H 3 PO 4 .
• the phosphorus compound of the impregnating solution of step a) of the process according to the invention may also be advantageously chosen from the group formed by dibutyl phosphate, triisobutyl phosphate, phosphate esters and phosphate ethers, taken alone. or in mixture.
• the phosphorus compound of the impregnating solution of step a) of the process according to the invention may also be advantageously chosen from the group formed by ammonium phosphate NH 4 H 2 PO 41 diammonium phosphate (NILi) 2 HPO 4 , and ammonium polyphosphate (NKO 4 P 2 O 7 , taken alone or in admixture.
• Said phosphorus compound is advantageously introduced into the impregnation solution of step a) of the process according to the invention in an amount corresponding to a molar ratio of phosphorus P per metal (metals) of group VIB of said catalytic precursor of between 0.001 to 3 mole / mole, preferably between 0.005 to 2 mole / mole, preferably between 0.005 and 1 mole / mole and very preferably between 0.01 and 1 mole / mole.
• the phosphorus compound is introduced onto the dried and / or calcined catalytic precursor by at least one impregnation step and preferably by a single step of impregnating a solution. impregnating said dried and / or calcined catalytic precursor described above.
• Said phosphorus compound may advantageously be deposited either by slurry impregnation, or by excess impregnation, or by dry impregnation, or by any other means known to those skilled in the art.
• step a) of the preparation process according to the invention is only a dry impregnation step.
• the impregnation solution of step a) consists of at least one phosphorus compound, and preferably of a single phosphorus compound in solution in at least one polar solvent of dielectric constant greater than 20.
• each of the solvent constituents of the polar solvent mixture advantageously has a dielectric constant greater than 20, and preferably greater than 24.
• said impregnation solution consists of at least one phosphorus compound and preferably of a single phosphorus compound in solution in a single polar solvent a dielectric constant greater than 20.
• said impregnation solution consists of at least one phosphorus compound and preferably of a single phosphorus compound in solution in a single polar solvent with a dielectric constant greater than 24.
• said impregnation solution consists of at least one phosphorus compound and preferably of a single phosphorus compound in solution in a mixture of two polar solvents, each of two polar solvents having a dielectric constant greater than 20.
• said impregnation solution consists of at least one phosphorus compound and preferably of a single phosphorus compound in solution in a mixture of two polar solvents, each of the two polar solvents having a dielectric constant greater than
• said impregnation solution consists solely of at least one phosphorus compound and preferably only a single phosphorus compound in solution in at least one a polar solvent, free of metals, with a dielectric constant greater than 20.
• said impregnation solution consists solely of at least one phosphorus compound and preferably only a single phosphorus compound in solution in a single polar solvent, free of metals, with a dielectric constant greater than 20.
• said impregnating solution consists solely of at least one phosphorus compound and preferably only a single phosphorus compound in solution in a mixture of two polar solvents, free of metals, each of the two polar solvents having a dielectric constant greater than 20.
• said impregnating solution consists solely of at least one phosphorus compound and preferably only of a single phosphorus compound in solution in at least one polar solvent, free of metals, with a dielectric constant greater than 24.
• said impregnation solution consists solely of at least one phosphorus compound and preferably only a single phosphorus compound in solution in a single polar solvent, free of metals, with a dielectric constant greater than 24.
• said impregnating solution consists solely of at least one phosphorus compound and preferably only a single phosphorus compound in solution in a mixture of two polar solvents, free of metals, each of the two polar solvents having a dielectric constant greater than 24.
• Said polar solvent used in step a) of the process according to the invention is advantageously chosen from the group of polar protic solvents chosen from methanol, ethanol, water, phenol, cyclohexanol and 1,2-dichloroethane. ethanediol, taken alone or as a mixture.
• Said polar solvent used in step a) of the process according to the invention may also be advantageously chosen from the group formed by propylene carbonate, DMSO (dimethylsulfoxide) or sulfolane, taken alone or as a mixture.
• a polar protic solvent is used.
• step a) of the preparation process according to the invention it is possible to carry out several successive impregnation steps using an impregnating solution consisting of at least one phosphorus compound, and preferably of a single phosphorus compound in solution in a suitable polar solvent defined above.
• step b) of the preparation process according to the invention the impregnated catalytic precursor from the impregnation step a) is subjected to a maturation stage that is particularly important for the invention.
• Stage b) of maturation of said impregnated catalytic precursor resulting from stage a) is advantageously carried out at atmospheric pressure and at a temperature between room temperature and 60 ° C. and during a maturation period of between 12 hours and 340 hours. and preferably between 24 hours and 170 hours.
• the duration of the maturation is advantageously a function of the temperature at which this step is performed.
• One way to verify that the ripening time is sufficient is to characterize the distribution of the phosphorus in the impregnated catalytic precursor from step a) of the process according to the invention, by techniques, such as a Castaing microprobe giving a distribution profile of the various elements, a transmission electron microscopy coupled to a X analysis of the catalyst components, or even by establishing a distribution map of the elements present in the catalyst by electron microprobe.
• the phosphorus will be distributed in crust with respect to said catalytic precursor when it contains phosphorus.
• step c) of the preparation process according to the invention the catalytic precursor from step b) is subjected to a drying step, without a subsequent calcination step of said catalyst precursor from step b).
• the purpose of this step is advantageously to remove all or part of the solvent that allowed the introduction of said phosphorus compound.
• the c) drying step of the process according to the invention is advantageously carried out by any technique known to those skilled in the art.
• the drying step c) of the process according to the invention is advantageously carried out in an oven at atmospheric pressure or under reduced pressure and at a temperature of between 50 and 200 ° C., preferably between 60 and 190 ° C., and very preferred, between 60 and 150 0 C, for a drying time of between 30 minutes and 4 hours and preferably between 1 hour and 3 hours. Drying can advantageously be carried out in crossed bed using air or any other hot gas.
• the gas used is either air or an inert gas such as argon or nitrogen.
• step c) of the process according to the invention a dried catalyst is obtained which is not subjected to any subsequent calcination step.
• step c) of the process according to the invention said dried catalyst obtained is advantageously subjected to a step d) of sulphurization, without intermediate calcination step.
• Said dried catalyst obtained at the end of stage c) of the process according to the invention is advantageously sulphurized ex situ or in situ.
• the sulfurizing agents are advantageously the H 2 S gas or any other sulfur-containing compound used to activate hydrocarbon feeds to sulphurize the catalyst.
• Said sulfur-containing compounds are advantageously chosen from alkyldisulphides such as, for example, dimethyl disulphide, alkyl sulphides, such as, for example, dimethyl sulphide, n-butyl mercaptan or polysulfide compounds of the tertiononyl polysulfide type such as, for example, TPS-37 or TPS. -54 marketed by Arkema, or any other compound known to those skilled in the art to obtain a good sulfuration of the catalyst.
• the dried catalysts obtained by the process according to the invention and having previously undergone a step d) of sulfurization are advantageously used for the hydrorefining and hydroconversion reactions of hydrocarbon feedstocks such as petroleum fractions, coal cuts or hydrocarbons produced from natural gas and more particularly for the hydrogenation, hydrodenitrogenation, hydrodeoxygenation, hydrodearomatization, hydrodesulfurization, hydrodemetallation and hydroconversion reactions of hydrocarbon feedstocks containing aromatic compounds and or olefinic and / or naphthenic and / or paraffinic, said fillers optionally containing metals and / or nitrogen and / or oxygen and / or sulfur.
• the catalysts obtained by the process according to the invention and having optionally previously undergone a step d) of sulfurization have an improved activity compared to the catalysts of the prior art.
• amorphous dried catalysts obtained by the process according to the invention and having previously undergone a step d) of sulfurization may also be advantageously used for the hydrocracking reactions.
• the feedstocks employed in the processes employing the hydrorefining and hydroconversion reactions of hydrocarbon feedstocks described above are advantageously gasolines, gas oils, vacuum gas oils, atmospheric residues, vacuum residues, atmospheric distillates, vacuum distillates, heavy fuels, oils, waxes and paraffins, used oils, residues or deasphalted crudes, fillers derived from thermal or catalytic conversion processes, alone or in mixtures. They advantageously contain heteroatoms such as sulfur, oxygen and nitrogen and / or at least one metal.
• the operating conditions used in the processes implementing the hydrorefining and hydroconversion reactions of hydrocarbon feedstocks described above are generally the following: the temperature is advantageously between 180 and 450 0 C, and preferably between 250 and 440 0 C, the pressure is advantageously between 0.5 and 30 MPa, and preferably between 1 and 18 MPa, the speed
• the hourly volume volume is advantageously between 0.1 and 20 h -1 and preferably between 0.2 and 5 h -1
• the hydrogen / charge ratio expressed as a volume of hydrogen, measured under normal conditions of temperature and pressure. per volume of liquid charge is advantageously between 501/1 to 2000 1/1.
• the dried catalysts obtained by the process according to the invention and having optionally previously undergone a step d) of sulfurization may also advantageously be used during the pretreatment of the catalytic cracking feedstock and in the first step of a hydrocracking or a mild hydroconversion. They are then generally used upstream of an acidic, zeolitic or non-zeolitic catalyst used in the second stage of the treatment.
• a matrix composed of ultrafine tabular boehmite or alumina gel sold under the name SB3 by Condisputeda Chemie GmbH was used. This gel was mixed with an aqueous solution containing 66% nitric acid (7% by weight of acid per gram of dry gel), then kneaded for 15 minutes. At the end of this mixing, the paste obtained is passed through a die having cylindrical orifices with a diameter of 1.6 mm. The extrudates are then dried overnight at 120 ° C. and then calcined at 540 ° C. for 2 hours in moist air containing 40 g of water per kg of dry air.
• Cylindrical extrudates 1.2 mm in diameter with a specific surface area of 300 m 2 / g, a pore volume of 0.70 cm 2 / g and a monomodal pore size distribution centered on 93 ⁇ are thus obtained.
• the analysis of the matrix by X-ray diffraction reveals that it is composed only of cubic gamma alumina of low crystallinity.
• the final contents of metal oxides and the specific surface area of the catalysts Cl' and Cl are then the following:
• the calcined catalyst C2 is prepared in the same manner as the calcined catalyst C1, from shaped alumina (70.7 g), molybdenum trioxide (24.23 g), cobalt hydroxide (5, 21 g) and a smaller amount of phosphoric acid (3.25 g).
• the final contents of metal oxides and the specific surface area of the C2 'and C2 catalysts are then as follows:
• the calcined catalyst C3 was prepared in the same way as Cl and C2 catalysts calcined but using a different impregnating solution based heteropolyanion type Co 2 Mo 10 O 38 H 4 6 ".
• the preparation of such solutions The impregnation method is described in patent application EP 393 802 (A1), as in Examples 1 and 2, the catalyst C 3 'corresponds to the dried catalyst obtained after the drying step
• the final contents of metal oxides and the specific surface area of the catalysts C3 'and C3 are then as follows:
• this catalyst which does not contain phosphorus in its impregnation solution, has a surface area that is even higher than that of C2 and even more so than that of Cl.
• the catalyst C4 (respectively the catalyst C4 1 ) is obtained by impregnation according to step a) of the process according to the invention of the calcined catalyst CoMoP Cl (respectively dry catalyst Cl ') so that the amount of phosphorus introduced during of this impregnation step is 0.05 (mol of P) / (mol of Mo present on calcined catalytic precursors C1 and dried Cl ').
• the phosphorus precursor used is phosphoric acid dissolved in a polar solvent consisting of a 50/50 volume water / ethanol mixture, each of the constituents of said mixture having a dielectric constant greater than 20 (the dielectric constant of water is 78.4 and the dielectric constant of ethanol is 24.5).
• the extrudates are dried at 120 ° C. for 2 hours under a pressure of 100 mbar.
• the final contents of metal oxides, the specific surface area of the C4 and C4 'catalysts and the total phosphorus molar ratio on Ptotal / Mo metals deposited in the calcined catalysts C4 and dried C4' are then as follows:
• this catalyst contains more phosphorus but its BET surface is only slightly modified by the addition of phosphorus by impregnating a solution on the catalysts Cl and Cl 'according to step a) of the process according to the invention. 'invention.
• Catalyst C5 (respectively catalyst C5 1 ) is obtained by impregnation according to step a) of the process according to the invention of calcined catalyst CoMoP C2 (respectively dried catalyst C2 ') so that the amount of phosphorus introduced during of this impregnation step is 0.44 (mol of P) / (mol of Mo present on calcined catalytic precursors C2 and dried C2 ').
• the molar ratio of total phosphorus to Ptotal / Mo metals deposited in calcined catalysts C4 and C5 and dried C4 'and C5' are thus identical, that is to say equal to 0.613 (mol of P) / (mol of Mo) .
• the phosphorus precursor used is phosphoric acid dissolved in a polar solvent consisting of a 50/50 volume water / ethanol mixture, each of the constituents of said mixture having a dielectric constant greater than 20 (the dielectric constant of water is 78.4 and the dielectric constant of ethanol is 24.5).
• a polar solvent consisting of a 50/50 volume water / ethanol mixture, each of the constituents of said mixture having a dielectric constant greater than 20 (the dielectric constant of water is 78.4 and the dielectric constant of ethanol is 24.5).
• the extrudates are dried at 120 ° C. for 2 hours under a pressure of 100 mbar.
• the final contents of metal oxides, the specific surface of the Catalysts C5 and C5 'and the total phosphorus molar ratio on Ptotal / Mo metals deposited in calcined catalysts C4 and dried C4' are then as follows:
• these catalysts have the same final formulation as the catalyst C4 and C4 'except that it has a greater amount of phosphorus introduced by step a) of the process according to the invention. Its specific surface area is higher than that of catalyst C4, in particular when this surface is expressed per gram of alumina present in the catalyst.
• the catalyst C6 (respectively the catalyst C6 ') is obtained by an impregnation according to step a) of the process according to the invention of the catalyst CoMo C3 (respectively catalyst C3') so that the amount of phosphorus introduced during this impregnation step of 0.613 (mol of P) / (mol of Mo present on calcined catalyst precursors C3 and dried C3 ').
• the total phosphorus molar ratio on Ptotal / Mo metals in the C6 calcined and C6 'dried catalysts are identical to that of the calcined catalysts C4 and C5 and dried C4' and CS ', that is to say equal to 0.613 ( mol of P) / (mol of Mo initially present on the catalytic precursor).
• the phosphorus precursor used is phosphoric acid dissolved in a polar solvent consisting of a 50/50 volume water / ethanol mixture, each of the constituents of said mixture having a dielectric constant greater than 20 (the dielectric constant of water is 78.4 and the dielectric constant of ethanol is 24.5).
• S BET Specific surface area
• these catalysts C6 and C have a molar ratio P tota i / Mo identical to that of catalysts C4, C4 ', C5 and C5' except that they have a greater amount of phosphorus introduced according to step a) of the process according to the invention. Its specific surface area is higher than that of catalysts C5 and C5 'and even more so catalysts C4 and C4'.
• Catalysts C6 and C6 ' are calcined in dry air at 450 ° C. for two hours.
• the catalysts obtained after calcination are respectively C9 and C9 '.
• the final contents of metal oxides and the specific surface area of catalysts C9 'and C9 are then as follows:
• Example 7 Comparative Test of Catalysts Cl. C3, Cl '. C2 ', C3'. C4. C4. C5. CS '. C6 and C6 ', C9 and C9' in hydrogenation of toluene in cyclohexane under pressure and in the presence of hydrogen sulfide.
• the previously described catalysts are sulfide in situ dynamically in the fixed bed fixed bed reactor through a pilot unit Catatest type (manufacturer: Geomechanical company), 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.
• the sulfurization and test load is composed of 5.8% dimethyl disulphide (DMDS), 20% toluene and 74.2% cyclohexane (by weight).
• DMDS dimethyl disulphide
• the stabilized catalytic activities of equal volumes of catalysts are thus measured in the hydrogenation reaction of toluene.
• the activity measurement conditions are as follows:
• T unconverted toluene
• MCC6 methylcyclohexane
• EtCC5 ethylcyclopentane
• DMCC5 dimethylcyclopentanes
• AHYD In (IO ( V (100-XHYD))
• Table 1 compares the relative hydrogenating activities of said catalysts, equal to the ratio of the activity of the catalyst under consideration to the activity of the catalyst C3 which is not in accordance with the invention and taken as a reference (activity 100%).
• Table 1 shows the significant activity gain obtained on the catalysts prepared according to the process according to the invention with respect to calcined reference catalysts, which do not comply with the invention, for which the entire phosphorus has been deposited on the catalyst in the impregnating solution.
• the gains are all the more important that the proportion of phosphorus introduced according to the invention relative to the total phosphorus is high.
• Table 1 also shows that there is no reduction in the specific surface area, calculated in m 2 per gram of alumina, between the starting catalyst precursor and the final catalyst obtained by the process according to the invention. This one remains constant.
• Table 2 compares the relative hydrogenating activities of the dried catalysts, equal to the ratio of the activity of the catalyst under consideration to the activity of the catalyst C3 'not in accordance with the invention and taken as a reference (activity 100%). .
• Table 2 shows the significant activity gain obtained on the dried catalysts prepared according to the process according to the invention with respect to dried reference catalysts, not according to the invention, for which the entire phosphorus has been deposited on the catalyst in the impregnating solution. It should be noted that the gain in terms of activity is greater when the invention is applied to dried catalysts than to calcined catalysts.
• the dried catalyst C7 'and its calcined version C7 are prepared in the same manner as their Cl' and Cl counterparts, except that the cobalt hydroxide is replaced by nickel hydroxycarbonate.
• the amounts of precursors used were as follows: 68.2 g of formed alumina, 24.0 g of molybdenum trioxide, 11.19 g of nickel hydroxycarbonate and 7.47 g of phosphoric acid.
• the catalyst C8 (respectively C8 ') is obtained by impregnation of the calcined NiMoP catalyst C7 (respectively dried catalyst C7') so that the amount of phosphorus introduced during this impregnation step according to step a) of method according to the invention is 0.05 mol P / mol of Mo present on the catalyst.
• the phosphorus precursor used is phosphoric acid and the solvent chosen from "Solvents and Solvent Effects in Organic Chemistry, C. Reichardt, Wiley. VCH, 3rd edition, 2003, pages 472-474 is the DMSO, with a dielectric constant of 46. After a maturation of 48 h, the extrudates are dried at 120 ° C. for 2 hours under a pressure of 100 mbar. The final contents of metal oxides and the specific surface area of the catalysts C8 and C8 'are then as follows:
• the test is conducted in an isothermal pilot reactor fixed bed traversed, flowing fluids from bottom to top. After sulfurization in situ at 350 ° C. in the unit under pressure using the test gas oil, to which 2% by weight of dimethyl disulphide is added, the hydrodesulfurization test was carried out under the following operating conditions:
• Table 3 shows the significant activity gain obtained on the catalysts. CoMo is also extrapolable to the NiMo catalysts in HDS of diesel fuel.
• the catalytic performances of the catalysts C7 'and C8' tested are given in Table 4, the dried catalyst C7 'being the reference catalyst.
• Table 3 also shows that there is no reduction in the specific surface area, calculated in m 2 per gram of alumina, between the starting calcined catalyst precursor C7 and the final catalyst obtained C8 by the process according to the invention. On the contrary, it remains constant.
• Table 4 shows the significant activity gain obtained on the CoMo catalysts is also extrapolable to NiMo catalysts in diesel HDS.
• the test is conducted in an isothermal pilot reactor fixed bed traversed, flowing fluids from bottom to top. After sulfurization in situ at 350 ° C. in the unit under pressure using a straight-run gas oil, to which 2% by weight of dimethyl disulphide is added, the hydrotreatment test was carried out under the following operating conditions:
• Table 6 shows the significant activity gain obtained on the catalyst prepared according to the invention relative to the reference catalyst.
• the calcined catalyst C9 is prepared in the same manner as the calcined catalyst C3, using the same impregnation solution, but diluted by a factor of 1.35.
• the final contents of metal oxides and the specific surface area of the calcined catalyst C9 are then as follows:
• the catalyst ClO is obtained by impregnating the calcined catalyst C9 so that the amount of phosphorus introduced during this impregnation step is 0.015 (mol of P) / (mol of Mo) present on the catalyst.
• the phosphorus precursor used is phosphoric acid, and the solvent chosen from Solvents and Solvent Effects in Organic Chemistry, C. Reichardt, Wiley-VCH, 3rd edition, 2003, pages 472-474 is methanol, a constant dielectric equal to 33. After a maturation of 96 h, the extrudates are dried at 120 ° C. for 2 hours under a pressure of 100 mbar The final metal oxide contents and the specific surface area of the C10 catalyst are then as follows:
• Example 14 Comparative test in selective hydrodesulfurization of a FCC type gasoline type charge.
• Catalysts C9 (non-compliant) and ClO (compliant) previously described were tested in the selective desulfurization reaction of a FCC type gasoline type charge.
• the test is carried out in a Grignard type reactor (in batch) at 200 ° C. under a pressure of 3.5 MPa in hydrogen which is kept constant.
• the model charge consists of 1000 ppm of 3-methylthiophene and 10% by weight of dimethyl 2,3-butene-2 in n-heptane.
• the volume of solution is 210 cm 3 cold, the mass of catalyst tested being 4 grams (before sulfuration).
• the catalyst Before testing, the catalyst is previously sulphurized in a sulfurization bench, under a mixture of H 2 SfR 2 (41 / h, 15% by volume of H 2 S) at 400 ° C. for two hours (ramp of 5 ° C./min) , then reduced under pure H 2 at 200 0 C for two hours. The catalyst is then transferred to the Grignard reactor in the absence of air.
• the rate constant (normalized per g catalyst) is calculated by assuming a sequence 1 for the desulfurization reaction (1-HDS), e t a 0 order for the hydrogenation reaction (k ⁇ oo) -
• the selectivity of a catalyst by the ratio of its rate constants, k ⁇ Ds / kHD0-
• the relative rate constants of the C9 and ClO catalysts and their selectivity are reported in Table 6 below. TABLE 6 Relative Rate Constants and Selectivity of Catalysts C9 (Non-Conforming) and ClO
• the ClO catalyst according to the invention is both more active in desulphurization and more selective than the calcined catalyst C9 (non-compliant).
• the dried catalyst CI1 'not according to the invention is prepared by impregnating the dried catalyst C2 1 with a control solution containing no phosphorus compound.
• the solvent selected from Solvents and Solvent Effects in Organic Chemistry, C.Richardhardt, Wiley-VCH, 3rd Edition, 2003, pp. 472-474 is 1,2-ethanediol, having a dielectric constant of 38.
• Catalyst C1 is a control catalyst prepared in the same manner from the calcined catalyst C2.
• Catalyst C12 ' is prepared according to the invention by impregnation with a solution containing 0.275 moles of phosphorus per mole of molybdenum present on the calcined catalyst C2.
• the phosphorus compound chosen is phosphoric acid.
• the solvent selected from Solvents and Solvent Effects in Organic Chemistry, C. Reichardt, Wiley-VCH, 3rd edition, 2003, pages 472-474 is also 1,2-ethanediol, with a dielectric constant of 38.
• the final contents in metal oxides and the specific surface area of the catalyst Cl 2 are then as follows:
• Catalyst Cl 3 ' is prepared by impregnating a solution containing 0.275 moles of phosphorus per mole of molybdenum present on the catalyst C2'.
• the phosphorus compound chosen is phosphoric acid.
• the solvent selected from Solvents and Solvent Effects in Organic Chemistry, C.Richardhardt, Wiley-VCH, 3rd edition, 2003, pages 472-474 is diethylene glycol diethyl ether with a dielectric constant of 5.7. very weakly polar and is therefore not in accordance with the invention
• the final contents of metal oxides recalculated taking into account the loss on ignition of the dried catalyst are:
• Catalysts C2, C2 '(non-compliant), CI1, CH' (non-compliant), Cl 2, Cl 2 '(compliant), Cl 3' (non-compliant) previously described were also compared in a hydrodesulfurization test. a diesel whose main characteristics are described in Example 10 of this document.
• Table 7 shows that the significant activity gain obtained on the CoMoP catalysts is well linked to the presence of the phosphorus compound introduced according to step a) of impregnating the process according to the invention.
• the catalytic performances of the catalysts CH ', C12' and C13 'tested are given in Table 8, catalyst C7' being the reference catalyst.
• Table 5 shows that, although the starting catalysts contain phosphorus which has never been calcined, a significant increase in activity is achieved by adding phosphorus in a polar solvent of higher dielectric constant than As 1,2-ethanediol in an impregnation step according to step a) of the process according to the invention.
• the gain observed for the catalyst CH ', not in accordance with the invention, impregnated with a solution containing no phosphorus compound is less. Furthermore, no increase in activity is obtained by adding phosphoric acid dissolved in a very weakly polar solvent such as diethylene glycol diethyl ether.

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