Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
  • C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
  • C10G45/36—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
  • C10G45/38—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with 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
  • 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
  • B01J35/64—Pore diameter
  • B01J35/653—500-1000 nm
• • 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
• • 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
  • 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
  • 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
  • B01J35/64—Pore diameter
  • B01J35/647—2-50 nm
• • 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
  • B01J35/64—Pore diameter
  • B01J35/651—50-500 nm
• • 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
  • B01J35/66—Pore distribution
• • 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
  • B01J35/66—Pore distribution
  • B01J35/69—Pore distribution bimodal
• • 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
  • B01J35/66—Pore distribution
  • B01J35/695—Pore distribution polymodal
• • 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
  • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
  • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
• • 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
  • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
  • B01J37/0063—Granulating
• • 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
  • B01J37/06—Washing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/08—Heat treatment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/08—Heat treatment
  • B01J37/10—Heat treatment in the presence of water, e.g. steam
• • 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
  • B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
  • B01J6/001—Calcining
• • 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
  • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
  • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1037—Hydrocarbon fractions
• • 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 hydrotreating gasoline cuts, in particular gasoline cuts from fluidized bed catalytic cracking units. More particularly, the present invention relates to the use of a catalyst in a process for the selective hydrogenation of a gasoline and for the weighting down of light mercaptans, and a process making it possible to jointly carry out the selective hydrogenation of polyunsaturated compounds into compounds monounsaturates contained in gasoline, as well as the weighting of light sulfur compounds by reaction with unsaturated compounds.
• conversion gasolines and more particularly those originating from catalytic cracking, which can represent 30 to 50% of the gasoline pool, have high olefin and sulfur contents.
• FCC gasoline Fluid Catalytic Cracking
• the process according to the invention is applicable to any gasoline cut containing a certain proportion of diolefins, and which may also contain some lighter compounds belonging to the C3 and C4 cuts.
• the gasolines from cracking units are generally rich in olefins and sulfur, but also in diolefins, the content of which, for gasolines from catalytic cracking, can be up to 5% by weight.
• Diolefins are unstable compounds which can easily polymerize and must generally be removed before any treatment of these gasolines, such as hydrodesulphurization treatments intended to meet the specifications on the sulfur content in gasolines.
• this hydrogenation must be selective to the diolefins and limit the hydrogenation of the olefins in order to limit the consumption of hydrogen as well as the loss of octane of the gasoline.
• the diene compounds present in the filler to be treated are unstable and tend to form gums by polymerization.
• This gum formation leads to progressive deactivation of the hydrodesulphurization catalyst located downstream or progressive clogging of the hydrodesulphurization reactor.
• catalysts which limit the formation of polymers i.e. catalysts with low acidity or whose porosity is optimized to facilitate the continuous extraction of polymers or precursors of gums by the hydrocarbons in the feed, to ensure maximum cycle time for the catalyst.
• Document US 6,589,908 discloses a method for preparing a catalyst support, which does not contain macroporosity and has a bimodal porous structure in the mesoporosity such that the two modes of porosity are separated by 1 to 20 nm.
• the support can be used in numerous catalytic applications, and in particular in hydrotreating, in particular in hydrodenitrogenation.
• Document US 5,266,300 discloses a method for preparing a porous alumina support for use as a hydrodesulphurization or hydrodemetallization catalyst support, said support comprising a total pore volume of between 0.65 and 1.30 cm 3 / g, said porous support comprising two populations of macropores, of which approximately 2 to 20% by volume relative to the total pore volume is in the form of macropores having a diameter of between 10,000 Angstroms and 100,000 Angstroms (1000 and 10000 nm), about 5-30% by volume of the total pore volume is in the form of macropores having a diameter between 1,000 Angstroms and 10,000 Angstroms (100 and 1000 nm), and about 50-93% by volume relative to the total pore volume is in the form of mesopores having a pore diameter between 30 Angstroms and 1000 Angstroms (3-100 nm).
• the documents CN108855197, CN104248987 and CN104248985 disclose catalysts for various catalytic applications (propane dehydrogenation, esterification) whose support has a tri-modal pore distribution, the mesopore populations being centered on three peaks respectively between 2 and 4 nm, 5 and 15nm and 10 and 40nm.
• US7,790,130 discloses an alumina for the capture of halides comprising a tri-modal porosity of which 40 to 49% by volume relative to the total pore volume of the support is in the form of pores having a diameter between 15 and 50 nm .
• documents FR 2,895,414 and FR 2,895,415 disclose a process for the selective hydrogenation of polyunsaturated compounds by a catalyst having a macroporosity whose volume is between 10 and 40% of the total pore volume.
• one of the objectives of the present invention is to propose a process making it possible to jointly carry out the selective hydrogenation of polyunsaturated compounds and more particularly diolefins, as well as the weighting of light sulfur compounds and more particularly mercaptans, in the presence of a supported catalyst exhibiting performance in terms of activity and selectivity, at least as good, or even better, than the known processes of the state of the art.
• the applicant has discovered that the use of a catalyst based on at least one group VIB metal, at least one group VIII metal, on a mesoporous and macroporous support, having both a bimodal mesoporous porosity, with a high mesoporous volume coupled with a determined macroporous volume has better activity and selectivity at least as good, or even better, in the hydrogenation of diolefins while allowing better conversion of light sulfur compounds compared to the catalysts disclosed in the prior art .
• the use of such a catalyst in a process for the selective hydrogenation of gasoline improves the phenomena of diffusion internal reactants and products by the presence of populations of different sizes of mesopores.
• the combined presence of macroporosity is particularly judicious when the feed to be treated contains a significant quantity of reactive olefins (unsaturated compounds), in particular diolefins, which is the case of gasolines, which can give rise to the formation of gums and thus blocking the porosity of the catalyst without the presence of macroporosity.
• the subject of the present invention is a process for the selective hydrogenation of a gasoline comprising polyunsaturated compounds and light sulfur compounds, in which process the gasoline, hydrogen is brought into contact with a catalyst, at a temperature of between 80 °C and 220°C, with a liquid space velocity between 1 h -1 and 10 Ir 1 and a pressure between 0.5 and 5 MPa, and with a molar ratio between hydrogen and diolefins to be hydrogenated greater than 1 and less than 100 mol/mol, said catalyst comprising at least one metal from group VIB, at least one metal from group VIII, and a mesoporous and macroporous alumina support comprising a bimodal distribution of mesopores and in which:
• the volume of mesopores with a diameter greater than or equal to 2 nm and less than 18 nm corresponds between 10 and 30% by volume of the total pore volume of said support;
• the volume of mesopores with a diameter greater than or equal to 18 nm and less than 50 nm corresponds between 30 and 50% by volume of the total pore volume of said support;
• the volume of macropores with a diameter greater than or equal to 50 nm and less than 8000 nm corresponds between 30 to 50% by volume of the total pore volume of said support.
• said support comprises a specific surface of between 50 and 210 m 2 /g.
• said support comprises a total pore volume of between 0.7 and 1.3 mL/g.
• the volume of mesopores with a diameter greater than or equal to 2 nm and less than 18 nm corresponds between 15 and 25% by volume of the total pore volume of said support.
• the volume of mesopores with a diameter greater than or equal to 18 nm and less than 50 nm corresponds between 35 and 45% by volume of the total pore volume of said support.
• the volume of the macropores with a diameter greater than or equal to 50 nm and less than 8000 nm corresponds between 35 to 50% by volume of the total porous volume of said support.
• the metal content of group VIB of said catalyst, expressed in oxide form, is between 1 and 30% by weight relative to the total weight of the catalyst.
• the group VIII metal content of said catalyst, expressed in oxide form, is between 1 and 20% by weight relative to the total weight of said catalyst.
• the molar ratio between the group VIII metal and the group VIB metal is between 0.3 and 3 mol/mol.
• the Group VIII metal is nickel.
• the Group VIB metal is molybdenum.
• the porous distribution of the mesopores with a diameter greater than or equal to 2 nm and less than 18 nm is centered on a range of values comprised between 10.5 and 14.5 nm.
• the porous distribution of the mesopores with a diameter greater than or equal to 18 nm and less than 50 nm is centered on a range of values comprised between 22 and 28 nm.
• the gasoline is a catalytic cracked gasoline.
• the support is in the form of balls with a diameter of between 2 and 4 mm.
• said support when the support is in the form of beads, said support is obtained according to the following steps: s1) dehydration of an aluminum hydroxide or an aluminum oxyhydroxide at a temperature between 400°C and 1200°C, preferably between 600°C and 900°C, for a time of between 0.1 second and 5 seconds, preferably between 0.1 second and 4 seconds, to obtain an alumina powder ; s2) shaping said alumina powder obtained in step s1) in the form of balls; s3) heat treatment of the alumina balls obtained in step s2) at a temperature greater than or equal to 200° C.; s4) hydrothermal treatment of the alumina balls obtained at the end of step s3) by impregnation with water or an aqueous solution, then residence in an autoclave at a temperature between 100° C. and 300° C.; s5) calcining the alumina balls obtained at the end of step s4) at a temperature between 500°C and 820°C.
• said catalyst does not include phosphorus.
• 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.
• micropores are understood to mean pores whose diameter is less than 2 nm, that is to say 0.002 ⁇ m; by mesopores pores whose diameter is greater than 2 nm, ie 0.002 pm and less than 50 nm, ie 0.05 pm and by macropores pores whose diameter is greater than or equal to 50 nm , i.e. 0.05 ⁇ m.
• total pore volume of the alumina or of the catalyst means the volume measured by intrusion with a mercury porosimeter according to the ASTM D4284-83 standard at a maximum pressure of 4000 bar (400 MPa), using a surface tension of 484 dyne/cm and a contact angle of 140°.
• the wetting angle was taken as equal to 140° by following the recommendations of the book “Engineering techniques, analysis and characterization treatise”, p.1050-5, written by Jean Charpin and Bernard Rasneur.
• the value of the total pore volume in ml/g given in the following text corresponds to the value of the total mercury volume (total pore volume measured by intrusion with a mercury porosimeter) in ml/g measured on the sample minus the mercury volume value in ml/g measured on the same sample for a pressure corresponding to 30 psi (approximately 0.2 MPa).
• the volume of macropores and mesopores is measured by mercury intrusion porosimetry according to ASTM D4284-83 at a maximum pressure of 4000 bar (400 MPa), using a surface tension of 484 dyne/cm and a contact angle of 140°.
• the value from which the mercury fills all the intergranular voids is fixed at 0.2 MPa, and it is considered that beyond that the mercury penetrates into the pores of the sample.
• the macropore volume of the catalyst is defined as being the cumulative volume of mercury introduced at a pressure of between 0.2 MPa and 30 MPa, corresponding to the volume contained in the pores with an apparent diameter greater than 50 nm.
• the mesoporous volume of the catalyst is defined as being the cumulative volume of mercury introduced at a pressure of between 30 MPa and 400 MPa, corresponding to the volume contained in the pores with an apparent diameter of between 2 and 50 nm.
• the pore modes correspond to the inflection points of the function represented.
• the group VIII metal and group VIB metal contents are measured by X-ray fluorescence.
• the catalyst used in the context of the selective hydrogenation process according to the invention comprises an active phase formed of at least one metal from group VIB and at least one metal from group VIII.
• the group VIB metal present in the active phase of the catalyst is preferably chosen from molybdenum and tungsten, more preferably molybdenum.
• the group VIII metal present in the active phase of the catalyst is preferably chosen from cobalt, nickel and the mixture of these two elements, more preferably nickel.
• the active phase consists of molybdenum and nickel.
• the total content of group VIII metal is generally between 1 and 20% by weight, expressed in the oxide form of the group VIII metal relative to the total weight of the catalyst, preferably between 2 and 15% by weight, preferably between 3 and 13% by weight relative to the total weight of the catalyst.
• the metal content is expressed as CoO or NiO respectively.
• the group VIB metal content is generally between 1 and 30% by weight, expressed in the oxide form of the group VIB metal relative to the total weight of the catalyst, preferably between 5 and 20% by weight, and even more preferably between 8 and 15% by weight relative to the total weight of the catalyst.
• the metal is molybdenum or tungsten
• the metal content is expressed in Mo0 3 or W0 3 respectively.
• the molar ratio between the group VIII metal and the group VIB metal is advantageously between 0.3 and 3 mol/mol, preferably between 0.4 and 2.5 mol/mol, and very preferably between 0 .5 and 2 mol/mol.
• the Group VIII metal is preferably nickel.
• the Group VIB metal is preferably molybdenum.
• the catalyst does not contain phosphorus.
• the catalyst generally comprises a specific surface of between 50 and 200 m 2 /g, preferably between 60 and 170 m 2 /g and preferably between 70 and 130 m 2 /g.
• the pore volume of the catalyst is generally between 0.5 mL/g and 1.3 mL/g, preferably between 0.6 mL/g and 1.1 mL/g.
• the alumina support of the catalyst used in the context of the selective hydrogenation process according to the invention is a macroporous and mesoporous alumina support comprising a bimodal distribution of mesopores in which:
• the volume of mesopores with a diameter greater than or equal to 2 nm and less than 18 nm corresponds between 10 and 30% by volume of the total pore volume of said support;
• the volume of mesopores with a diameter greater than or equal to 18 nm and less than 50 nm corresponds between 30 and 50% by volume of the total pore volume of said support;
• the volume of macropores with a diameter greater than or equal to 50 nm and less than 8000 nm corresponds between 30 to 50% by volume of the total pore volume of said support.
• the volume of the mesopores of the support with a diameter greater than or equal to 2 nm and less than 18 nm corresponds to between 15 and 25% by volume of the total porous volume of said support.
• the volume of the mesopores of the support with a diameter greater than or equal to 18 nm and less than 50 nm corresponds to between 35 and 45% by volume of the total porous volume of said support.
• the volume of the macropores of the support with a diameter greater than or equal to 50 nm and less than 8000 nm corresponds between 35 to 50% by volume of the total porous volume of said support.
• the porous distribution of the mesopores with a diameter greater than or equal to 2 nm and less than 18 nm is centered on a range of values comprised between 10.5 and 14.5 nm, preferably between 12 and 13 nm.
• the porous distribution of the mesopores with a diameter greater than or equal to 18 nm and less than 50 nm is centered on a range of values comprised between 22 and 28 nm, preferably between 23 and 27 nm.
• the support generally comprises a specific surface comprised between 50 and 210 m 2 /g, preferably comprised between 70 and 180 m 2 /g and preferably comprised between 70 and 160 m 2 /g.
• the pore volume of the support is generally between 0.7 mL/g and 1.3 mL/g, preferably between 0.8 mL/g and 1.2 mL/g.
• the support is in the form of balls with a diameter of between 0.8 and 10 mm, preferentially between 1 and 5 mm, and more preferentially between 2 and 4 mm.
• the catalyst consists of an active phase consisting of molybdenum and nickel catalyst and the mesoporous and macroporous alumina support comprising a bimodal distribution of mesopores and in which:
• the volume of mesopores with a diameter greater than or equal to 2 nm and less than 18 nm corresponds between 10 and 30% by volume of the total pore volume of said support;
• the volume of mesopores with a diameter greater than or equal to 18 nm and less than 50 nm corresponds between 30 and 50% by volume of the total pore volume of said support;
• the volume of macropores with a diameter greater than or equal to 50 nm and less than 8000 nm corresponds between 30 to 50% by volume of the total pore volume of said support.
• alumina support of the catalyst used in the context of the selective hydrogenation process according to the invention can be synthesized by any method known to those skilled in the art.
• the alumina support used according to the invention is in the form of beads.
• the preparation of the support comprises the following steps: s1) dehydration of an aluminum hydroxide or an aluminum oxyhydroxide at a temperature between 400° C. and 1200° C., preferably between 600° C.
• alumina powder for a period of between 0.1 second and 5 seconds, preferably between 0.1 second and 4 seconds, to obtain an alumina powder; s2) shaping of said alumina powder obtained in step s1) in the form of balls; s3) heat treatment of the beads obtained in step s2) at a temperature greater than or equal to 200° C.; s4) hydrothermal treatment of the alumina balls obtained at the end of step s3) by impregnation with water or a preferentially acidic aqueous solution, then residence in an autoclave at a temperature between 100° C. and 300° C, preferably between 150°C and 250°C; s5) calcining said alumina balls obtained at the end of step s4) at a temperature between 500°C and 820°C.
• Steps s1) to s5) are described in detail below.
• step s1) dehydration of an aluminum hydroxide or an aluminum oxyhydroxide is carried out at a temperature between 400° C. and 1200° C., preferably between 600° C. and 900° C., for a period of between 0.1 second and 5 seconds, preferably between 0.1 second and 4 seconds, to obtain an alumina powder.
• the aluminum hydroxide can be chosen from hydrargillite, gibbsite or bayerite.
• the aluminum oxyhydroxide can be chosen from boehmite or diaspore.
• step s1) is carried out using hydrargillite.
• step s1) is carried out in the presence of a current of hot gas, such as dry air or moist air, making it possible to quickly eliminate and entrain the evaporated water.
• a current of hot gas such as dry air or moist air
• the active alumina powder obtained after the dehydration of the aluminum hydroxide or oxyhydroxide is ground to a particle size of between 10 to 200 ⁇ m.
• the active alumina powder obtained after the dehydration of aluminum hydroxide or oxyhydroxide is washed with water or an acidic aqueous solution.
• any mineral or organic acid may be used, preferably nitric acid, hydrochloric acid, perchloric or sulfuric acid for mineral acids, and a carboxylic acid (formic, acetic or malonic acid), a sulphonic acid (para-toluene sulphonic acid) or a sulfuric ester (lauryl sulphate) for organic acids.
• step s2) the said alumina powder obtained at the end of step s1) is shaped.
• the shaping of said alumina powder is carried out so as to obtain balls, called granulation, is generally carried out by means of rotating technology such as a rotating bezel or a rotating drum.
• This type of process makes it possible to obtain balls of controlled diameter and pore distributions, these dimensions and these distributions being, in general, created during the agglomeration step.
• the porosity can be created by various means, such as the choice of the particle size of the alumina powder or the agglomeration of several alumina powders of different particle sizes. Another method consists in mixing with the alumina powder, before or during the agglomeration step, one or more compounds, called porogens, which disappear on heating and thus create porosity in the balls.
• pore-forming compounds used mention may be made, by way of example, of wood flour, charcoal, activated carbon, carbon black, sulfur, tars, plastic materials or emulsions of plastic materials such as polyvinyl chloride, polyvinyl alcohols, naphthalene or the like.
• the amount of pore-forming compounds added is determined by the volume desired to obtain beads with a raw filling density of between 500 and 1100 kg/m 3 , preferably between 700 and 950 kg/m 3 , and with a diameter of between 0.8 and 10 mm, preferably between 1 and 5 mm, and ink more preferably between 2 and 4 mm.
• a selection by sieving of the balls obtained can be carried out according to the desired particle size.
• a heat treatment is carried out on the alumina powder shaped in the form of balls obtained at the end of step s2) at a temperature greater than or equal to at 200°C, preferably between 200°C and 1200°C, preferably between 300 and 900°C, very preferably between 400°C and 750°C, for a period generally between 1 and 24 hours, from preferably between 1 and 6 hours.
• the beads obtained at this intermediate step comprise a specific surface between 50 and 420 m 2 /g, preferably between 60 and 350 m 2 /g, and even more preferably between 80 and 300 m 2 /g.
• step s4) the alumina balls obtained at the end of step s3) undergo a hydrothermal treatment by impregnation with water or a preferably acidic aqueous solution, then stay in an autoclave at a temperature between between 100°C and 300°C, preferably between 150°C and 250°C.
• the hydrothermal treatment is generally carried out at a temperature of 100° C. to 300° C., preferentially from 150° C. to 250° C., for a duration greater than 45 minutes, preferentially from 1 to 24 hours, very preferentially from 1.5 to 12 hours.
• the hydrothermal treatment is generally carried out using an aqueous acid solution comprising one or more mineral and/or organic acids, preferably nitric acid, hydrochloric acid, perchloric acid, sulfuric acid, weak whose solution has a pH lower than 4 such as acetic acid or formic acid.
• said acidic aqueous solution also comprises one or more compounds capable of releasing anions capable of combining with aluminum ions, preferably compounds comprising a nitrate ion (such as aluminum nitrate), chloride, sulphate, perchlorate, chloroacetate, trichloroacetate, bromoacetate, dibromoacetate, and anions of general formula: R-COO such as formates and acetates.
• a nitrate ion such as aluminum nitrate
• chloride sulphate, perchlorate, chloroacetate, trichloroacetate, bromoacetate, dibromoacetate, and anions of general formula: R-COO such as formates and acetates.
• R-COO such as formates and acetates.
• the alumina balls obtained at the end of step s4) undergo calcination at a temperature of between 500° C. and 820° C., preferably between 550° C. and 750° C., and for a period generally between 1 and 24 hours, preferably between 1 and 6 hours.
• the alumina balls obtained comprise a specific surface between 50 and 210 m 2 /g, preferably between 70 and 180 m 2 /g, and even more preferably between 70 and 160 m 2 /g .
• the catalyst used in the context of the selective hydrogenation process according to the invention can be prepared by means of any technique known to those skilled in the art, and in particular by impregnation of the elements of groups VIII and VIB on the selected support.
• This impregnation can for example be carried out according to the method known to those skilled in the art under the terminology of dry impregnation, in which just the quantity of desired elements is introduced in the form of salts soluble in the chosen solvent, for example demineralized water, so as to fill as exactly as possible the pores of the support.
• the precursor of the active phase based on the element of group VIII and the precursor of the active phase of the element of group VIB can be introduced simultaneously or successively.
• the impregnation of each precursor can advantageously be carried out in at least two stages.
• the different precursors can thus be advantageously impregnated successively with a different impregnation and maturation time.
• One of the precursors can also be impregnated several times.
• the support thus filled with the solution is left to mature at a temperature below 50° C., preferably at room temperature, for a period of between 0.5 hour and 12 hours, preferably between 0.5 hour and 6 hours, and even more preferably between 0.5 and 3 hours.
• the catalyst precursor After introduction of the precursors of the active phase, the catalyst precursor undergoes an activation treatment.
• This treatment generally aims to transform the molecular precursors of the elements into the oxide phase. In this case, it is an oxidizing treatment but a simple drying of the catalyst can also be carried out.
• the catalyst precursor is dried at a temperature of between 50° C. and 200° C., preferably between 70 and 180° C., for a period typically of between 0.5 and 12 hours, and even more preferably for a period of 0.5 to 5 hours.
• 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.
• an oxidizing treatment also called calcination
• this is generally carried out in air or in dilute oxygen
• the treatment temperature is generally between 200° C. and 550° C., preferably between 300° C. C and 500°C, and advantageously for a period typically between 0.5 and 24 hours, preferably for a period of 0.5 to 12 hours, and even more preferably for a duration of 0.5 to 10 hours.
• the oxidizing treatment 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 oxidizing treatment is carried out in a traversed bed in the presence of air.
• metal salts of molybdenum and nickel that can be used in the process for preparing the catalyst are, for example, nitrate of nickel and ammonium heptamolybdate. Any other salt known to those skilled in the art having sufficient solubility and decomposing during the activation treatment can also be used.
• the drying and the oxidizing treatment are both carried out during the catalyst preparation process.
• 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 catalyst is preferably used at least partly in its sulfurized form.
• the introduction of the sulfur can take place before or after any activation step, that is to say drying or calcination.
• the sulfur or a sulfur compound can be introduced ex situ, that is to say outside the reactor where the process according to the invention is carried out, or in situ, that is to say in the reactor used for the process according to the invention.
• these ex situ sulfurizations are characterized by a final passivation step. Indeed, the sulphide phases have a very high reactivity with respect to the ambient air (self-heating character by oxidation) prohibiting their subsequent handling without additional treatment aimed at limiting this reactivity.
• the catalyst is sulfurized by passing a charge containing at least one sulfur compound, which, once decomposed, leads to the fixing of sulfur on the catalyst.
• This charge can be gaseous or liquid, for example hydrogen containing ITH S, or a liquid containing at least one sulfur compound.
• the invention relates to a process for treating a gasoline comprising any type of chemical family and in particular diolefins, mono-olefins, and sulfur compounds in the form of mercaptans and light sulphides.
• the present invention finds particular application in the transformation of conversion gasolines, and in particular gasolines originating from catalytic cracking, from fluidized bed catalytic cracking (FCC), from a coking process, from a visbreaking process, or a pyrolysis process.
• the feed is a gasoline from catalytic cracking units.
• the fillers to which the invention applies generally have a boiling point of between 0°C and 280°C.
• the fillers can also contain hydrocarbons with 3 or 4 carbon atoms.
• gasolines from catalytic cracking units contain, on average, between 0.5% and 5% by weight of diolefins, between 20% and 50% by weight of mono-olefins, between 10 ppm and 0, 5% weight of sulphur, 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 gasoline treatment described in this selective hydrogenation process mainly consists of:
• the sulfur compounds which it is sought to convert are mainly mercaptans.
• the main transformation reaction of mercaptans consists of a thioetherification reaction between the mono-olefins and the mercaptans. This reaction is illustrated below by the addition of propane-2-thiol to pent-2-ene to form a propyl-pentyl sulfide.
• the compounds likely to be thus transformed and made heavier are the sulphides and mainly CS2, COS, thiophane, methyl-thiophane.
• the charge to be treated is mixed with hydrogen before being brought into contact with the catalyst.
• the amount of hydrogen injected is such that the molar ratio between the hydrogen and the diolefins to be hydrogenated is greater than 1 (stoichiometry) and less than 100, and preferably between 1 and 10 mol/mol. Too much excess hydrogen can lead to strong hydrogenation of mono-olefins and consequently a reduction in the octane number of gasoline.
• the entire feed is generally injected at the reactor inlet. However, it may be advantageous, in certain cases, to inject a fraction or all of the charge between two beds consecutive catalysts placed in the reactor. This embodiment makes it possible in particular to continue to operate the reactor if the inlet of the reactor is clogged by deposits of polymers, particles, or gums present in the charge.
• the mixture consisting of gasoline and hydrogen is brought into contact with the catalyst at a temperature between 80°C and 220°C, and preferably between 90°C and 200°C, with a liquid space velocity ( LHSV) between 1 lr 1 and 10 h 1 , the unit of the liquid space velocity being the liter of charge per liter of catalyst and per hour (l/l.h).
• LHSV liquid space velocity
• the pressure is adjusted so that the reaction mixture is mainly in liquid form in the reactor.
• the pressure is between 0.5 MPa and 5 MPa and preferably between 1 and 4 MPa.
• the gasoline treated under the conditions stated above has a reduced content of diolefins and mercaptans.
• the gasoline produced contains less than 1% by weight of diolefins, and preferably less than 0.5% by weight of diolefins.
• Light sulfur compounds whose boiling point is lower than that of thiophene (84°C) are generally converted at more than 50%. It is therefore possible to separate the light fraction from the gasoline by distillation and send this fraction directly to the gasoline pool without additional hydrodesulphurization treatment.
• the light end of gasoline generally has an end point below 120°C, and preferably below 100°C and most preferably below 80°C.
• the selective hydrogenation process according to the invention is particularly suitable for being implemented in the context of the desulphurization process described in patent application EP 1 077247.
• the present application also relates to a gasoline desulphurization process comprising sulfur compounds, comprising at least the following stages: a) a selective hydrogenation stage implementing the process described above; b) a step of separating the gasoline obtained in step a) into two fractions comprising respectively a light gasoline and a heavy gasoline; c) a stage of hydrodesulfurization of the heavy gasoline separated in stage b) on a catalyst making it possible to at least partially decompose the sulfur compounds into HS.
• Stage b) of separation is preferably carried out by means of a conventional distillation column, also called a splitter.
• This fractionation column must make it possible to separate a light fraction of the gasoline containing less than 10 ppm by weight of sulphur.
• This column generally operates at a pressure between 0.1 and 2 MPa and preferably between 0.2 and 1 MPa.
• the number of theoretical plates of this separation column is generally between 10 and 100 and preferably between 20 and 60.
• the reflux rate expressed as being the ratio of the liquid flow in the column divided by the flow of distillate expressed in kg / h, is generally less than 1 and preferably less than 0.8.
• the light gasoline obtained at the end of the separation generally contains at least all of the C5 olefins, preferably the C5 compounds and at least 20% of the C6 olefins.
• this light fraction has a sulfur content of less than 10 ppm by weight of sulphur, that is to say that it is not necessary to treat the light cut by an additional hydrodesulphurization step before using it as fuel. .
• Step c) desulphurization is preferably a hydrodesulphurization step carried out by passing heavy gasoline, in the presence of hydrogen, over a catalyst comprising at least one element from group VIII and/or at least one element from group VIB at least partly in sulfide form, at a temperature of between about 210°C and about 350°C, preferably between 220°C and 320°C, under a pressure generally of between about 1 and about 4 MPa, preferably between 1.5 and 3 MPa.
• the space velocity of the liquid is between approximately 1 and approximately 20 h -1 (expressed in volume of liquid per volume of catalyst and per hour), preferably between 1 and 10 ir 1 , very preferably between 3 and 8 ir 1 .
• the H 2 /charge ratio is between 100 and 600 Nl/l and preferably between 300 and 600 Nl/l.
• the group VIII metal content, expressed as oxide, is generally between 0.5 and 15% by weight, preferably between 1 and 10% by weight relative to the weight of the catalyst.
• the group VIB metal content, expressed as oxide, is generally between 1.5 and 60% by weight, preferably between 3 and 50% by weight relative to the weight of catalyst.
• the group VIII element when present, is preferably cobalt
• the group VIB element when present, is generally molybdenum or tungsten. Combinations such as cobalt-molybdenum are preferred.
• the catalyst support is usually a porous solid, such as for example an alumina, a silica-alumina or other porous solids, such as for example magnesia, silica or titania, alone or in combination. mixture with alumina or silica-alumina.
• a catalyst in which the group VIB metal density, expressed in % by weight of group VIB metal in oxide form (the % by weight being expressed relative to the total weight of the catalyst) per unit of specific surface area is greater than 0, 07 and preferably greater than 0.12.
• the catalyst according to step c) preferably has a specific surface of less than 250 m 2 /g, more preferably less than 230 m 2 /g, and very preferably less than 190 m 2 /g.
• the deposition of the metals on the support is obtained by any method known to those skilled in the art such as, for example, dry impregnation, by excess of a solution containing the metal precursors.
• the impregnation solution is chosen so as to be able to dissolve the metal precursors in the desired concentrations.
• the molybdenum precursor can be molybdenum oxide, ammonium heptamolybdate and while the cobalt precursor can be for example cobalt nitrate, l hydroxide, cobalt carbonate.
• the precursors are generally dissolved in a medium allowing their solubilization in the desired concentrations.
• the catalyst is activated in a first stage.
• This activation can correspond either to an oxidation then to a reduction, or to a direct reduction, or to a calcination only.
• the calcination step is generally carried out at temperatures ranging from around 100 to around 600° C. and preferably between 200 and 450° C., under a flow of air.
• the reduction step is carried out under conditions allowing at least a part of the oxidized forms of the base metal to be converted into metal. Generally, it consists in treating the catalyst under a flow of hydrogen at a temperature preferably at least equal to 300°C.
• the reduction can also be carried out in part by means of chemical reducing agents.
• the catalyst used in step c) is preferably used at least partly in its sulfurized form.
• the introduction of the sulfur can take place before or after any activation step, that is to say calcination or reduction.
• the sulfur or a sulfur compound can be introduced ex situ, that is to say outside the hydrodesulphurization reactor, or in situ, that is to say in the hydrodesulphurization reactor.
• these ex situ sulfurizations are characterized by a final passivation step. Indeed, the sulphide phases have a very high reactivity with respect to the ambient air (self-heating character by oxidation) prohibiting their subsequent handling without additional treatment aimed at limiting this reactivity.
• the catalyst is preferably reduced under the conditions described previously, then sulphurised by passing through a charge containing at least one sulfur compound, which, once decomposed, leads to the fixing of sulfur on the catalyst.
• This charge can be gaseous or liquid, for example hydrogen containing H 2 S, or a liquid containing at least one sulfur compound.
• Example 1 Catalyst A (according to the invention)
• Support S1 of catalyst A is prepared by dehydration of hydrargillite ( EMPLURA® , MerckTM) in order to obtain an alumina powder.
• the temperature is set at 800° C. and the contact time of the material to be dehydrated with a flow of dry air is 1 second.
• the alumina powder obtained is ground to a particle size of between 10 and 200 ⁇ m and then washed three times with a volume of distilled water equal to twice the volume of the powder used.
• Said alumina powder is shaped in the presence of carbon black (N990 Thermax ® ) with a plate granulator (GRELBEXTM P30) equipped with a conical cylindrical bowl at an angle of 30° and a rotation speed at 40 revolutions per minute so as to obtain balls with a diameter mainly comprised between 2 and 4 mm after sieving the solid.
• the quantity of carbon black is adjusted to obtain a raw filling density of the objects of 800 kg/m 3 .
• Said balls undergo a heat treatment in air at 720° C. so as to give them a specific surface area of 200 m 2 /g.
• a hydrothermal treatment is applied to said balls by impregnation of the porous volume with an aqueous solution of nitric acid (0.1 N, MerckTM).
• the hydrothermal treatment is carried out at a temperature of 200° C. for 6.5 hours, in a rotating basket autoclave.
• the balls thus obtained undergo a final calcination treatment in air at 650° C. for 2 hours.
• the support S1 has a specific surface of 141 m 2 /g, a total pore volume of 0.97 mL/g as well as the following pore distribution given by mercury porosimetry:
• - a volume of mesopores with a diameter greater than or equal to 18 nm and less than 50 nm, whose pore distribution is centered on 26 nm, of 0.43 mL/g corresponding to 44% of the total pore volume; - a volume of macropores with a diameter greater than or equal to 50 nm and less than 8000 nm of 0.39 mL/g, corresponding to 40% of the total pore volume.
• Support S1 has a water uptake volume of 0.95 mL/g.
• the impregnation solution is prepared by diluting 6.07 grams of ammonium heptamolybdate (Mq 7 (NH 4 ) 6 q 24.4H 2 0, 99.98%, MerckTM), 17.43 grams of nickel nitrate (Ni(N0 3 ) 2 , 6H 2 0, 99.5%, MerckTM) in 36.2 mL of distilled water. After dry impregnation of 40 grams of support and a maturation step for 12 hours in an atmosphere saturated with humidity, the solid is dried for 12 hours at 120°C. The solid is then calcined in air at 450° C. for 2 hours.
• Catalyst A has a total pore volume of 0.83 mL/g and a specific surface of 103 m 2 /g.
• Example 2 Catalyst B not compliant (Catalyst and monomodal mesoporous orand)
• Support S2 of catalyst B is prepared by dehydration of hydrargillite ( EMPLURA® , Merck) in order to obtain an active alumina powder.
• the temperature is set at 800° C. and the contact time of the material to be dehydrated with a flow of dry air is 1 second.
• the active alumina powder obtained is ground to a particle size of between 10 and 200 ⁇ m and is then washed three times with a volume of distilled water equal to twice the volume of the powder used.
• Said active alumina powder is shaped with a plate granulator (GRELBEXTM P30) equipped with a conical cylindrical bowl at an angle of 30° and a rotation speed of 40 revolutions per minute so as to obtain balls with a diameter mostly between 2 and 4 mm (after sieving the solid) and a raw filling density of the objects of 780 kg/m 3 .
• Said balls undergo a heat treatment in air at 700° C. so as to give them a specific surface area of 250 m 2 /g.
• a hydrothermal treatment is applied to said balls by impregnation of the porous volume with an aqueous solution of nitric acid (0.1 N, MerckTM). The hydrothermal treatment is carried out at a temperature of 200° C.
• the support S2 has a specific surface of 71 m 2 /g, a total pore volume of 0.56 mL/g as well as the following porous distribution given by mercury porosimetry:
• - a volume of mesopores with a diameter greater than or equal to 10 nm and less than 50 nm, whose pore distribution is centered on 20 nm, of 0.35 mL/g corresponding to 63% of the total pore volume; - a volume of macropores with a diameter greater than or equal to 50 nm and less than 8000 nm of 0.21 mL/g, corresponding to 38% of the total pore volume.
• Support S2 has a water uptake volume of 0.54 mL/g.
• the impregnation solution is prepared by diluting 2.76 grams of ammonium heptamolybdate (Mq 7 (NH 4 ) 6 q 24.4H 2 0, 99.98%, MerckTM), 8.80 grams of nickel nitrate (Ni(N0 3 ) 2 , 6H 2 0, 99.5%, MerckTM) in 20.7 mL of distilled water. After dry impregnation of 40 grams of support and a maturation step for 12 hours in an atmosphere saturated with humidity, the solid is dried for 12 hours at 120°C.
• a second impregnation step is carried out with a solution prepared by diluting 3.18 grams of ammonium heptamolybdate (Mq 7 (NH 4 ) 6 q 24 .4H 2 0, 99.98%, MerckTM), 7.69 grams of nickel nitrate (Ni(NC>3)2, 6H 2 0, 99.5%, MerckTM) in 18.8 mL of distilled water. After dry impregnation of 40 grams of support and a maturation step for 12 hours in an atmosphere saturated with humidity, the solid is dried for 12 hours at 120°C. The solid is then calcined in air at 450° C. for 2 hours.
• Catalyst B has a total pore volume of 0.45 mL/g and a specific surface of 59 m 2 /g.
• a commercial support S3 (SA52124, UniSpheres® NorPro) is provided in the form of beads with a diameter of between 2 and 4 mm.
• the S3 support has a specific surface area of 8 m 2 /g, a total pore volume of 0.33 mL/g as well as the following pore distribution given by mercury porosimetry:
• - a volume of macropores with a diameter greater than or equal to 50 nm and less than 8000 nm of 0.33 mL/g, corresponding to 100% of the total pore volume.
• Support S3 has a water uptake volume of 0.47 mL/g.
• the impregnation solution is prepared by diluting 2.76 grams of ammonium heptamolybdate (Mq 7 (NH 4 ) 6 q 24.4H 2 0, 99.98%, MerckTM), 8.80 grams of nickel nitrate (Ni(NC>3)2, 6H 2 0, 99.5%, MerckTM) in 18 mL of distilled water. After dry impregnation of 40 grams of support and a maturation step for 12 hours in an atmosphere saturated with humidity, the solid is dried for 12 hours at 120°C.
• a second impregnation step is carried out with a solution prepared by diluting 3.18 grams of ammonium heptamolybdate (Mq 7 (NH 4 ) 6 q 24 .4H 2 0, 99.98%, MerckTM), 7.69 grams of nickel nitrate (Ni(NC>3)2, 6H 2 0, 99.5%, MerckTM) in 16.4 mL of distilled water. After dry impregnation of 40 grams of support and a maturation step for 12 hours under an atmosphere saturated with humidity, the solid is dried for 12 hours at 120°C. The solid is then calcined in air at 450° C. for 2 hours.
• Catalyst C has a total pore volume of 0.23 mL/g and a specific surface of 4 m 2 /g.
• a commercial support S4 (SA6578, NorProTM) is supplied as a 5 mm diameter extrudate.
• the S4 support has a specific surface of 175 m 2 /g, a total pore volume of 0.82 mL/g as well as the following pore distribution given by mercury porosimetry:
• - a volume of mesopores with a diameter greater than or equal to 2 nm and less than or equal to 20 nm, whose pore distribution is centered on 13 nm, of 0.82 mL/g corresponding to 100% of the total pore volume.
• the S4 support has a water uptake volume of 0.81 mL/g.
• the impregnation solution is prepared by diluting 6.06 grams of ammonium heptamolybdate (Mq 7 (NH 4 ) 6 q 24 .4H 0.99.98%, MerckTM), 17.40 grams of nitrate of nickel (Ni(NC>3)2, 6H 2 0, 99.5%, MerckTM) in 30.7 mL of distilled water. After dry impregnation of 40 grams of support and a maturation step for 12 hours in an atmosphere saturated with humidity, the solid is dried for 12 hours at 120°C. The solid is then calcined in air at 450° C. for 2 hours.
• Catalyst D has a total pore volume of 0.74 mL/g and a specific surface of 127 m 2 /g.
• Example 5 Non-compliant catalyst E (monomodal macroporous and small mesoporous catalyst)
• a commercial support S5 (SA6176, NorProTM) is provided in the form of an extrudate 1.6 mm in diameter.
• the S5 support has a specific surface of 250 m 2 /g, a total pore volume of 1.05 mL/g as well as the following porous distribution given by mercury porosimetry:
• the S5 support has a water uptake volume of 1.02 mL/g.
• the impregnation solution is prepared by diluting 6.00 grams of ammonium heptamolybdate (Mq 7 (NH 4 ) 6 q 24 .4H 0.99.98%, MerckTM), 17.40 grams of nitrate of nickel (Ni(NC>3)2, 6H 2 0, 99.5%, MerckTM) in 39.1 mL of distilled water.
• Catalyst E has a total pore volume of 0.84 mL/g and a specific surface of 207 m 2 /g.
• catalysts A, B, C, D and E The activity of catalysts A, B, C, D and E is evaluated by a test of selective hydrogenation of a mixture of model molecules carried out in a stirred 500 ml autoclave reactor.
• a test of selective hydrogenation of a mixture of model molecules carried out in a stirred 500 ml autoclave reactor.
• Typically between 2 and 6 grams of catalyst are sulfurized at atmospheric pressure in a sulfurization bench under an H 2 S/H 2 mixture consisting of 15% by volume of H 2 S at 1 l/g. h of catalyst and at 400°C for two hours (ramp of 5°C/min) followed by a plateau of 2 hours under pure hydrogen at 200°C.
• This protocol makes it possible to obtain sulfurization rates greater than 70% for all the catalysts in accordance with the invention.
• the catalyst thus sulfurized is transferred to the reactor in the absence of air and then brought into contact with 250 ml of model charge under a total pressure of 1.5 MPa and a temperature of 160°C.
• the pressure is kept constant during the test by supplying hydrogen.
• the charge used for the activity test has the following composition: 1000 ppm weight of sulfur of thiophene compounds in the methyl 3-thiophene form, 500 ppm weight of sulfur of mercaptans in the form of propane-2-thiol, 10% weight of olefin in the form of hexene-1, and 1% by weight diolefin in the form of isoprene, in n-heptane.
• the duration of the test is fixed at 200 minutes and the gas phase chromatographic analysis of the liquid effluent obtained makes it possible to evaluate the activities of the various catalysts in hydrogenation of isoprene (formation of methylbutenes), hydrogenation of hexene 1 (formation n-hexane) and heavier propane-2-thiol (disappearance of propane-2-thiol).
• the catalyst activity for each reaction is defined relative to the rate constant obtained for each reaction normalized per gram of catalyst.
• the rate constants are calculated assuming an order 1 for the reaction. Activities are normalized to 100% for catalyst A.
• the selectivity of the catalyst with respect to the hydrogenation of isoprene is equal to the ratio of the activities of the catalyst in the hydrogenation of isoprene and of hexene-1 A(isoprene)/A(hexene-1).
• the selectivity is normalized to 100% for catalyst A.
• the results obtained on the various catalysts are reported in Table 1 below.
• catalyst A according to the invention has an activity in diolefin hydrogenation and in mercaptan weighting which is systematically greater than that of the other catalysts.
• the selectivities are always among the highest for catalyst A according to the invention.

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