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
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  • 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
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  • 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
  • B01J23/74—Iron group metals
  • B01J23/755—Nickel
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  • B01J33/00—Protection of catalysts, e.g. by coating
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
  • B01J35/391—Physical properties of the active metal ingredient
  • B01J35/393—Metal or metal oxide crystallite size
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  • 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
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  • 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
  • B01J35/633—Pore volume less than 0.5 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
  • B01J35/635—0.5-1.0 ml/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • 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
  • B01J35/643—Pore diameter less than 2 nm
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • 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
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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • 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
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  • 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
  • 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
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
• • 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
  • B01J37/03—Precipitation; Co-precipitation
• • 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
  • B01J37/03—Precipitation; Co-precipitation
  • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/04—Mixing
• • 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
  • B01J37/16—Reducing
• • 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
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
  • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
  • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
  • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
  • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
  • C07C5/05—Partial hydrogenation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
  • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
  • C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
• • 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
  • C10G45/40—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing platinum group metals or compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/44—Hydrogenation of the aromatic hydrocarbons
  • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
  • C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/44—Hydrogenation of the aromatic hydrocarbons
  • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
  • C10G45/52—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing platinum group metals or compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
  • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
  • C07C2521/04—Alumina
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
  • C07C2523/74—Iron group metals
  • C07C2523/755—Nickel
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/14—The ring being saturated
• • 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
  • C10G2300/70—Catalyst aspects
  • C10G2300/705—Passivation

Definitions

• the subject of the invention is a co-axial nickel active phase catalyst having a texture and a formulation which are favorable for hydrogenation reactions, in particular reactions for the selective hydrogenation of polyunsaturated compounds or for the hydrogenation of aromatics.
• the invention also relates to the process for preparing said catalyst as well as its use in hydrogenation reactions.
• the most active catalysts in hydrogenation reactions are conventionally based on noble metals such as palladium or platinum. These catalysts are used industrially in refining and in petrochemistry for the purification of certain petroleum fractions by hydrogenation, in particular in reactions of selective hydrogenation of polyunsaturated molecules such as diolefins, acetylenics or alkenylaromates, or in hydrogenation reactions. aromatic. It is often proposed to substitute palladium for nickel, a less active metal than palladium, which is therefore necessary to have a larger quantity in the catalyst. Thus, nickel-based catalysts generally have a metal content of between 5 and 60 wt.% Nickel relative to the catalyst.
• the speed of the hydrogenation reaction is governed by several criteria, such as the diffusion of the reagents on the surface of the catalyst (external diffusional limitations), the diffusion of the reagents in the porosity of the support towards the active sites (internal diffusion limitations) and the intrinsic properties of the active phase such as the size of the metal particles and the distribution of the active phase within the support.
• the porous distribution of macropores and mesopores is adapted to the reaction. desired to ensure the diffusion of the reagents in the porosity of the support to the active sites and the diffusion of the formed products to the outside.
• the importance of a suitable porous distribution and in particular the presence of macropores in a selective hydrogenation reaction of a pyrolysis gasoline in the case of a palladium-based catalyst has for example been described by Z. Zhou, T. Zeng, Z. Cheng, W. Yuan, in AICHE Journal, 201 1, Vol. 57, No. 8, pages 2198-2206.
• the catalyst is all the more active as the size of the metal particles is small.
• the most conventional way of preparing these catalysts is the impregnation of the support with an aqueous solution of a nickel precursor, followed generally by drying and calcination. Before their use in hydrogenation reactions these catalysts are generally reduced in order to obtain the active phase which is in metallic form (that is to say in the state of zero valence).
• the nickel-based catalysts on alumina prepared by a single impregnation step generally make it possible to attain nickel contents of between 12 and 15% by weight of nickel, depending on the pore volume of the alumina used.
• several successive impregnations are often necessary to obtain the desired nickel content, followed by at least one drying step, then possibly a calcination step between each impregnation.
• WO201 1/080515 discloses a nickel-based catalyst on hydrogenation-active alumina, in particular aromatics, said catalyst having a nickel content greater than 35% by weight, and a large dispersion of nickel metal on the surface of a nickel. alumina with very open porosity and high surface area.
• the catalyst is prepared by at least four successive impregnations. The preparation of nickel catalysts having a high nickel content by the impregnation thus involves a sequence of many steps which increases the associated manufacturing costs.
• coprecipitation Another route of preparation also used to obtain catalysts with a high nickel content is coprecipitation.
• the coprecipitation generally consists of a simultaneous casting in a batch reactor of both an aluminum salt (aluminum nitrate for example) and a nickel salt (nickel nitrate for example). Both salts precipitate simultaneously. Then calcination at high temperature is necessary to make the transition from alumina gel (boehmite for example) to alumina. By this preparation route, contents up to 70% by weight of nickel are reached.
• Catalysts prepared by coprecipitation are described, for example, in US 4,273,680, US Pat. No. 5,518,851 and US 2010/01 1 6717.
• Comalaxing generally consists of a mixture of a nickel salt with an alumina gel such as boehmite, said mixture being subsequently shaped, generally by extrusion, then dried and calcined.
• US 5,478,791 discloses a nickel-on-alumina catalyst having a nickel content of between 10 and 60 wt.% And a nickel particle size of 15 to 60 nm prepared by the comalaxing of a nickel compound. with an alumina gel, followed by shaping, drying and reduction.
• one of the objectives of the present invention is to provide a co-axial nickel active phase catalyst with hydrogenation performance in terms of activity at least as good as the catalysts known from the state of the art. More particularly, the invention relates to a catalyst comprising a calcined predominantly aluminum oxide matrix and an active phase comprising nickel, said active phase being at least partly comalaxed within said oxide matrix, which is predominantly aluminized, the nickel content being between 5 and 65% by weight of said element relative to the total mass of the catalyst, said active phase not comprising a group VIB metal, the nickel particles having a diameter less than 15 nm, said catalyst having a median mesoporous diameter of between 8 and 25 nm, a macroporous median diameter greater than 300 nm, a mesoporous volume measured by mercury porosimetry greater than or equal to 0.30 ml. and a total pore volume measured by mercury porosimetry greater than or equal to 0.34 ml / g.
• the Applicant has discovered that the comalaxing of a predominantly calcined aluminum oxide matrix derived from a particular alumina gel prepared according to the method of preparation described below with an active phase comprising nickel, makes it possible to obtain a catalyst. which has a porous distribution and a size of nickel particles particularly suitable for hydrogenation reactions, in particular reactions for selective hydrogenation of polyunsaturated molecules such as diolefins, acetylenics or alkenylaromatician, or hydrogenation reactions of aromatics.
• the resulting porous distribution of the method of preparation by comalaxing a calcined aluminum oxide matrix obtained from a specific alumina gel, and in particular the presence of macropores makes it possible to provide a porosity that is particularly suitable for promoting the diffusion of the reagents into the porous medium and then their reaction with the active phase.
• the advantage of a comalaxing compared to an impregnation is that it avoids any risk of reducing the pore volume, or even partial blockage of the porosity of the support during the deposition of the active phase and thus the appearance of internal diffusion limitations.
• the catalyst according to the invention has the particularity of being able to contain high amounts of active phase. Indeed, the fact of preparing the catalyst according to the invention by comalaxing makes it possible to strongly charge this catalyst in the active phase in a single pass.
• the catalyst according to the invention differs structurally from a catalyst obtained by simple impregnation of a metal precursor on the alumina support in which the alumina forms the support and the active phase is introduced into the pores of this support.
• the process for preparing the catalyst according to the invention by comalaxing a particular aluminous porous oxide with one or more nickel precursors of the active phase makes it possible to obtain a composite in which the nickel particles and the The alumina is intimately mixed thereby forming the catalyst structure with a porosity and an active phase content suitable for the desired reactions.
• the catalyst has a macroporous volume of between 10 and 40% of the total pore volume. According to one variant, the catalyst does not have micropores.
• the nickel content is between 10 and 34% by weight of said element relative to the total mass of the catalyst.
• the nickel particles have a diameter of between 1.5 and 12 nm.
• the active phase is entirely comalaxed. According to another variant, part of the active phase is impregnated on the predominantly aluminized calcined oxide matrix.
• the invention also relates to the process for preparing said catalyst.
• the invention also relates to the use of the catalyst in a hydrogenation process in which the catalyst according to the invention or capable of being prepared according to the preparation method according to the invention is brought into contact in the presence of hydrogen with a hydrocarbon feed containing polyunsaturated and / or aromatic molecules so as to obtain an effluent that is at least partially hydrogenated.
• the catalyst according to the invention is in the form of a composite comprising a calcined aluminum predominantly oxide matrix within which is distributed the active phase comprising nickel.
• the characteristics of the gel having led to obtaining the alumina contained mainly in said oxide matrix, and that the textural properties obtained with the active phase confer on the catalyst according to the invention its specific properties.
• the invention relates to a catalyst comprising a calcined predominantly aluminum oxide matrix and an active phase comprising nickel, said active phase being at least partly comalaxed within said oxide matrix, which is predominantly aluminized, the nickel content being between 5 and 65% by weight of said element relative to the total mass of the catalyst, said active phase not comprising a group VIB metal, the nickel particles having a diameter of less than 15 nm, said catalyst having a median mesoporous diameter of between 8 and 25 nm, a macroporous median diameter greater than 300 nm, a mesoporous volume measured by mercury porosimetry greater than or equal to 0.30 ml / g and a total pore volume measured by mercury porosimetry greater than or equal to 0.34 ml / boy Wut.
• the nickel content is between 5 and 65% by weight of said element relative to the total mass of the catalyst, preferably between 8 and 55% by weight, more preferably between 10 and 40% by weight, and particularly preferably preferred between 10 and 34% by weight.
• the Ni content is measured by X-ray fluorescence.
• the nickel content is advantageously between 5 and 25% by weight, preferably between 8 and 25% by weight, and more preferably between 10 and 23% by weight of said element relative to the total mass of the catalyst.
• the nickel content is advantageously between 15 and 65% by weight, preferably between 18 and 55% by weight, and more preferably between between 19 and 34% by weight of said element relative to the total mass of the catalyst.
• the size of the nickel particles in the catalyst according to the invention is less than 15 nm, preferably of between 1.5 and 12 nm, and preferably of between 2 and 10 nm.
• the active phase of the catalyst may further comprise at least one additional metal selected from Group VIII metals, Group IB metals and / or tin.
• the additional metal of group VIII is chosen from platinum, ruthenium and rhodium, as well as palladium.
• the additional metal of group IB is chosen from copper, gold and silver.
• the additional metal (s) of the group VIII and / or of the group IB is (are) preferably present at a content representing from 0.01 to 20% by weight of the mass of the catalyst, preferably from 0.05 to 10% by weight of the catalyst mass and even more preferably from 0.05 to 5% by weight of the mass of said catalyst.
• the tin is preferably present at a content representing from 0.02 to 15% by weight of the catalyst mass, such that the Sn / Ni molar ratio is between 0.01 and 0.2, preferably between 0.025 and 0.055, and even more preferably between 0.03 to 0.05.
• the active phase of the catalyst does not include a Group VIB metal. It does not include molybdenum or tungsten.
• the catalyst according to the invention has a good compromise between a high pore volume, a high macroporous volume, a small size of nickel particles thus making it possible to have performance in hydrogenation in terms of activity at least as good as the catalysts known from the state of the art.
• the catalyst according to the invention also comprises a predominantly calcined aluminum oxide matrix.
• Said matrix has a calcined alumina content greater than or equal to 90% by weight relative to the total weight of said matrix, optionally supplemented with silica and / or phosphorus to a total content of at most 10% by weight in SiO 2 equivalent and / or P 2 0 5 , preferably less than 5% by weight, and very preferably less than 2% by weight relative to the total weight of said matrix.
• Silica and / or phosphorus can be introduced by any technique known to those skilled in the art, during the synthesis of the alumina gel or during the comalaxing.
• the predominantly calcined aluminum oxide matrix consists of alumina.
• the alumina present in said matrix is a transition alumina such as gamma, delta, theta, chi, rho or eta alumina, alone or as a mixture. More preferably, the alumina is a gamma, delta or theta transition alumina, alone or as a mixture.
• Said catalyst with active phase comalaxée according to the invention is generally presented in all the forms known to those skilled in the art, for example in the form of beads (generally having a diameter of between 1 and 6 mm), extruded tablets , hollow cylinders. Preferably, it consists of extrudates of diameter generally between 0.5 and 10 mm, preferably between 0.8 and 3.2 mm and very preferably between 1.0 and 2.5 mm.
• This may advantageously be in the form of cylindrical, multilobed, trilobed or quadrilobed extrudates. Preferably its shape will be trilobed or quadrilobed. The shape of the lobes can be adjusted according to all known methods of the prior art.
• the comalaxed catalyst according to the invention has particular textural properties, in particular a specific porous distribution, where the macroporous and mesoporous volumes are measured by mercury intrusion and the microporous volume is measured by nitrogen adsorption.
• Macropores means pores whose opening is greater than 50 nm.
• mesopores is meant pores whose opening is between 2 nm and 50 nm, limits included.
• micropores pores whose opening is less than 2 nm.
• total pore volume of the catalyst the volume measured by mercury porosimeter intrusion 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 anchoring angle was taken equal to 140 ° according to the recommendations of the book “Techniques of the engineer, treated analysis and characterization", pages 1050-1055, written by Jean Charpin and Bernard Rasneur.
• the value of the total pore volume corresponds to the value of the total pore volume measured by mercury porosimeter intrusion measured on the sample minus the value of the total pore volume measured by mercury porosimeter intrusion measured on the same sample for a pressure corresponding to 30 psi (about 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 at which mercury fills all the intergranular voids is fixed at 0.2 MPa, and it is considered that beyond this mercury enters the pores of the sample.
• the macroporous volume of the catalyst is defined as the cumulative volume of mercury introduced at a pressure of between 0.2 MPa and 30 MPa, corresponding to the volume contained in the pores with an apparent diameter greater than 50 nm.
• the mesoporous volume of the catalyst is defined as the cumulative volume of mercury introduced at a pressure of between 30 MPa and 400 MPa, corresponding to the volume contained in the pores with an apparent diameter of between 2 and 50 nm.
• the micropore volume is measured by nitrogen porosimetry.
• the quantitative analysis of the microporosity is carried out using the "t" method (Lippens-De Boer method, 1965) which corresponds to a transformation of the starting adsorption isotherm as described in the book “Adsorption by powders and porous solids. Principles, methodology and applications "written by F. Rouquérol, J. Rouquérol and K. Sing, Academy Press, 1999.
• the mesoporous median diameter is also defined as being the diameter such that all the pores, among all the pores constituting the mesoporous volume, of size less than this diameter constitute 50% of the total mesoporous volume determined by intrusion into the mercury porosimeter.
• the macroporous median diameter is also defined as the diameter such that all the pores, among all the pores constituting the macroporous volume, of size less than this diameter constitute 50% of the total macroporous volume determined by intrusion into the mercury porosimeter.
• the specific surface of the catalyst is meant the specific surface B.E.T. determined by nitrogen adsorption according to ASTM D 3663-78 established from the BRUNAUER-EMMETT-TELLER method described in the journal "The Journal of the American Society", 60, 309, (1938).
• the groups of chemical elements are given according to the classification CAS (CRC Handbook of Chemistry and Physics, publisher CRC press, editor-in-chief D. R. Lide, 81 st edition, 2000-2001).
• group VIII according to the CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IUPAC classification.
• the catalyst according to the invention has a total pore volume of at least 0.34 ml / g, preferably at least 0.40 ml / g, and preferably between 0.45 and 0.85 ml / g. .
• the catalyst advantageously has a macroporous volume of between 10 and 40% of the total pore volume, preferably between 15 and 38% of the total pore volume, and particularly preferably between 20 and 35% of the total pore volume.
• the mesoporous volume of the catalyst is at least 0.30 ml / g, preferably at least 0.35 ml / g, and particularly preferably between 0.35 ml / g and 0.55 ml / g. .
• the median mesoporous diameter is between 8 nm and 25 nm, and preferably between 9 and 22 nm, and particularly preferably between 10 and 20 nm.
• the catalyst has a macroporous median diameter greater than 300 nm generally between 310 and 1500 nm, preferably between 350 and 1000 nm and even more preferably between 390 and 800 nm.
• the catalyst according to the present invention has a BET specific surface area of at least 40 m 2 / g, preferably at least 50 m 2 / g, and even more preferably between 55 and 250 m 2 / g.
• the catalyst has a low microporosity, very preferably it has no microporosity.
• the present invention also relates to a process for preparing said catalyst according to the invention.
• the catalyst according to the invention with a comalaxed active phase is prepared from a specific alumina gel.
• the particular porous distribution observed in the catalyst is in particular due to the process of preparation from the specific alumina gel.
• the preparation of said alumina gel comprises the successive steps: a step of dissolving an aluminum acid precursor, a step of adjusting the pH of the suspension by means of a basic precursor, and a coprecipitation step at least one acidic precursor and at least one basic precursor, at least one of which contains aluminum and a filtration step.
• the gel is then subjected to a drying step to obtain a powder.
• the powder is then subjected to a heat treatment to obtain a calcined aluminous porous oxide.
• the calcined aluminous porous oxide is then mixed with a solution comprising the salt (s) of the precursor (s) of the active phase in order to obtain a paste.
• This paste is then shaped and dried to obtain a dried catalyst.
• the dried catalyst is optionally subjected to heat treatment, then generally reduced and subjected to a passivation treatment. More particularly, the process for preparing the catalyst according to the invention comprises the following steps:
• step b) a step of adjusting the pH by adding to the suspension obtained in step a) at least one basic precursor chosen from sodium aluminate, potassium aluminate, ammonia, hydroxide and sodium and potassium hydroxide, at a temperature between 20 and 90 ° C, and at a pH between 7 and 10, for a period of between 5 and 30 minutes,
• step e) a step of drying said alumina gel obtained in step d) to obtain a powder
• step f) a step of heat treatment of the powder obtained at the end of step e) at a temperature of between 500 and 1000 ° C., with or without a flow of air containing up to 60% by volume of water, for a period of between 2 and 10 hours, to obtain a calcined aluminous porous oxide
• step f) a step of mixing the calcined aluminous porous oxide obtained in step f) with a solution comprising at least one nickel precursor to obtain a paste
• Step a) is a step of dissolving an aluminum acid precursor chosen from aluminum sulphate, aluminum chloride and aluminum nitrate in water, at a temperature between and 90 ° C, at a pH of between 0.5 and 5, for a period of between 2 and 60 minutes.
• Step a) is carried out at a temperature between 20 and 90 ° C, preferably between 20 and 75 ° C, and more preferably between 30 and 70 ° C.
• the pH of the suspension obtained is between 0.5 and 5, preferably between 1 and 4, preferably between 1.5 and 3.5.
• This step advantageously contributes to an amount of alumina introduced relative to the final alumina of between 0.5 and 4%, preferably between 1 and 3%, very preferably between 1.5 and 2.5%.
• the suspension is left stirring for a period of between 2 and 60 minutes, and preferably 5 to 30 minutes.
• the step of adjusting the pH b) consists in adding to the suspension obtained in step a) at least one basic precursor chosen from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide.
• the basic precursor is chosen from sodium aluminate and potassium aluminate.
• the basic precursor is sodium aluminate.
• Step b) is carried out at a temperature between 20 and 90 ° C, preferably between 20 and 80 ° C and more preferably between 30 and 70 ° C and at a pH between 7 and 10, preferably between 8 and 10, preferably between 8.5 and 10 and very preferably between 8.7 and 9.9.
• the duration of step b) of pH adjustment is between 5 and 30 minutes, preferably between 8 and 25 minutes, and very preferably between 10 and 20 minutes.
• Step c) is a step of coprecipitation of the suspension obtained at the end of step b) by adding to this suspension an aqueous solution of at least one basic precursor chosen from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide and at least one acidic precursor selected from aluminum sulphate, aluminum chloride, aluminum nitrate, sulfuric acid, hydrochloric acid and nitric acid, at least one of the basic precursors or acid comprising aluminum, said precursors being selected identical or not to the precursors introduced in steps a) and b).
• at least one basic precursor chosen from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide and at least one acidic precursor selected from aluminum sulphate, aluminum chloride, aluminum nitrate, sulfuric acid, hydrochloric acid and nitric acid, at least one of the basic precursors or acid comprising aluminum, said precursors being selected identical or not to the precursors introduced in steps
• the relative flow rate of the acidic and basic precursors being chosen so as to obtain a pH of the reaction medium of between 7 and 10 and the flow rate of the acidic and basic precursor (s) containing aluminum being adjusted so as to obtain a final alumina concentration. in the suspension of between 10 and 38 g / l, preferably between 13 and 35 g / l and more preferably between 15 and 33 g / l.
• the coprecipitation step is conducted at a temperature between 20 and 90 ° C, and more preferably between 30 and 70 ° C.
• Step c) of coprecipitation is carried out at a pH of between 7 and 10, preferably between 8 and 10, preferably between 8.5 and 10, and very preferably between 8.7 and 9.9.
• Step c) of coprecipitation is carried out for a period of between 1 and 60 minutes, and preferably between 5 and 45 minutes.
• steps a), b) and c) are carried out in the absence of organic additive.
• steps a), b) and c) are carried out with stirring.
• the process for preparing the alumina according to the invention also comprises a step d) of filtering the suspension obtained at the end of step c) so as to obtain an alumina gel.
• Said filtration step is carried out according to the methods known to those skilled in the art.
• Said filtration step is advantageously followed by at least one washing step, with an aqueous solution, preferably with water and preferably from one to three washing steps, with a quantity of water equal to the amount of water. precipitate filtered.
• the alumina gel obtained at the end of the precipitation step c), followed by a filtration step d), is dried in a drying step e) in order to obtain a powder.
• Said drying step is generally carried out at a temperature greater than or equal to 120 ° C. or by atomization or by any other drying technique known to those skilled in the art.
• said drying step d) can advantageously be carried out in a closed and ventilated oven.
• said drying step is carried out at a temperature between 120 and 300 ° C, very preferably at a temperature between 150 and 250 ° C.
• drying step e) is carried out by atomization
• the "cake" obtained at the end of the second precipitation step, followed by a filtration step is resuspended.
• Said suspension is then sprayed in fine droplets, in a vertical cylindrical chamber in contact with a stream of hot air to evaporate the water according to the principle well known to those skilled in the art.
• the powder obtained is driven by the heat flow to a cyclone or a bag filter that will separate the air from the powder.
• the atomization is carried out according to the operating protocol described in the publication Asep Bayu Dani Nandiyanto, Kikuo Okuyama, Advanced Powder Technology, 22, 1-19 , 201 1.
• the powder obtained at the end of the drying step e) is then subjected to a heat treatment step f) at a temperature of between 500 and 1000 ° C., for a duration advantageously between 2 and 10 ° C. hours, with or without a flow of air containing up to 60% by volume of water, to obtain a calcined aluminum porous oxide.
• heat treatment can be carried out in the presence of a flow of air containing up to 60% by volume of water, also called hydrothermal heat treatment.
• heat treatment or hydrothermal means the temperature treatment respectively without presence or in the presence of water. In the latter case, the contact with the water vapor can take place at atmospheric pressure ("steaming") or autogenous pressure (autoclaving).
• steaming atmospheric pressure
• autoclaving autogenous pressure
• Said f) heat treatment step allows the transition of the boehmite to the final alumina.
• the alumina has a crystallographic structure of the type transition alumina gamma, delta, theta, chi, rho or eta, alone or in mixture. More preferably, the alumina is a gamma, delta or theta transition alumina, alone or as a mixture. The existence of the different crystallographic structures is related to the conditions of implementation of the f) heat treatment step.
• the calcined aluminous porous oxide obtained in step f) is kneaded with a solution comprising at least one nickel precursor to obtain a paste.
• the active phase is provided by one or more solutions containing at least nickel.
• the said solution (s) may be aqueous or consist of an organic solvent or a mixture of water and at least one organic solvent (for example ethanol or toluene).
• the solution is aqueous.
• the pH of this solution may be modified by the possible addition of an acid.
• the aqueous solution may contain ammonia or ammonium ions NH 4 + .
• said nickel precursor is introduced in aqueous solution, for example in the form of nitrate, carbonate, acetate, chloride, hydroxide, hydroxycarbonate, oxalate, complexes formed by a polyacid or an acid-alcohol and its salts, complexes formed with acetylacetonates, or any other soluble inorganic derivative in aqueous solution, which is brought into contact with said calcined aluminous porous oxide.
• nickel precursor nickel nitrate, nickel chloride, nickel acetate or nickel hydroxycarbonate is advantageously used.
• the nickel precursor is nickel nitrate or nickel hydroxycarbonate.
• said nickel precursor is introduced into an ammoniacal solution by introducing a nickel salt, for example nickel hydroxide or nickel carbonate, into an ammoniacal solution or into an ammonium carbonate or ammonium carbonate solution. ammonium hydrogen carbonate.
• a nickel salt for example nickel hydroxide or nickel carbonate
• the quantities of the nickel precursor (s) introduced into the solution are chosen such that the total nickel content is between 5 and 65% by weight, preferably between 8 and 55% by weight, preferably between 10 and 40% by weight. weight, and particularly preferably between 10 and 34% by weight of said element relative to the total mass of the catalyst.
• the contents in Nickel are generally suitable for the intended hydrogenation reaction as described above in the paragraph of the catalyst description.
• Any other additional element may be introduced into the mixing tank during the comalaxing step or in the solution containing the metal salt or salts of the precursors of the active phase.
• a silicic precursor solution or emulsion may be introduced.
• a salt chosen from nitrate, sulphate, chloride or any other precursor is advantageously used as precursor. conventional.
• An additive for example a chelating agent of organic nature, may advantageously be introduced into the solution if the person skilled in the art deems it necessary.
• Comalaxing is advantageously carried out in a kneader, for example a "Brabender" kneader, well known to those skilled in the art.
• the calcined alumina powder obtained in step f) and one or more optional additional elements are placed in the tank of the kneader.
• the solution comprising at least one nickel precursor, optionally one or more additional element (s), and optionally deionized water is added to the syringe or with any other means for a period of a few minutes, typically about 2 minutes at a given kneading speed.
• kneading can be continued for a few minutes, for example about 15 minutes at 50 rpm.
• the solution comprising at least one nickel precursor can also be added in several times during this comalaxing phase.
• the paste obtained at the end of the comalaxing step g) is then shaped according to any technique known to those skilled in the art, for example extrusion forming methods, pelletizing, by the method of the drop of oil (dripping) or by granulation at the turntable.
• the paste is shaped by extrusion in the form of extrudates of diameter generally between 0.5 and 10 mm, preferably 0.8 and 3.2 mm, and very preferably between 1, 0 and 2 , 5 mm.
• This may advantageously be in the form of cylindrical, trilobed or quadrilobed extrudates. Preferably its shape will be trilobed or quadrilobed.
• said comalling step g) and said shaping step h) are combined in a single kneading-extruding step.
• the paste obtained after the mixing can be introduced into a piston extruder through a die having the desired diameter, typically between 0.5 and 10 mm.
• the shaped dough undergoes drying i) at a temperature of between 15 and less than 250 ° C., preferably between 80 and 200 ° C., according to any technique known to those skilled in the art, during a duration typically between 10 minutes and 24 hours.
• a dried catalyst is obtained.
• the catalyst thus dried can then undergo a complementary step of thermal or hydrothermal treatment j) at a temperature of between 250 and 1000 ° C. and preferably between 250 and 750 ° C., for a duration of typically between 15 minutes and 10 hours, presence or absence of water.
• thermal or hydrothermal treatment j at a temperature of between 250 and 1000 ° C. and preferably between 250 and 750 ° C., for a duration of typically between 15 minutes and 10 hours, presence or absence of water.
• the catalyst precursor comprises nickel in oxide form, that is to say in NiO form.
• the contact with the steam can take place at atmospheric pressure ("steaming") or autogenous pressure (autoclaving).
• the water content is preferably between 150 and 900 grams per kilogram of dry air, and even more preferably between 250 and 650 grams per kilogram of dry air.
• a portion of the metal precursor (s) may be introduced into the catalyst resulting from stage i). or j) or k), according to any method known to those skilled in the art, the most common being that of dry impregnation.
• One or more additional element (s) may also be introduced, such as an additional metal selected from Group VIII metals, Group IB metals and / or tin, or an additive such as a chelating agent of organic nature by any technique known to those skilled in the art, for example by impregnation. In these cases, said impregnation is advantageously followed by drying and optionally heat treatment.
• the drying can be carried out at a temperature between 70 and 250 ° C, preferably between 80 and 200 ° C, generally for a period of between 1 and 24 hours.
• the heat treatment can be carried out at a temperature of between 200 and 1000 ° C., preferably between 250 and 750 ° C., generally for a period of between 15 minutes and 10 hours. It is possible to carry out several impregnations, each impregnation advantageously being followed by drying and possibly heat treatment.
• all or the precursor (s) metal (s) is introduced during the preparation by co-kneading of the oxide matrix calcined predominantly aluminum and no additional impregnation step will therefore be necessary.
• the metal precursor (s) of the active phase are fully co-kneaded within the predominantly calcined aluminum oxide matrix. Step k) Reduction by a reducing gas
• At least one reducing treatment step k) is carried out in the presence of a reducing gas after steps i) or ) to obtain a catalyst comprising nickel at least partially in metallic form.
• This treatment makes it possible to activate the said catalyst and to form metal particles, in particular nickel in the zero state.
• Said reducing treatment can be carried out in situ or ex situ, that is to say after or before the catalyst is loaded into the hydrogenation reactor.
• Said step k) of reducing treatment can be implemented on the catalyst which has or has not been subjected to the passivation step I), described below.
• the reducing gas is preferably hydrogen.
• the hydrogen can be used pure or as a mixture (for example a hydrogen / nitrogen mixture, hydrogen / argon, hydrogen / methane). In the case where the hydrogen is used as a mixture, all proportions are possible.
• Said reducing treatment is carried out at a temperature between 120 and 500 ° C, preferably between 150 and 450 ° C.
• the reducing treatment is carried out at a temperature between 350 and 500 ° C, preferably between 350 and 450 ° C.
• the reducing treatment is generally carried out at a temperature of between 120 and 350 ° C, preferably between 150 and 350 ° C.
• the duration of the reducing treatment is generally between 2 and 40 hours, preferably between 3 and 30 hours.
• the rise in temperature to the desired reduction temperature is generally slow, for example set between 0.1 and 10 ° C / min, preferably between 0.3 and 7 ° C / min.
• the flow rate of hydrogen is between 0.1 and 100 L / hour / g of catalyst, preferably between 0.5 and 10. L / hour / g of catalyst, even more preferably between 0.7 and 5 L / hour / g of catalyst.
• the catalyst according to the invention may optionally undergo a passivation step (step I) with a sulfur or oxygen-containing compound or with CO 2 before or after the reducing treatment step k) .
• This passivation step may be performed ex situ or in situ.
• the passivation step is carried out by the implementation of methods known to those skilled in the art.
• the sulfur passivation step makes it possible to improve the selectivity of the catalysts and to avoid thermal runaways when starting new catalysts ("run away" according to the English terminology).
• Passivation generally consists in irreversibly poisoning with the sulfur compound the most virulent active sites of the nickel which exist on the new catalyst and thus in attenuating the activity of the catalyst in favor of its selectivity.
• the passivation step is carried out by the implementation of methods known to those skilled in the art and in particular, for example by the implementation of one of the methods described in patent documents EP0466567, US51531 63 , FR2676184, WO2004 / 098774, EP0707890.
• the sulfur compound is for example chosen from the following compounds: thiophene, thiophane, alkylmonosulfides such as dimethylsulfide, diethylsulfide, dipropylsulphide and propylmethylsulphide or an organic disulfide of formula HO-RrS-SR 2 -OH such as di-thio-di- ethanol of formula HO-C 2 H 4 -SSC 2 H 4 -OH (often called DEODS).
• the sulfur content is generally between 0.1 and 2% by weight of said element relative to the mass of the catalyst.
• the passivation step with an oxygenated compound or with CO 2 is generally carried out after a reducing treatment beforehand at elevated temperature, generally between 350 and 500 ° C., and makes it possible to preserve the metallic phase of the catalyst in the presence of air. .
• the oxygenated compound is generally air or any other stream containing oxygen.
• the present invention also relates to the use of the catalyst according to the invention in a hydrogenation process and in particular in a process for selective hydrogenation of polyunsaturated molecules such as diolefins, acetylenics or alkenylaromatician, also called styrenics.
• Monounsaturated organic compounds such as, for example, ethylene and propylene, are at the source of the manufacture of polymers, plastics and other value-added chemicals. These compounds are obtained from natural gas, naphtha or gas oil which have been treated by steam cracking or catalytic cracking processes.
• Selective hydrogenation is the main treatment developed to specifically remove undesired polyunsaturated compounds from these hydrocarbon feeds. It allows the conversion of the polyunsaturated compounds to the corresponding alkenes or aromatics, avoiding their total saturation and thus the formation of the corresponding alkanes or naphthenes. In the case of steam cracking gasolines used as a filler, the selective hydrogenation also makes it possible to selectively hydrogenate alkenyl aromatics to aromatics by avoiding the hydrogenation of the aromatic rings.
• the hydrocarbon feedstock treated in the selective hydrogenation process has a final boiling point of less than or equal to 250 ° C and contains at least 2 carbon atoms per molecule and comprises at least one polyunsaturated compound.
• polyunsaturated compounds means compounds comprising at least one acetylenic function and / or at least one diene function and / or at least one alkenylaromatic function.
• the filler is selected from the group consisting of a C2 steam cracking cut, a steam cracking C3 cut, a steam cracking C4 cut, a steam cracking C5 cut and a steam cracking gasoline also called pyrolysis gasoline.
• the steam-cracking gasoline or pyrolysis gasoline corresponds to a hydrocarbon fraction whose boiling point is generally between 0 and 250 ° C., preferably between 10 and 220 ° C.
• the polyunsaturated hydrocarbons to be hydrogenated present in said steam cracking gasoline are, in particular, diolefinic compounds (butadiene, isoprene, cyclopentadiene, etc.), styrenic compounds (styrene, alpha-methylstyrene, etc.) and indene compounds (indene). ).
• Steam cracking gasoline generally comprises the C5-C12 cut with traces of C3, C4, C13, C14, C15 (for example between 0.1 and 3% by weight for each of these cuts).
• a charge formed of pyrolysis gasoline generally has the following composition: 5 to 25% by weight of paraffins, 40 to 70% by weight of aromatic compounds, 5 to 20% by weight of mono-olefins, 5 to 40% by weight of diolefins, 1 to 10% by weight of alkenylaromatic compounds and from 20 to 300 ppm by weight of sulfur, all the compounds forming 100%.
• the polyunsaturated hydrocarbon feedstock treated according to the selective hydrogenation process according to the invention is a steam-cracking gasoline.
• the selective hydrogenation process according to the invention aims at eliminating said polyunsaturated hydrocarbons present in said feedstock to be hydrogenated without hydrogenating the monounsaturated hydrocarbons.
• the selective hydrogenation process aims to selectively hydrogenate acetylene.
• the selective hydrogenation process aims to selectively hydrogenate propadiene and methylacetylene.
• a C4 cut is intended to eliminate butadiene, vinylacetylene (VAC) and butyne
• VAC vinylacetylene
• butyne in the case of a C5 cut, it is intended to eliminate pentadienes.
• the selective hydrogenation process aims to selectively hydrogenate said polyunsaturated hydrocarbons present in said feed to be treated so that the diolefinic compounds are partially hydrogenated to mono-olefins and that the styrenic and indene compounds are partially hydrogenated to corresponding aromatic compounds by avoiding the hydrogenation of aromatic rings.
• the technological implementation of the selective hydrogenation process is carried out, for example, by injection, in ascending or descending current, of the polyunsaturated hydrocarbon feedstock and hydrogen in at least one fixed bed reactor.
• Said reactor may be of the isothermal or adiabatic type. An adiabatic reactor is preferred.
• the polyunsaturated hydrocarbon feedstock may advantageously be diluted by one or more re-injection (s) of the effluent, from said reactor where the selective hydrogenation reaction occurs, at various points of the reactor, located between the inlet and the outlet. the reactor outlet to limit the temperature gradient in the reactor.
• the technological implementation of the selective hydrogenation process according to the invention can also be advantageously carried out by implanting at least one of said supported catalyst in a reactive distillation column or in reactor-exchangers.
• the flow of hydrogen can be introduced at the same time as the feedstock to be hydrogenated and / or at one or more different points of the reactor.
• the selective hydrogenation of the C2, C3, C4, C5 and C5 + cuts can be carried out in the gas phase or in the liquid phase, preferably in the liquid phase for the C3, C4, C5 and C5 + cuts. Indeed, a reaction in the liquid phase makes it possible to lower the energy cost and to increase the cycle time of the catalyst.
• the selective hydrogenation is carried out at a temperature of between 0 and 500 ° C., at a pressure of between 0.1 and 20 MPa, at a molar ratio of hydrogen / (polyunsaturated compounds to be hydrogenated) between 0 and 500 ° C. , 1 and 10 and at an hourly volume velocity VVH (defined as the ratio of the volume flow rate of load on catalyst volume) between 0.1 and 200 h -1 for a liquid feed, between 100 and 15 000 h -1 for a gaseous feed of a hydrocarbon feed containing polyunsaturated compounds containing at least 2 atoms of carbon per molecule and having a final boiling point of less than or equal to 250 ° C.
• VVH defined as the ratio of the volume flow rate of load on catalyst volume
• a selective hydrogenation process is carried out in which the feedstock is a steam cracking gasoline containing polyunsaturated compounds, the molar ratio (hydrogen) / (polyunsaturated compounds to be hydrogenated) is generally between 1 and 2, the temperature is generally between 40 and 200 ° C, preferably between 50 and 180 ° C, the hourly volume velocity (VVH) is generally between 0.5 and 50 h "1 , preferably between 1 and 20 h " 1 and the pressure is generally between 0.3 and 6.5 MPa, preferably between 2.0 and 3.5 MPa.
• the hydrogen flow rate is adjusted in order to dispose of it in sufficient quantity to theoretically hydrogenate all of the polyunsaturated compounds and to maintain an excess of hydrogen at the outlet of the reactor.
• the present invention also relates to the use of the catalyst according to the invention in a hydrogenation process and in particular in a process for the hydrogenation of aromatics for converting aromatic compounds of petroleum or petrochemical cuts by converting aromatic rings to naphthenic rings.
• the hydrocarbon feedstock treated in the aromatic hydrogenation process has a final boiling point less than or equal to 650 ° C, generally between 20 and 650 ° C, and preferably between 20 and 450 ° C, and contains at least less an aromatic or polyaromatic compound.
• Examples of petroleum or petrochemical cuts containing aromatic compounds include, for example, kerosene, light gas oil, heavy gas oil and cracking distillates, such as FCC recycle oil, coker unit gas oil, distillates and the like. hydrocracking, and the reformate of catalytic reforming.
• the content of aromatic hydrocarbons in a feed treated in the hydrogenation process is generally between 0.1 and 80% by weight, preferably between 1 and 50% by weight, and particularly preferably between 2 and 35% by weight, the percentage by weight.
• the aromatics present are, for example, benzene or alkylaromatics such as toluene, ethylbenzene, ⁇ -xylene, m-xylene or p-xylene, or else aromatics having a plurality of aromatic (polyaromatic) rings such as naphthalene. .
• the sulfur or chlorine content of the feedstock is generally less than 5000 ppm by weight of sulfur or chlorine respectively, preferably less than 100 ppm by weight, and particularly preferably less than 10 ppm.
• the hydrogenation of the aromatics can be carried out in the gas phase or in the liquid phase, preferably in the liquid phase.
• the hydrogenation of the aromatics is carried out at a temperature of between 30 and 350 ° C., preferably between 50 and 325 ° C., at a pressure of between 0.1 and 20 MPa, preferably between 0 and 20 ° C. , 5 and 10 MPa, at a hydrogen / (aromatic compounds to be hydrogenated) molar ratio between 0.1 and 10 and at a VVH hourly volume velocity of between 0.05 and 50 h -1 , preferably between 0.1 and 10 h "1 of a hydrocarbon feedstock containing aromatic compounds and having a final boiling point less than or equal to 650 ° C.
• the hydrogen flow rate is adjusted in order to dispose of it in sufficient quantity to theoretically hydrogenate all of the polyunsaturated compounds and to maintain an excess of hydrogen at the outlet of the reactor.
• the conversion of the aromatic or polyaromatic compounds is generally greater than 20 mol%, preferably greater than 40 mol%, more preferably greater than 80 mol%, and particularly preferably greater than 90 mol% of the aromatic compounds. or polyaromatic content contained in the hydrocarbon feedstock. The conversion is calculated by dividing the difference between the total moles of the aromatic or polyaromatic compounds in the hydrocarbon feedstock and in the product by the total moles of the aromatic or polyaromatic compounds in the hydrocarbon feedstock.
• the catalyst according to the invention is used in a process for the hydrogenation of a benzene-containing hydrocarbon feedstock such as, for example, reformate from a catalytic reforming unit.
• a benzene-containing hydrocarbon feedstock such as, for example, reformate from a catalytic reforming unit.
• the benzene content is generally between 0.1 and 40% by weight, preferably between 0.5 and 35% by weight, and particularly preferably between 2 and 30% by weight, the percentage by weight being based on the total weight of the hydrocarbon load.
• the sulfur or chlorine content of the feedstock is generally less than 10 ppm by weight of sulfur or chlorine respectively, and preferably less than 2 ppm by weight.
• the hydrogenation of the feed containing benzene can be carried out in the gas phase or in the liquid phase, preferably in the liquid phase.
• a solvent may be present.
• the hydrogenation of benzene is carried out at a temperature of between 30 and 250 ° C., preferably between 50 and 200 ° C., and more preferably between 80 and 180 ° C., at a pressure comprised between between 0.1 and 10 MPa, preferably between 0.5 and 4 MPa, at a hydrogen / (benzene) molar ratio between 0.1 and 10 and at a hourly volume velocity VVH between 0.05 and 50 h -1 preferably between 0.5 and 10 h -1 .
• the conversion of benzene is generally greater than 50 mol%, preferably greater than 80 mol%, more preferably greater than 90 mol% and particularly preferably greater than 98 mol%.
• solution S The aqueous solution of Ni precursors used for the preparation of catalysts A, B, C and D is prepared by dissolving 46.1 g of nickel nitrate (NiNO 3 , supplier Strem Chemicals®) in a volume of 13 mL of distilled water. Solution S is obtained whose NiO concentration is 20.1% by weight (relative to the mass of the solution).
• NiNO 3 nickel nitrate
• Example 2 Preparation of the Comalaxed Catalyst A According to the Invention
• Catalyst A according to the invention is prepared by comalaxing alumina A1 and solution S of Ni precursors.
• alumina A1 The synthesis of alumina A1 according to the invention is carried out in a laboratory reactor with a capacity of about 7000 ml. The synthesis is carried out at 70 ° C with stirring in six steps, named a) to f) below. It is sought to prepare 5 L of solution at a concentration fixed at 27 g / L of alumina in the final suspension (obtained at the end of step c) and with a contribution rate of the first step (a) to 2 , 1% of the total alumina.
• Adjustment of the pH 70 ml of NaAl100 sodium aluminate are gradually added. The goal is to reach a pH between 7 and 10 in a period of 5 to 15 minutes.
• the pH is between 8.7 and 9.9.
• step c) The suspension obtained at the end of step c) is filtered by displacement on a sintered Buchner tool P4 and washed several times with distilled water. An alumina gel is obtained.
• step d) Drying: The alumina gel obtained at the end of step d) is dried in an oven overnight at 200 ° C.
• step e) Heat treatment: The powder obtained at the end of step e) is then calcined at 750 ° C. for 2 hours to obtain the transition from boehmite to alumina. Alumina A1 is then obtained.
• Catalyst A is then prepared from alumina A1 and solution S of Ni precursors, prepared above, according to the following four steps, named below g) to j):
• a "Brabender" mixer is used with a tank of 80 cm 3 and a kneading speed of 30 rpm.
• Alumina powder A1 is placed in the tank of the kneader.
• solution S of Ni precursors is added to the syringe for about 2 minutes at 15 rpm. After obtaining a paste, the kneading is maintained for 15 minutes at 50 rpm.
• Catalyst B is prepared by comalaxing boehmite (calcined alum gel) and solution S of Ni precursors.
• the synthesis of the boehmite is carried out in a laboratory reactor with a capacity of about 7000 ml following the first five steps, a) to e), of Example 2 described above. As in Example 2 described above, the synthesis is carried out at 70 ° C. with stirring and it is sought to prepare 5 L of solution at a concentration of 27 g / L of alumina in the final suspension (obtained at the end of step c) and with a contribution rate of the first step (a) to 2.1% of the total alumina.
• step e The operating conditions of the five steps a) to e) are strictly identical to those described in Example 2 above.
• a boehmite powder B1 is obtained.
• This boehmite powder B1 is then mixed with the solution S of Ni precursors (described in Example 1). No calcination occurs between step e) and the step of comalaxing.
• Catalyst B is then prepared according to the four steps g) to j) described in Example 2.
• the operating conditions are strictly identical, with the exception of the following two points:
• step g) of comalaxing the boehmite powder B1 is mixed with the solution S of precursors of Ni.
• the calcination is carried out at 750 ° C. in order to transform the boehmite into alumina. This calcination at high temperature gave rise to refractory phases of nickel aluminate type.
• the characteristics of the calcined catalyst B thus obtained are reported in Table 1. Compared with the catalyst A, the macroporous volume is much higher, the mesoporous volume and mesoporous median diameter are much lower. Catalyst B also has microporosity, unlike catalyst A. Catalyst B also has NiO crystallites much larger than those of Catalyst A.
• Catalyst C is prepared by dry impregnation of alumina A1 described in Example 2 with solution S of Ni precursors.
• the synthesis of alumina A1 is carried out by following the six steps, steps a) to f), of Example 2 described above. The operating conditions are strictly identical. However, a step of shaping the dried alumina gel from step e) is inserted between steps e) and f): The shaping of this powder is carried out on a "Brabender" type kneader with a acid level of 1% (total acid level, expressed relative to dry alumina), a neutralization rate of 20% and acid and basic fire losses of 62% and 64% respectively.
• extrusion is then carried out on a piston extruder through a 2.1 mm diameter die. After extrusion, the extrudates are dried overnight at 80 ° C. At the end of the f) calcination step, extrudates of alumina A1 are obtained.
• Alumina A1 is then impregnated with solution S of precursors of Ni, described in Example 1, according to the so-called dry impregnation method; a volume of 1.15 ml of solution S is added dropwise to a mass of 10.5 g of alumina A1 for a period of 10 minutes. After impregnation, the solid is dried in an oven at 120 ° C. overnight, and then calcined under an air flow of 1 L / hr / g of catalyst, at 450 ° C. for 2 hours (ramp for raising the temperature 5 ° C / min). The calcined catalyst C is then obtained.
• Catalyst D is prepared by comalaxing alumina D1 and solution S of precursors of Ni.
• the synthesis of alumina D1 is carried out in a 5 L reactor in six stages, named below a) to f).
• the concentration of the acidic and basic aluminum precursors is as follows: aluminum sulphate Al 2 (SO 4 ) 3 at 102 g / l in Al 2 O 3 and sodium aluminate NaAlOO at 155 g / l in Al 2 O 3 . It seeks final alumina concentration of 45 g / L in the suspension obtained at the end of the second step c) of precipitation.
• step d) Filtration of the suspension obtained at the end of step c) by displacement on a sintered Buchner tool P4, followed by three successive washes with 5 L of distilled water.
• step f) A calcination of the powder obtained at the end of step e) at 750 ° C. for 2 hours. D1 alumina is obtained.
• the catalyst D is then prepared by comalaxing the alumina D1 and the solution S of precursors of Ni described in Example 1 according to the four steps g) to j) described in Example 2. The operating conditions are strictly identical . At the end of step j), the calcined catalyst D is then obtained.
• Catalysts A, B, C and D described in the above examples are tested for the selective hydrogenation reaction of a mixture containing styrene and isoprene.
• composition of the filler to be selectively hydrogenated is as follows: 8% by weight styrene (Sigma AIdrich® supplier, purity 99%), 8% by weight isoprene (Sigma AIdrich® supplier, purity 99%), 84% by weight n-heptane (solvent ) (VWR® supplier, purity> 99% chromanorm HPLC).
• This feed also contains sulfur compounds in very low content: 10 ppm wt of sulfur introduced in the form of pentanethiol (supplier Fluka®, purity> 97%) and 100 ppm wt of sulfur introduced in the form of thiophene (Merck® supplier, purity 99 %).
• This composition corresponds to the initial composition of the reaction mixture.
• This mixture of model molecules is representative of a pyrolysis species.
• the selective hydrogenation reaction is carried out in a 500 ml autoclave made of stainless steel, equipped with magnetic stirring mechanical stirring and capable of operating at a maximum pressure of 100 bar and temperatures of between 5 ° C. and 200 ° C. .
• a quantity of 3 mL of catalyst Prior to its introduction into the autoclave, a quantity of 3 mL of catalyst is reduced ex situ under a flow of hydrogen of 1 L / h / g of catalyst, at 400 ° C. for 1 6 hours (temperature rise ramp 1 ° C / min), then it is transferred to the autoclave, protected from the air. After addition of 214 mL of n-heptane (supplier VWR®, purity> 99% chromanorm HPLC), the autoclave is closed, purged, then pressurized under 35 bar (3.5 MPa) of hydrogen, and brought to temperature. test equal to 30 ° C.
• the methyl-butenes are in turn hydrogenated to isopentane. Hydrogen consumption is also monitored over time by the pressure decrease in a reservoir bottle located upstream of the reactor. The catalytic activity is expressed in moles of H 2 consumed per minute and per gram of Ni.
• Table 2 Comparison of the performances in selective hydrogenation of a mixture containing styrene and isoprene (A H YDI) and hydrogenation of toluene (A H YD2) -
• Catalysts A, B, C and D described in the above examples are also tested against the hydrogenation reaction of toluene.
• the selective hydrogenation reaction is carried out in the same autoclave as that described in Example 6.
• a quantity of 2 ml of catalyst Prior to its introduction into the autoclave, a quantity of 2 ml of catalyst is reduced ex situ under a flow of hydrogen of 1 L / hr / g of catalyst, at 400 ° C. for 1 6 hours (ramp for raising the temperature 1 ° C / min), then it is transferred to the autoclave, protected from the air. After addition of 21 6 ml of n-heptane (supplier VWR®, purity> 99% chromanorm HPLC), the autoclave is closed, purged and then pressurized under 35 bar (3.5 MPa) of hydrogen, and brought to the test temperature equal to 80 ° C.
• toluene SDS® supplier, purity> 99.8%
• the agitation is started at 1600 rpm.
• the pressure is kept constant at 35 bar (3.5 MPa) in the autoclave using a reservoir bottle located upstream of the reactor.
• the progress of the reaction is monitored by taking samples of the reaction medium at regular time intervals: toluene is completely hydrogenated to methylcyclohexane. Hydrogen consumption is also monitored over time by the pressure decrease in a reservoir bottle located upstream of the reactor. The catalytic activity is expressed in moles of H 2 consumed per minute and per gram of Ni.
• the catalytic activities measured for the catalysts A, B, C and D are reported in Table 2. They are related to the catalytic activity measured for the catalyst A (A H YD 2). The improved performances of the catalyst A prepared are found. according to the invention.

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