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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
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/14—Phosphorus; Compounds thereof
  • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
  • B01J27/19—Molybdenum
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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
  • B01J23/75—Cobalt
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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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  • 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
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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
  • B01J23/76—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
  • B01J23/888—Tungsten
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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
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/14—Phosphorus; Compounds thereof
  • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
  • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0201—Oxygen-containing compounds
  • B01J31/0204—Ethers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0201—Oxygen-containing compounds
  • B01J31/0205—Oxygen-containing compounds comprising carbonyl groups or oxygen-containing derivatives, e.g. acetals, ketals, cyclic peroxides
  • B01J31/0207—Aldehydes or acetals
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0201—Oxygen-containing compounds
  • B01J31/0205—Oxygen-containing compounds comprising carbonyl groups or oxygen-containing derivatives, e.g. acetals, ketals, cyclic peroxides
  • B01J31/0208—Ketones or ketals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0215—Sulfur-containing compounds
  • B01J31/0229—Sulfur-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0214
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
  • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/28—Phosphorising
• • 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
  • B01J38/00—Regeneration or reactivation of catalysts, in general
  • B01J38/02—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
  • 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
  • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
  • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
  • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
  • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
  • C10G45/24—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with hydrogen-generating compounds
  • C10G45/28—Organic compounds; Autofining
  • C10G45/30—Organic compounds; Autofining 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
  • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
  • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
  • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
  • C10G47/12—Inorganic carriers
• • 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
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/12—Silica and alumina

Definitions

• the invention relates to a furanic compound additive catalyst, its method of preparation and its use in the field of hydrotreatment and / or hydrocracking.
• a hydrotreating catalyst for hydrocarbon cuts is intended to eliminate the sulfur or nitrogen compounds contained therein in order, for example, to bring a petroleum product to the required specifications (sulfur content, aromatic content, etc.). for a given application (automotive fuel, gasoline or diesel, heating oil, jet fuel). It may also be pretreat this load in order to remove impurities or hydrogenate before subjecting it to various transformation processes to modify the physico-chemical properties, such as reforming processes, for example. hydrocracking of vacuum distillates, catalytic cracking, hydroconversion of atmospheric residues or under vacuum.
• the composition and use of the hydrotreatment catalysts are particularly well described in the article by B. S. Clausen, H. T. Topsoe, and F. E. Massoth, from Catalysis Science and Technology, Volume 11 (1996), Springer-Verlag.
• Conventional hydrotreatment catalysts generally comprise an oxide support and an active phase based on Group VIB and VIII metals in their oxide forms as well as phosphorus.
• the preparation of these catalysts generally comprises a step of impregnating the metals and phosphorus on the support, followed by drying and calcination to obtain the active phase in their oxide forms.
• these catalysts are generally subjected to sulphidation in order to form the active species.
• a family of compounds now well known in the literature relates to chelating nitrogen compounds (EP0181035, EP1043069 and US6540908) with, for example, ethylenediaminetetraacetic acid (EDTA), ethylenediamine, diethylenetriamine or nitrilotriacetic acid ( NTA).
• EDTA ethylenediaminetetraacetic acid
• NTA nitrilotriacetic acid
• the invention relates to a catalyst comprising a support based on alumina or silica or silica-alumina, at least one group VIII element, at least one group VIB element and a furan compound.
• the catalyst according to the invention shows an increased activity compared with the catalysts which are not additivated and the dried catalysts with known additives.
• the temperature necessary to reach a desired sulfur or nitrogen content for example 10 ppm of sulfur in the case of a diesel fuel charge, in ULSD or Ultra Low Sulfur Diesel mode according to the Anglo-Saxon terminology
• the stability is increased because the cycle time is prolonged thanks to the necessary temperature reduction.
• the furanic compound is of formula (I)
• radicals R3 and R4 advantageously represent, respectively, a hydrogen atom.
• the furanic compound is chosen from 2-methylfuran, 2,5-dimethylfuran, furfuryl alcohol, 1 - (2-furyl) ethanol, 2,5-bis (hydroxymethyl) furan, - (hydroxymethyl) furfural, 5-hydroxymethyl-2-furoic acid, 2-methoxyfuran, 2-furaldehyde, 5-methyl-2-furaldehyde, 5- (ethoxymethyl) furan-2-carboxaldehyde, Acetoxymethyl-2-furaldehyde, 5-chloromethylfurfural, 2,5-diformylfuran, 2-acetylfuran, 2-acetyl-5-methylfuran, furoic acid, 5-ethylfuroic acid, 5- formyl-2-furoic acid, 2,5-furandicarboxylic acid, dimethyl 2,5-furandicarboxylate, methyl 2-furoate, methyl 5-methyl-2-furoate, furfuryl acetate, propionate furfury
• the furanic compound is a polyfuranic compound of formula (II) wherein Z is selected from an oxygen atom, a sulfur atom, a linear or branched or cyclic hydrocarbon radical having from 1 to 20 carbon atoms.
• the furanic compound is chosen from bis (5-formylfurfuryl) ether, 2,2 '- (thiodimethylene) difurane and 5,5-bis (5-methyl-2-furanyl) -2-pentanone.
• the element content of group VIB is between 5 and 40% by weight expressed as Group VIB metal oxide relative to the total weight of the catalyst and the group VIII element content is between 1 and 10% by weight. expressed as Group VIII metal oxide with respect to the total weight of the catalyst.
• the molar ratio element of group VIII to group VIB element in the catalyst is between 0.1 and 0.8.
• the catalyst additionally contains phosphorus, the phosphorus content being between 0.1 and 20% by weight expressed as P 2 0 5 relative to the total weight of the catalyst and the phosphorus to phosphorus ratio on the group element.
• VIB in the catalyst is greater than or equal to 0.05.
• the content of furan compound is between 1 and 45% by weight relative to the total weight of the catalyst.
• the catalyst further contains an organic compound other than the furan compound containing oxygen and / or nitrogen and / or sulfur.
• the organic compound is chosen from a compound comprising one or more chemical functional groups chosen from a carboxylic function, alcohol, thiol, thioether, sulphone, sulphoxide, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, oxime, urea and amide.
• the organic compound other than the furanic compound is chosen from g-valerolactone, 2-acetylbutyrolactone, triethylene glycol, diethylene glycol, ethylene glycol, ethylenediaminetetraacetic acid (EDTA), maleic acid, malonic acid, citric acid, g-cetovaleric acid, dimethylformamide, N-methylpyrrolidone, propylene carbonate, 2-methoxyethyl 3-oxobutanoate, 2-methacryloyloxyethyl 3-oxobutanoate, bicine , tricine or a lactam.
• g-valerolactone 2-acetylbutyrolactone
• triethylene glycol diethylene glycol
• ethylene glycol ethylenediaminetetraacetic acid (EDTA)
• EDTA ethylenediaminetetraacetic acid
• maleic acid malonic acid
• citric acid citric acid
• g-cetovaleric acid dimethylformamide
• the catalyst is at least partially sulphurized.
• the invention also relates to processes for preparing the catalyst according to the invention as described in the claims.
• the invention also relates to the use of the catalyst according to the invention in a process for hydrotreatment and / or hydrocracking of hydrocarbon cuts.
• group VIII according to the CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IUPAC classification.
• Hydroprocessing is understood to include reactions including hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and aromatic hydrogenation (HDA).
• HDS hydrodesulfurization
• HDN hydrodenitrogenation
• HDA aromatic hydrogenation
• the catalyst according to the invention is a catalyst additive to a furan compound. More particularly, the catalyst according to the invention comprises a support based on alumina or silica or silica-alumina, at least one element of group VIII, at least one element of group VIB and a furan compound.
• furanic compound means any compound having at least one aromatic ring composed of 4 carbon atoms and one oxygen atom.
• the catalyst according to the invention may be a fresh catalyst, that is to say a catalyst which has not been used as catalyst previously in a catalytic unit and in particular in hydrotreatment and / or hydrocracking.
• the catalyst according to the invention may also be a rejuvenated catalyst.
• the term "rejuvenated catalyst” means a catalyst which has been used as a catalyst in a catalytic unit and in particular in hydrotreatment and / or hydrocracking and which has been subjected to at least one stage of partial or total elimination of the coke, for example by calcination. (regeneration). This regenerated catalyst is then additive at least with a furan compound to obtain the rejuvenated catalyst.
• This rejuvenated catalyst may contain one or more other organic additive (s) which may be added before, after or at the same time as the furan compound.
• the hydrogenating function of said catalyst also called the active phase, is provided by at least one group VIB element and at least one group VIII element.
• the preferred group VIB elements are molybdenum and tungsten.
• the preferred group VIII elements are non-noble elements and in particular cobalt and nickel.
• the hydrogenating function is chosen from the group formed by the combinations of cobalt-molybdenum, nickel-molybdenum, nickel-tungsten or nickel-cobalt-molybdenum, or nickel-molybdenum-tungsten elements.
• the hydrogenating function is advantageously provided by the combination of nickel and molybdenum; a combination of nickel and tungsten in the presence of molybdenum may also be advantageous.
• cobalt-nickel-molybdenum combinations can be advantageously used.
• the total content of Group VIB and Group VIII elements is advantageously greater than 6% by weight expressed as oxide relative to the total weight of the catalyst.
• the content of group VIB element is between 5 and 40% by weight, preferably between 8 and 35% by weight, and more preferably between 10 and 30% by weight expressed as Group VIB metal oxide relative to the total weight of the product. catalyst.
• the element content of group VIII is between 1 and 10% by weight, preferably between 1.5 and 9% by weight, and more preferably between 2 and 8% by weight expressed as Group VIII metal oxide with respect to weight. total catalyst.
• the molar ratio of Group VIII element to Group VIB element in the catalyst is preferably between 0.1 and 0.8, preferably between 0.15 and 0.6 and even more preferably between 0.2 and 0.5.
• the catalyst according to the invention advantageously also comprises phosphorus as a dopant.
• the dopant is an added element which in itself has no catalytic character but which increases the catalytic activity of the active phase.
• the phosphorus content in said catalyst is preferably between 0.1 and 20% by weight expressed as P 2 0 5 relative to the total weight of the catalyst, preferably between 0.2 and 15% by weight expressed as P 2 0 5 , and very preferably between 0.3 and 11% by weight expressed as P 2 Os.
• the phosphorus molar ratio on the group VIB element in the catalyst is greater than or equal to 0.05, preferably greater than or equal to 0.07, preferably between 0.08 and 1, preferably between 0.01 and 0.9 and very preferably between 0.15 and 0.8.
• the catalyst according to the invention may advantageously also contain at least one dopant chosen from boron, fluorine and a mixture of boron and fluorine.
• the boron content is preferably between 0.1 and 10% by weight expressed as boron oxide relative to the total weight of the catalyst, preferably between 0.2 and 7% by weight, and very preferred between 0.2 and 5% by weight.
• the fluorine content is preferably between 0.1 and 10% by weight expressed as fluorine relative to the total weight of the catalyst, preferably between 0.2 and 7% by weight, and very preferably between 0.2 and 5% by weight.
• the total content of boron and fluorine is preferably between 0.1 and 10% by weight expressed as boron oxide and fluorine relative to the total weight of the catalyst, preferably between 0 and 10% by weight. , 2 and 7% by weight, and very preferably between 0.2 and 5% by weight.
• the catalyst according to the invention comprises a support based on alumina or silica or silica-alumina.
• the support of said catalyst is based on alumina, it contains more than 50% by weight of alumina relative to the total weight of the support and, in general, it contains only alumina or silica-alumina such that defined below.
• the support comprises alumina, and preferably extruded alumina.
• the alumina is gamma alumina.
• the alumina support advantageously has a total pore volume of between 0.1 and 1.5 cm 3 .g -1 , preferably between 0.4 and 1.1 cm 3 .g -1 .
• the total pore volume is measured by mercury porosimetry according to ASTM standard D4284 with a wetting angle of 140 °, as described in the book Rouquerol F.; Rouquerol J.; Singh K. "Adsorption by Powders & Porous Solids: Principle, methodology and applications", Academy Press, 1999, for example by means of a model Autopore III TM apparatus of the brand Micromeritics TM.
• the specific surface area of the alumina support is advantageously between 5 and 400 m 2 ⁇ g 1 , preferably between 10 and 350 m 2 ⁇ g 1 , more preferably between 40 and 350 m 2 ⁇ g 1 .
• the specific surface is determined in the present invention by the BET method according to ASTM D3663, a method described in the same work cited above.
• the support of said catalyst is a silica-alumina containing at least 50% by weight of alumina with respect to the total weight of the support.
• the silica content in the support is at most 50% by weight relative to the total weight of the support, most often less than or equal to 45% by weight, preferably less than or equal to 40%.
• Silicon sources are well known to those skilled in the art. By way of example, mention may be made of silicic acid, silica in powder form or in colloidal form (silica sol), tetraethylorthosilicate Si (OEt) 4 .
• the support of said catalyst is based on silica, it contains more than 50% by weight of silica relative to the total weight of the support and, in general, it contains only silica.
• the support consists of alumina, silica or silica-alumina.
• the support may also advantageously contain from 0.1 to 50% by weight of zeolite relative to the total weight of the support.
• zeolite is chosen from the group FAU, BEA, ISV, IWR, IWW, MEI, UWY and, preferably, the zeolite is chosen from the group FAU and BEA, such as zeolite Y and / or beta.
• the support may also contain at least a portion of metal (s) VIB and VIII, and / or at least a portion of dopant (s) including phosphorus and / or at least a portion of (s) organic compound (s) containing oxygen (the furanic compound or other) and / or nitrogen and / or sulfur which have been introduced outside the impregnations (introduced for example during the preparation of the support).
• metal s
• VIB and VIII / or at least a portion of dopant (s) including phosphorus and / or at least a portion of (s) organic compound (s) containing oxygen (the furanic compound or other) and / or nitrogen and / or sulfur which have been introduced outside the impregnations (introduced for example during the preparation of the support).
• the support is advantageously in the form of balls, extrudates, pellets or irregular and non-spherical agglomerates whose specific shape can result from a crushing step.
• the catalyst according to the invention also comprises a furan compound.
• the furanic compound may be a monofuranic or polyfuranic compound.
• the furanic compound is of formula (I)
• the furanic compound is a polyfuranic compound of formula (II) in which Z is chosen from an oxygen atom, a sulfur atom, a linear or branched or cyclic hydrocarbon radical containing from 1 to 20 carbon atoms and which may also comprise a heteroatom, a halogen and / or at least one functional group.
• the furanic compound is preferably selected from 2-methylfuran (also known as Sylvan), 2,5-dimethylfuran (also known as 2,5-DMF), furfuryl alcohol (also known as furfuranol), 1- (2-furyl) ethanol, 2,5-bis (hydroxymethyl) furan, 5- (hydroxymethyl) furfural (also known as 5- (Hydroxymethyl) -2-furaldehyde or 5-HMF), 5-hydroxymethyl-2-furoic acid, 2-methoxyfuran, 2-furaldehyde (also known as furfural), 5-methyl-2-furaldehyde (also known as 5-methyl-furfural), 5- (ethoxymethyl) furan-2-carboxaldehyde, 5-acetoxymethyl-2-furaldehyde, 5-chloromethylfurfural, 2,5-diformylfuran, 2-acetylfuran , 2-acetyl-5-methylfuran, furoic acid, 5-ethylfuroic acid, 5-form
• the furanic compound is a polyfuranic compound of formula (II), it is preferably chosen from bis (5-formylfurfuryl) ether, 2,2'- (thiodimethylene) difurane and 5,5-bis (5-methyl) -2-furanyl) -2-pentanone (also known as Sylvan trimer).
• the furanic compound is selected from 2-furaldehyde (also known as furfural), 5-hydroxymethylfurfural (also known as 5- (hydroxymethyl) -2-furaldehyde or 5-HMF), 2-acetylfuran 5-methyl-2-furaldehyde, methyl 2-furoate, furfuryl alcohol (also known as furfuranol) and furfuryl acetate.
• 2-furaldehyde also known as furfural
• 5-hydroxymethylfurfural also known as 5- (hydroxymethyl) -2-furaldehyde or 5-HMF
• 2-acetylfuran 5-methyl-2-furaldehyde methyl 2-furoate
• furfuryl alcohol also known as furfuranol
• furfuryl acetate furfuryl acetate
• the presence of the furan compound on the catalyst makes it possible to observe an increased activity relative to the non-additive catalysts and to the known dried additivated catalysts.
• the content of furanic compound on the catalyst according to the invention is between 1 and 45% by weight, preferably between 2 and 30% by weight, and more preferably between 3 and 25% by weight relative to the total weight of the catalyst.
• the drying step (s) consecutive to the introduction of the furanic compound is (are) carried out at a temperature below 200 ° C. so as to preserve preferably at least 30%, preferably at least 50%, and very preferably preferred at least 70% of the amount of the introduced furan compound calculated on the basis of the carbon remaining on the catalyst.
• the furanic compound may be derived from the traditional chemical industry with generally high purities.
• the furanic compound may also come from the treatment of biomass, which will be called a biofurized furanic compound, the product of this treatment preferably containing predominantly the furan compound which may or may not be purified before use.
• biomass which will be called a biofurized furanic compound
• the product of this treatment preferably containing predominantly the furan compound which may or may not be purified before use.
• first- or second-generation saccharifying biomasses such as starch, inulin, sucrose, cellulose, hemicellulose containing sugars such as glucose and fructose.
• mention may be made of the process for obtaining furfuraldeveloped by Shell (WO2012 / 041990) which makes it possible, starting from lignocellulosic biomass, to produce a mixture containing at least 50% by weight of furfural.
• the catalyst according to the invention may comprise, in addition to the furanic compound, another organic compound or a group of organic compounds known for their role as additives.
• the function of the additives is to increase the catalytic activity compared to the non-additive catalysts.
• the catalyst according to the invention may further comprise one or more oxygen-containing organic compounds other than the furan compound and / or one or more nitrogen-containing organic compounds and / or one or more organic compounds containing sulfur.
• the catalyst according to the invention may further comprise one or more oxygen-containing organic compounds other than the furan compound and / or one or more organic compounds containing nitrogen.
• the organic compound contains at least 2 carbon atoms and at least one oxygen and / or nitrogen atom.
• the organic compound is chosen from a compound comprising one or more chemical functions chosen from a carboxylic function, alcohol, thiol, thioether, sulfone, sulfoxide, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, oxime, urea and amide.
• the organic compound is chosen from a compound comprising two alcohol functions and / or two carboxylic functions and / or two ester functions and / or at least one amide function.
• the oxygen-containing organic compound may be one or more selected from compounds having one or more chemical functions selected from a carboxylic, alcohol, ether, aldehyde, ketone, ester or carbonate function.
• the organic oxygen-containing compound may be one or more selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (with a molecular weight between 200 and 1500 g mol), propylene glycol, 2-butoxyethanol, 2- (2-butoxyethoxy) ethanol, 2- (2-methoxyethoxy) ethanol, triethylene glycol dimethyl ether, glycerol, acetophenone, 2,4-pentanedione, pentanone, acetic acid, maleic acid, malic acid, malonic acid, oxalic acid, gluconic acid, tartaric acid, citric acid, g-ketovaleric acid, succinate C1 - C4 dialkyl, methyl acetoacetate, ethyl ace
• the nitrogen-containing organic compound may be one or more selected from compounds having one or more chemical functions selected from an amine or nitrile function.
• the nitrogen-containing organic compound may be one or more selected from the group consisting of ethylenediamine, diethylenetriamine, hexamethylenediamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, acetonitrile octylamine, guanidine or carbazole.
• the organic compound containing oxygen and nitrogen may be one or more chosen from compounds comprising one or more chemical functional groups chosen from a carboxylic acid, alcohol, ether, aldehyde, ketone, ester, carbonate or amine function. nitrile, imide, amide, urea or oxime.
• the organic compound containing oxygen and nitrogen may be one or more selected from the group consisting of 1,2-cyclohexanediaminetetraacetic acid, monoethanolamine (MEA), N-methylpyrrolidone, dimethylformamide, ethylenediaminetetraacetic acid (EDTA), alanine, glycine, nitrilotriacetic acid (NTA), N- (2-hydroxyethyl) ethylenediamine-N, N ', N'-triacetic acid (HEDTA) , diethylenetriaminepentaacetic acid (DTPA), tetramethylurea, glutamic acid, dimethylglyoxime, bicine, tricine, or a lactam.
• MEA monoethanolamine
• EDTA ethylenediaminetetraacetic acid
• NDA nitrilotriacetic acid
• HEDTA N- (2-hydroxyethyl) ethylenediamine-N, N ', N'-triacetic acid
• the sulfur-containing organic compound may be one or more selected from compounds having one or more chemical functions selected from a thiol, thioether, sulfone or sulfoxide function.
• the sulfur-containing organic compound may be one or more selected from the group consisting of thioglycolic acid, 2-hydroxy-4-methylthiobutanoic acid, a sulfonated derivative of a benzothiophene or a sulfoxidized derivative of a benzothiophene.
• the organic compound contains oxygen, most preferably it is selected from g-valerolactone, 2-acetylbutyrolactone, triethylene glycol, diethylene glycol, ethylene glycol, ethylenediaminetetraacetic acid (EDTA), maleic acid, malonic acid, citric acid, g-ketovaleric acid, dimethylformamide, N-methylpyrrolidone, propylene carbonate, 2-methoxyethyl 3-oxobutanoate, 2- (3-oxobutanoate) methacryloyloxyethyl, bicine, or tricine.
• oxygen most preferably it is selected from g-valerolactone, 2-acetylbutyrolactone, triethylene glycol, diethylene glycol, ethylene glycol, ethylenediaminetetraacetic acid (EDTA), maleic acid, malonic acid, citric acid, g-ketovaleric acid, dimethylformamide, N-methylpyrrolidone, propylene carbonate, 2-
• the content of the organic compound (s) with additive function (s) containing oxygen (other than the furan compound) and / or nitrogen and / or sulfur on the catalyst according to the invention is between 1 and 30% by weight, preferably between 1.5 and 25% by weight, and more preferably between 2 and 20% by weight relative to the total weight of the catalyst.
• the catalyst according to the invention can be prepared according to any method of preparation of a supported catalyst additive with an organic compound known to those skilled in the art.
• the catalyst according to the invention may be prepared by implementing a step of impregnation of said furan compound, advantageously with the aid of a solution containing a solvent in which the furan compound is diluted.
• the process for preparing said catalyst implements a step of adding said furan compound by the liquid phase. After impregnation, a drying step is then necessary to remove the solvent and / or the excess of the furanic compound and thus release the porosity necessary for the implementation of the catalyst.
• the catalyst according to the invention may be prepared by implementing a step of adding said furan compound by the gaseous phase.
• the catalyst according to the invention may be prepared according to a preparation process comprising the following steps:
• step b) drying said catalyst precursor from step a) at a temperature below 200 ° C, without subsequently calcining it.
• the contacting step a) comprises several modes of implementation which are distinguished in particular by the moment of the introduction of the furan compound which can be carried out either at the same time as the impregnation of the metals (co-impregnation) or after the impregnation of metals (post-impregnation), or finally before the impregnation of metals (pre-impregnation).
• the contacting step can combine at least two modes of implementation, for example co-impregnation and post-impregnation. These different modes of implementation will be described later. Each mode, taken alone or in combination, can take place in one or more stages.
• the catalyst according to the invention during its preparation process does not undergo calcination after the introduction of the furan compound or any other organic compound containing oxygen and / or nitrogen and / or or sulfur to preserve at least a part of the furan compound or any other organic compound in the catalyst.
• calcination here means a heat treatment under a gas containing air or oxygen at a temperature greater than or equal to 200 ° C.
• the catalyst precursor may undergo a calcination step before the introduction of the furan compound or any other organic compound containing oxygen and / or nitrogen and / or sulfur, especially after the impregnation of the elements.
• group VIB and VIII post-impregnation
• the hydrogenating function comprising the elements of group VIB and group VIII of the catalyst according to the invention, also called the active phase, is then in an oxide form.
• the catalyst precursor does not undergo a calcination step after the impregnation of the elements of group VIB and VIII (after impregnation), it is simply dried.
• the hydrogenating function including the elements of group VIB and group VIII of the catalyst according to the invention, also called the active phase, is not then in an oxide form.
• the contacting step a) generally comprises at least one impregnation step, preferably a dry impregnation step, in which the support is impregnated with a solution of impregnation comprising at least one group VIB element, at least one group VIII element, and optionally phosphorus.
• this impregnation solution further comprises at least one furan compound.
• Group VIB and group VIII elements are generally introduced by impregnation, preferably by dry impregnation or by impregnation in excess of solution.
• all the elements of Group VIB and Group VIII are introduced by impregnation, preferably by dry impregnation and this regardless of the mode of implementation.
• Group VIB and group VIII elements may also be introduced in part during the shaping of said support at the time of mixing with at least one alumina gel chosen as a matrix, the rest of the hydrogenating elements then being introduced by impregnation .
• the proportion of Group VIB element introduced during this step is less than 5% by weight of the total amount of element. group VIB introduced on the final catalyst.
• the group VIB element is introduced at the same time as the group VIII element, regardless of the mode of introduction.
• molybdenum precursors that can be used are well known to those skilled in the art.
• oxides and hydroxides molybdic acids and their salts, in particular ammonium salts such as ammonium molybdate, ammonium heptamolybdate, phosphomolybdic acid ( 3 H 2 O RMqi 40) and salts thereof, and optionally silicomolybdic acid (H 4 2 0 4 SiMoi o) and its salts.
• Molybdenum sources can also be heteropolycomposed Keggin type, Keggin lacunary, Keggin substituted, Dawson, Anderson, Strandberg, for example. Molybdenum trioxide and heteropolyanions of the Strandberg, Keggin, Keggin lacunary or substituted Keggin type are preferably used.
• the tungsten precursors that can be used are also well known to those skilled in the art.
• the sources of tungsten it is possible to use oxides and hydroxides, tungstic acids and their salts, in particular ammonium salts such as ammonium tungstate, ammonium metatungstate, phosphotungstic acid and their salts. salts, and optionally silicotungstic acid (H 4 SiW 2 0 4 o) and its salts.
• the sources of tungsten may also be heteropolycomposed Keggin type, Keggin lacunary, Keggin substituted, Dawson, for example.
• Oxides and ammonium salts such as ammonium metatungstate or heteropolyanions of the Keggin, Keggin lacunary or substituted Keggin type are preferably used.
• the precursors of the group VIII elements which may be used are advantageously chosen from the oxides, hydroxides, hydroxycarbonates, carbonates and nitrates of the group VIII elements, for example nickel hydroxycarbonate, carbonate or hydroxide. cobalt are used in a preferred manner.
• Phosphorus when present, may be introduced in whole or in part by impregnation. Preferably, it is introduced by an impregnation, preferably dry, using a solution containing the precursors of Group VIB elements and Group VIII.
• Said phosphorus may advantageously be introduced alone or as a mixture with at least one of the group VIB and group VIII elements, and in any of the steps of impregnation of the hydrogenating function if this is introduced. several times. Said phosphorus may also be introduced, all or part, during the impregnation of the furanic compound if it is introduced separately from the hydrogenating function (case of the post-and pre-impregnation described later) and this in the presence or absence of an organic compound other than the furan compound containing oxygen and / or nitrogen and / or sulfur. It can also be introduced as soon as the synthesis of the support, at any stage of the synthesis thereof. It can thus be introduced before, during or after the kneading of the chosen alumina gel matrix, such as for example and preferably the aluminum oxyhydroxide (boehmite) precursor of alumina.
• the chosen alumina gel matrix such as for example and preferably the aluminum oxyhydroxide (boehmite) precursor of
• the preferred phosphorus precursor is orthophosphoric acid H 3 PO 4 , but its salts and esters such as ammonium phosphates are also suitable. Phosphorus may also be introduced together with the group VIB element (s) as Keggin, Keggin lacunary, Keggin substituted or Strandberg heteropolyanions.
• the furanic compound is advantageously introduced into an impregnating solution which, according to the method of preparation, may be the same solution or a solution different from that containing the elements of group VIB and VIII, in a corresponding total amount:
• a molar ratio of the furanic compound to element (s) of the group VIB of the catalyst precursor of between 0.01 to 5 mol / mol, preferably of between 0.05 to 3 mol / mol, and preferably of between 0 , 1 and 1, 5 mol / mol and very preferably between 0.2 and 1 mol / mol, calculated on the basis of the components introduced into the impregnation solution (s), and
• a molar ratio of the furanic compound to element (s) of the group VIII of the catalyst precursor of between 0.02 and 17 mol / mol, preferably between 0.1 and 10 mol / mol, and preferably between 0 and 10 mol / mol; , 2 and 5 mol / mol and very preferably between 0.4 and 3.5 mol / mol, calculated on the basis of the components introduced into the impregnating solution (s).
• any impregnation solution described in the present invention may comprise any polar solvent known to those skilled in the art.
• Said polar solvent used is advantageously chosen from the group formed by methanol, ethanol, water, phenol and cyclohexanol, taken alone or as a mixture.
• Said polar solvent can also be advantageously chosen from the group formed by propylene carbonate, DMSO (dimethylsulfoxide), N-methylpyrrolidone (NMP) or sulfolane, alone or as a mixture.
• DMSO dimethylsulfoxide
• NMP N-methylpyrrolidone
• sulfolane alone or as a mixture.
• a polar protic solvent is used.
• a list of conventional polar solvents as well as their dielectric constant can be found in the book "Solvents and Solvent Effects in Organic Chemistry", C.
• the solvent used is water or ethanol, and particularly preferably, the solvent is water.
• the solvent may be absent in the impregnating solution, in particular during a pre- or post-impregnation preparation.
• the introduction of this dopant (s) can be done in the same manner as the introduction of the phosphorus described. above at various stages of preparation and in various ways.
• Said dopant when there is one, is advantageously introduced in admixture with the precursor (s) of the elements of the group VIB and of the group VIII, in whole or in part on the shaped support, by an impregnation dry of said support with a solution, preferably aqueous, containing the precursors of the metals, the phosphorus precursor and the precursor (s) of the dopant (s), (and also containing the furanic compound in the mode of co-impregnation).
• a solution preferably aqueous
• Boron precursors may be boric acid, orthoboric acid H 3 B0 3 , biborate or ammonium pentaborate, boron oxide, boric esters. Boron may be introduced for example by a solution of boric acid in a water / alcohol mixture or in a water / ethanolamine mixture. Preferably the boron precursor, if boron is introduced, is orthoboric acid.
• fluorine precursors that can be used are well known to those skilled in the art.
• fluoride anions can be introduced as an acid hydrofluoric acid or its salts. These salts are formed with alkali metals, ammonium or an organic compound. In the latter case, the salt is advantageously formed in the reaction mixture by reaction between the organic compound and the hydrofluoric acid.
• the fluorine may be introduced for example by impregnation with an aqueous solution of hydrofluoric acid, or ammonium fluoride or ammonium bifluoride.
• the catalyst further comprises an additional additive (in addition to the furan compound) or a further group of additives selected from an organic compound other than the furan compound containing oxygen and / or nitrogen and / or sulfur this may be introduced into the impregnating solution of step a).
• the molar ratio of organic compound (s) containing oxygen and / or nitrogen and / or sulfur by element (s) of group VIB on the catalyst is between 0.05 to 5 mol / mol, preferably between 0.1 to 4 mol / mol, preferably between 0.2 and 3 mol / mol, calculated on the basis of the components introduced into the impregnating solution (s).
• the molar ratio of organic compound (s) containing oxygen and / or nitrogen and / or sulfur per furan compound is between 0.05 and 5 mol / mol, preferably between 0, 1 and 4 mol / mol, preferably between 0.2 and 3 mol / mol, calculated on the basis of the components introduced into the impregnating solution (s).
• the impregnated support is allowed to mature.
• the maturation allows the impregnating solution to disperse homogeneously within the support.
• Any maturation step described in the present invention is advantageously carried out at atmospheric pressure, in an atmosphere saturated with water and at a temperature of between 17 ° C. and 50 ° C., and preferably at ambient temperature.
• a ripening time of between ten minutes and forty-eight hours and preferably between thirty minutes and five hours, is sufficient. Longer durations are not excluded, but do not necessarily improve.
• step b) of the preparation process according to the invention the catalyst precursor obtained in step a) optionally matured is subjected to a drying step at a temperature below 200 ° C without subsequent calcination step.
• Any drying step after the introduction of the furanic compound described in the present invention is carried out at a temperature below 200 ° C, preferably between 50 and 180 ° C, preferably between 70 and 150 ° C and so very preferred between 75 and 130 ° C.
• the drying step is advantageously carried out by any technique known to those skilled in the art. It is advantageously carried out at atmospheric pressure or under reduced pressure. This step is preferably carried out at atmospheric pressure. It is advantageously carried out in crossed bed using air or any other hot gas.
• the gas used is either air or an inert gas such as argon or nitrogen.
• the drying is carried out in a bed traversed in the presence of nitrogen and / or air.
• the drying step has a short duration of between 5 minutes and 4 hours, preferably between 30 minutes and 4 hours and very preferably between 1 hour and 3 hours.
• the drying is then carried out so as to preferentially retain at least 30% of the furan compound introduced during an impregnation step, preferably this amount is greater than 50% and even more preferably greater than 70%, calculated on the carbon base remaining on the catalyst.
• the drying step is carried out so as to preferably retain at least 30%, preferably at least 50%, and very preferably at least 70% of the amount added calculated on the basis of the carbon remaining on the catalyst.
• step a) of the catalyst preparation process fresh
• the said compounds comprising the elements of group VIB, of group VIII, of the furan compound and optionally of phosphorus are deposited on said support, by one or more steps of co-impregnation, that is to say that said compounds comprising the elements of Group VIB, Group VIII, the furan compound and optionally phosphorus are introduced simultaneously into said support ("co- impregnation ").
• step a) is the following step:
• a ' is impregnated with a support based on alumina or silica or silica-alumina by at least one solution containing at least one compound comprising a group VIB element, at least one compound comprising a group VIII element, the compound furanic and optionally phosphorus so as to obtain a catalyst precursor.
• the co-impregnation step (s) is (are) preferably carried out by dry impregnation or impregnation in excess of solution.
• each co-impregnation step is preferably followed by an intermediate drying step at a temperature below 200 ° C, advantageously between 50 and 180 ° C, preferably between 70 and 150 ° C, very preferably between 75 and 130 ° C and optionally a period of maturation has been observed between the impregnation and drying.
• the elements of group VIB and group VIII, the furan compound, optionally phosphorus, optionally another dopant selected from boron and / or fluorine and optionally an organic compound other than the furanic compound containing oxygen and / or nitrogen and / or sulfur are introduced in step a) in their entirety after the shaping of said support, by dry impregnation of said support with the help with a solution aqueous impregnation agent containing the precursors of group VIB and group VIII elements, the furan compound, optionally the phosphorus precursor, optionally the dopant precursor chosen from boron and / or fluorine and optionally the organic compound other than the compound furanic material containing oxygen and / or nitrogen and / or sulfur.
• step a) of the process for preparing the (fresh) catalyst according to the invention at least one furan compound is brought into contact with a dried and optionally calcined impregnated support comprising at least one element.
• group VIB, at least one group VIII element and optionally phosphorus said support being based on alumina or silica or silica-alumina, so as to obtain a catalyst precursor.
• This second embodiment is a "post-impregnation" preparation of the furanic compound. This is carried out for example by dry impregnation.
• the contacting according to step a) comprises the following successive steps which will be detailed below: a1) impregnating a support based on alumina or silica or silica; alumina with at least one solution containing at least one compound comprising a group VIB element, at least one compound comprising a group VIII element and optionally phosphorus to obtain an impregnated support,
• step a2) drying the impregnated support obtained in step a1) at a temperature below 200 ° C to obtain a dried impregnated support, and optionally drying the dried impregnated support to obtain a calcined impregnated support,
• step a3) the dried and optionally calcined impregnated support obtained in step a2) is impregnated with an impregnating solution comprising at least the furan compound so as to obtain a catalyst precursor, a4) optionally, the catalyst precursor obtained in step a3) is allowed to mature.
• step a1) of the implementation by post-impregnation the introduction of the elements of group VIB and group VIII and possibly phosphorus on the support can be advantageously carried out by one or more impregnations in excess of solution on the support, or preferably by one or more dry impregnations, and, preferably, by a single dry impregnation of said support, using solution (s), preferably aqueous (s) containing the one or more precursors of metals and preferably the precursor of phosphorus.
• each impregnation step is preferably followed by an intermediate drying step at a temperature below 200 ° C., advantageously between 50 and 180 ° C., preferably between 70 and 150 ° C. ° C, very preferably between 75 and 130 ° C and optionally a period of maturation was observed between the impregnation and drying.
• Each intermediate drying step, prior to the introduction of the furan compound can be followed by a calcination step under the conditions described below for step a2).
• the elements of group VIB and group VIII and optionally phosphorus, optionally another dopant selected from boron and / or fluorine and optionally an organic compound other than the compound furan containing oxygen and / or nitrogen and / or sulfur are introduced in step a1) in full after the shaping of said support, by dry impregnation of said support with a aqueous impregnating solution containing the precursors of the group VIB and group VIII elements, the phosphorus precursor, and optionally the dopant precursor chosen from boron and / or fluorine and optionally the organic compound other than the furan compound containing oxygen and / or nitrogen and / or sulfur.
• the elements of group VIB and group VIII and optionally phosphorus, optionally another dopant selected from boron and / or fluorine and optionally an organic compound other than the furan compound containing oxygen and / or nitrogen and / or sulfur can be introduced in step a1) successively by several impregnating solutions containing one or more of the components.
• the impregnated support obtained in step a1) is allowed to mature under the conditions described for the above ripening.
• step a2) the impregnated support obtained in step a1) is dried at a temperature below 200 ° C to obtain a dried impregnated support under the conditions described for drying above.
• the dried impregnated support can then be calcined.
• the calcination is generally carried out at a temperature of between 200 ° C. and 900 ° C., preferably between 250 ° C. and 750 ° C.
• the calcination time is generally between 0.5 hours and 16 hours, preferably between 1 hour and 5 hours. It is usually done under air. Calcination makes it possible to convert the precursors of Group VIB and VIII metals into oxides.
• step a3) the dried impregnated support obtained in step a2) is impregnated with an impregnating solution comprising at least the furan compound so as to obtain a catalyst precursor.
• the furanic compound may advantageously be deposited in one or more stages either by excess impregnation, or by dry impregnation, or by any other means known to those skilled in the art.
• the furanic compound is introduced in dry impregnation, in the presence or absence of a solvent as described above.
• the solvent in the impregnating solution used in step a3) is water, which facilitates the implementation on an industrial scale.
• the furanic compound is advantageously introduced into the impregnation solution of step a3) with the molar ratios per element of group VIB or group VIII described above.
• an additional additive in addition to the furan compound
• a group of additional additives chosen from an organic compound containing oxygen and / or nitrogen and / or sulfur the latter may be introduced into the impregnating solution of step a1) and / or into the impregnation solution of step a3) or else by an additional impregnation step at any time of the preparation process before the final drying of step b), it being understood that no calcination step is carried out after its introduction.
• This compound is introduced in the proportions described above.
• step a4) the catalyst precursor obtained in step a3) is optionally allowed to mature, and this under the conditions of maturation described above.
• step b) of the preparation process according to the invention the catalyst precursor which has been optionally matured in step a4) is subjected to a drying step at a temperature below 200 ° C without a step of subsequent calcination, as described above.
• step a) of the process for preparing the (fresh) catalyst according to the invention at least one compound comprising a group VIB element is brought into contact with at least one compound comprising an element.
• group VIII optionally phosphorus with the support based on alumina or silica or silica-alumina which contains a furan compound so as to obtain a catalyst precursor.
• This third mode of implementation is a preparation by "pre-impregnation" of the furanic compound. This is carried out for example by dry impregnation.
• the contacting according to step a) comprises the following successive steps which will be detailed hereinafter: a1 ') is prepared a support comprising at least one furan compound and optionally at least one part of phosphorus,
• step a2 ' the support obtained in step a1') is impregnated with an impregnating solution comprising at least one compound comprising a group VIB element, at least one compound comprising a group VIII element and optionally phosphorus so as to obtain a catalyst precursor, a3 ') optionally, is allowed to mature the catalyst precursor obtained in step a2').
• a support is prepared comprising at least one furan compound and optionally at least a portion of the phosphorus.
• the furanic compound may be introduced at any time during the preparation of the support, and preferably during shaping or by impregnation on an already formed support.
• step a3) If one chooses the introduction of the furanic compound on the support previously shaped, then this can be carried out as indicated for step a3) of the post-impregnation. It will then be followed by an optional ripening step and drying at a temperature below 200 ° C under the conditions of ripening and drying as described above.
• said shaping is carried out by extrusion kneading, by pelletizing, by the method of drop coagulation (oil-drop according to the English terminology), by rotating plate granulation or any other method well known to those skilled in the art.
• said shaping is carried out by extrusion kneading, the furanic compound being able to be introduced at any time of the kneading extrusion.
• the formed material obtained at the end of the forming step is then advantageously subjected to a heat treatment step at a temperature such that at least a portion of the furan compound remains present, preferably at a temperature below 200 ° C.
• the phosphorus may be introduced at any time during the preparation of the support, and preferably during the shaping or by impregnation on a support already formed as described above. If the phosphorus is introduced alone to the shaping, that is to say without the furanic compound itself then introduced by impregnation, the calcination temperature subsequent to its introduction can then advantageously be carried out at a temperature below 1000 ° C.
• step a2 ') of the implementation by pre-impregnation the introduction of the elements of group VIB and group VIII and optionally phosphorus can be advantageously carried out by one or more impregnations in excess of solution on the support, or preferably by one or more dry impregnations, and, preferably, by a single dry impregnation of said support, using solution (s), preferably aqueous (s), containing the precursor (s) of metals and optionally the phosphorus precursor.
• the catalyst precursor obtained in step a2 ') is allowed to mature under the conditions of maturation described above.
• an additional additive in addition to the furan compound
• the latter may be introduced into the support of step a1 ') during shaping or by impregnation, and / or in the impregnating solution of step a2') or else by an additional impregnation step at n any time of the preparation process before the final drying of step b) it being understood that no calcination step is carried out after its introduction.
• the contacting according to step a) combines at least two contacting modes, for example the co-impregnation of an organic compound and the post-impregnation of an organic compound which may be the same or different from that used for the co-impregnation, since at least one of the organic compounds is a furan compound.
• the contacting according to step a) comprises the following successive steps:
• a1 is contacted by co-impregnation a solution containing at least one compound comprising a group VIB element, at least one compound comprising a group VIII element, at least one organic compound containing oxygen and / or nitrogen and / or sulfur, and optionally phosphorus with a support based on alumina or silica or silica-alumina so as to obtain an impregnated support,
• the impregnated support from step a1") is dried at a temperature below 200 ° C without subsequently calcining it to obtain a dried impregnated support
• step a3 the dried impregnated support resulting from step a2") is brought into contact with a solution of at least one organic compound containing oxygen and / or nitrogen and / or sulfur identical to or different from the one used in step a1 ") so as to obtain a catalyst precursor, a4") optionally, the catalyst precursor obtained in step a3 ") is allowed to mature. and at least one of the organic compounds of step a1 ") or step a3") is a furan compound.
• the catalyst according to the invention may be a rejuvenated catalyst.
• this catalyst can be prepared according to the preparation method comprising the following steps:
• a regenerated catalyst is contacted with a furan compound, so as to obtain a catalyst precursor.
• the regenerated catalyst is a catalyst which has been used as a catalyst in a catalytic unit and in particular in hydrotreatment and / or hydrocracking and which has been subjected to at least one stage of partial or total elimination of coke, for example by calcination (regeneration). ).
• the regeneration can be carried out by any means known to those skilled in the art. Regeneration is generally carried out by calcination at temperatures between 350 and 550 ° C, and most often between 400 and 520 ° C, or between 420 and 520 ° C, or between 450 and 520 ° C, lower temperatures. at 500 ° C being often advantageous.
• the regenerated catalyst contains a support based on alumina or silica or silica-alumina, at least one element of group VIB, at least one element of group VIII and optionally phosphorus in the respective proportions indicated above.
• the hydrogenating function comprising the elements of group VIB and group VIII of the regenerated catalyst is in an oxide form. It may also contain other dopants than phosphorus, as described above.
• the contacting according to step a) comprises the following successive steps: a regenerated catalyst containing a support based on alumina or silica or silica-alumina, at least one group VIB element, at least one group VIII element and optionally phosphorus with a solution of impregnation comprising at least one furan compound so as to obtain a catalyst precursor,
• the catalyst precursor obtained in step a1') is allowed to mature.
• the contacting of step a) is carried out by impregnating the regenerated catalyst with an impregnating solution comprising at least one furan compound so as to obtain a catalyst precursor.
• the furanic compound may advantageously be deposited in one or more stages either by excess impregnation, or by dry impregnation, or by any other means known to those skilled in the art.
• the furanic compound is introduced in dry impregnation, in the presence or absence of a solvent as described above.
• the solvent in the impregnating solution used is water, which facilitates the implementation on an industrial scale.
• the furanic compound is advantageously introduced into the impregnation solution with the molar ratios per group VIB element or group VIII described above.
• step a1 ' When it is desired to further introduce an additional additive (in addition to the furan compound) or a group of additional additives chosen from an organic compound containing oxygen and / or nitrogen and / or sulfur, the latter may be introduced into the impregnating solution of step a1 '") or by a further impregnation step at any time of the preparation process before final drying of step b) it being understood that no calcination step is carried out after its introduction.
• This compound is introduced in the proportions described above.
• step a2 "') the catalyst precursor obtained in step a1'" is optionally allowed to mature, and this under the ripening conditions described above.
• step b) of the preparation process according to the invention the catalyst precursor which has been optionally matured in step a2 '" is subjected to a drying step at a temperature below 200 ° C without subsequent calcination step as described above.
• the fresh catalyst according to the invention can be prepared by carrying out a step of adding said furan compound by the gaseous phase as described in the French applications filed under the national numbers 17 / 53.921 and 17. /53.922.
• the process for preparing said catalyst does not involve a conventional step of impregnating said furan compound. Therefore it is not necessary to carry out a drying step after introduction of the furan compound.
• the process for preparing the catalyst according to the invention comprises the following steps:
• the furanic compound is deposited on a support based on alumina or silica or silica-alumina by implementing a step in which said support is simultaneously brought into contact with the furan compound in the liquid and non-contact state; between the support and the furanic compound in the liquid state, at a temperature below the boiling temperature of the furan compound and under pressure and duration conditions such that a fraction of said furan compound is transferred to the state gaseous to the support,
• step i) being performed before or after steps ii) and iii) or during step iii).
• This second variant is characterized in that the addition of the furanic compound on the support is carried out without physical contact with the furan compound in the liquid state, that is to say without impregnation of the support with the liquid.
• the method is based on the principle of the existence of a vapor pressure of the furanic compound which is generated by its liquid phase at a given temperature and pressure. Thus part of the molecules of furanic compound in the liquid state passes to the gaseous state (vaporization) and is then transferred (gaseous) to the support.
• This step i) of bringing into contact is carried out for a time sufficient to reach the targeted content of furan compound in the support.
• step i) is carried out at an absolute pressure of between 0 and 1 MPa.
• the operating temperature of step i) is less than 200 ° C., preferably between 10 ° C. and 150 ° C., more preferably between 25 ° C. and 120 ° C.
• the process for preparing the catalyst according to the invention comprises the following steps:
• the furan compound is deposited on a support based on alumina or silica or silica-alumina by implementing a step in which the support is placed in a closed or open enclosure with a porous solid comprising a furan compound, this step being carried out under conditions of temperature, pressure and duration such that a fraction of said furanic compound is transferred by gas from the porous solid to the support,
• the addition of the furanic compound consists in bringing together, in an open or closed enclosure, a first batch of porous solid rich in a furan compound which has been previously deposited on said solid in the liquid state, with a support (second batch of porous solid poor in said furan compound).
• the purpose of this bringing the porous solids into contact is to allow a gas transfer of a part of the furanic compound contained in the first batch of porous solid into the second batch of porous solid.
• the term "poor in furanic compound" particularly covers the case where the second batch of porous solid is free of said furan compound.
• This third variant is based on the principle of the existence of a vapor pressure of the furan compound at a given temperature and pressure.
• a part of the furan compound molecules of the porous solid lot of furan compound passes in gaseous form (vaporization) and is then transferred (gaseous) to the support (solid poor furanic compound).
• the porous solid rich in furanic compound acts as a source of furan compound to enrich the furanic compound support (porous solid poor in furan compound).
• the porous solid rich in furanic compound is advantageously a porous support, preferably a support based on alumina or silica or silica-alumina may contain a group VIB element, at least one group VIII element, and optionally phosphorus .
• the mass ratio (first batch of solid rich in furanic compound) / (support or second batch of solid poor in furanic compound) is a function of the porous distribution of the solids and the objective in terms of the target quantity of furan compound on the solids from step a) of bringing into contact.
• This mass ratio is generally less than or equal to 10, preferably less than 2 and even more preferably between 0.05 and 1 inclusive.
• the step of contacting batches of porous solids is preferably conducted under controlled temperature and pressure conditions and so that the temperature is below the boiling temperature of said furan compound to be gas-transferred.
• the operating temperature is less than 150 ° C. and the absolute pressure is generally between 0 and 1 MPa, preferably between 0 and 0.5 MPa and more preferably between 0 and 0.2 MPa. It will thus be possible to carry out the step of placing in presence in an open or closed enclosure, possibly with a control of the composition of the gas present in the enclosure.
• the step of placing the porous solids in an open chamber it will be ensured that the driving of the furan compound out of the chamber is limited as much as possible.
• the step of bringing the porous solids into contact with one another may be carried out in a closed enclosure, for example in a container for storing or transporting the gas-tight solid with the external medium.
• interfacing refers to the fact that the solids are present at the same time in the enclosure without necessarily having a physical contact of the two batches of solids.
• the term "rich in furanic compound” reflects the fact that the solid contains more than 50% of the total amount of said furanic compound used in stage i), preferably at least 60%, preferably at least 80%, preferably at least 90% and preferably 100%.
• the porous solid rich in furan compound contains 100% of the total amount involved in step i) and the support (second batch of solid poor in furan compound) therefore contains 0% of the total amount. in said furanic compound.
• the two variants of preparation of the catalyst (fresh) by gas phase can be carried out according to two embodiments A) and B).
• the porous support is subjected to an impregnation step with a solution comprising a compound comprising a group VIB element, a compound comprising a group VIII element and optionally phosphorus, so as to deposit an active metal phase (step ii).
• the support impregnated with the active metal phase is optionally subjected to a maturation stage and is then dried (stage iii) in order to eliminate the solvent provided by stage ii).
• the dried support containing the active metal phase and optionally phosphorus is treated according to step i) or i ') of bringing into contact with a compound furan in the liquid state or a porous solid containing a furan compound so as to provide an additive catalyst of said furan compound.
• a catalyst support which does not contain an active phase.
• the carrier is first subjected to a step of adding the furanic compound so as to provide an additive-containing catalyst support of the organic compound (step i) or i ')), which after an optional phase of ripening, is sent to the step of impregnating the active phase (step ii).
• This step may consist in bringing the additive-containing support into contact with a solution containing at least one compound comprising a group VIB element, at least one compound comprising a group VIII element, and optionally phosphorus.
• the additive catalyst thus obtained is optionally left to mature and then subjected to a drying step (step iii) in order to remove the solvent provided during the step of impregnating the metal precursors of the active phase.
• the porous support may in particular already contain an additional organic compound other than the furan compound.
• the step ii) of deposition of the active metal phase can implement a solution containing at least one compound comprising a group VIB element, at least a compound having a group VIII element, and optionally phosphorus, and further one or more additional organic compounds different from that of step i) or i ') ⁇
• the step of adding said furan compound by the gaseous phase can also be carried out on a regenerated catalyst.
• the process for preparing the catalyst according to the invention comprises the following step:
• the furan compound is deposited on a regenerated catalyst containing a support based on alumina or silica or silica-alumina, at least one group VIB element, at least one element of group VIII and optionally phosphorus, by implementing a step in which said regenerated catalyst and the furan compound are simultaneously brought into the liquid state and without physical contact between the catalyst and the furanic compound in the liquid state, at a temperature below the boiling point of the furan compound and under pressure and time conditions such that a fraction of said furan compound is transferred in the gaseous state to the catalyst, or
• the furan compound is deposited on a regenerated catalyst containing a support based on alumina or silica or silica-alumina, at least one group VIB element, at least one group VIII element and optionally phosphorus, by implementing a step in which, in a closed or open enclosure, the catalyst is brought into contact with a porous solid containing a furan compound, this step being carried out under conditions of temperature, pressure and duration such that fraction of said furanic compound is transferred gaseously from the porous solid to the catalyst.
• the fresh or rejuvenated additive catalyst obtained by the introduction of the furan compound by gaseous phase as described above may also be treated by one or more subsequent steps to incorporate one or more additional organic compounds other than the one employed in the process. step i) i '), i ") or i'").
• the incorporation of one or more other additional organic additional compounds can be carried out by means of gas phase addition processes or according to any other method known to those skilled in the art, for example by impregnation of a solution containing the compound additional organic.
• the catalyst obtained according to any of the introduction modes described in the present invention into a sulphurized catalyst in order to form its active species.
• This activation or sulphurization step is carried out by the methods well known to those skilled in the art, and advantageously under a sulfo-reducing atmosphere in the presence of hydrogen and hydrogen sulfide.
• step b) At the end of step b) according to the different modes of preparation of the process according to the invention, said catalyst obtained is thus advantageously subjected to a sulphurization step, without intermediate calcination step.
• Said dried catalyst is advantageously sulphurized ex situ or in situ.
• the sulfurizing agents are H 2 S gas or any other sulfur-containing compound used to activate hydrocarbon feeds to sulphurize the catalyst.
• Said sulfur-containing compounds are advantageously chosen from alkyl disulfides such as, for example, dimethyl disulfide (DMDS), alkyl sulphides, such as, for example, dimethyl sulphide, thiols such as, for example, butyl mercaptan (or 1-butanethiol), polysulfide compounds tertiononylpolysulfide type, or any other compound known to those skilled in the art for obtaining a good sulfuration of the catalyst.
• DMDS dimethyl disulfide
• alkyl sulphides such as, for example, dimethyl sulphide
• thiols such as, for example, butyl mercaptan (or 1-butanethiol)
• the catalyst is sulfided in situ in the presence of a sulfurizing agent and a hydrocarbon feedstock.
• the catalyst is sulphurized in situ in the presence of a hydrocarbon feed additive of dimethyl disulfide.
• Another subject of the invention is the use of the catalyst according to the invention or prepared according to the preparation method according to the invention in processes for hydrotreatment and / or hydrocracking of hydrocarbon cuts.
• the catalyst according to the invention and preferably having previously undergone a sulfurization step is advantageously used for the hydrotreatment and / or hydrocracking reactions of hydrocarbonaceous feedstocks such as petroleum cuts, cuts from coal or hydrocarbons produced at from natural gas, possibly in mixtures or from a hydrocarbon fraction derived from biomass and more particularly for the reactions of hydrogenation, hydrodenitrogenation, hydrodearomatization, hydrodesulfurization, hydrodeoxygenation, hydrodemetallation or hydroconversion of hydrocarbon feeds.
• hydrocarbonaceous feedstocks such as petroleum cuts, cuts from coal or hydrocarbons produced at from natural gas, possibly in mixtures or from a hydrocarbon fraction derived from biomass and more particularly for the reactions of hydrogenation, hydrodenitrogenation, hydrodearomatization, hydrodesulfurization, hydrodeoxygenation, hydrodemetallation or hydroconversion of hydrocarbon feeds.
• the catalyst according to the invention and having preferably previously undergone a sulphurization step has an improved activity compared to the catalysts of the prior art.
• This catalyst can also advantageously be used during the pretreatment of catalytic cracking or hydrocracking feeds, or the hydrodesulfurization of residues or the high hydrodesulfurization of gas oils (ULSD Ultra Low Sulfur Diesel according to the English terminology).
• the feedstocks used in the hydrotreatment process are, for example, gasolines, gas oils, vacuum gas oils, atmospheric residues, vacuum residues, atmospheric distillates, vacuum distillates, heavy fuels, oils and waxes. and paraffins, waste oils, residues or deasphalted crudes, feeds from thermal or catalytic conversion processes, lignocellulosic feedstocks or more generally feedstocks from biomass, taken alone or as a mixture.
• the feeds which are treated, and in particular those mentioned above generally contain heteroatoms such as sulfur, oxygen and nitrogen and, for heavy loads, they most often also contain metals.
• the operating conditions used in the processes implementing the hydrocarbon feed hydrotreatment reactions described above are generally as follows: the temperature is advantageously between 180 and 450 ° C., and preferably between 250 and 440 ° C., pressure is advantageously between 0.5 and 30 MPa, and preferably between 1 and 18 MPa, the hourly volume velocity is advantageously between 0.1 and 20 h 1 and preferably between 0.2 and 5 h 1 , and the Hydrogen / charge ratio expressed as a volume of hydrogen, measured under normal conditions of temperature and pressure, per volume of liquid charge is advantageously between 50 l / l to 5000 l / l and preferably 80 to 2000 l / l.
• said hydrotreatment process according to the invention is a hydrotreatment process, and in particular hydrodesulphurization (HDS) of a gas oil fraction produced in the presence of at least one catalyst according to the invention .
• Said hydrotreatment process according to the invention aims to eliminate the sulfur compounds present in said diesel fuel cup so as to achieve the environmental standards in force, namely a sulfur content of up to 10 ppm. It also makes it possible to reduce the aromatics and nitrogen contents of the diesel fraction to be hydrotreated.
• Said gasoil fraction to be hydrotreated according to the process of the invention contains from 0.02 to 5.0% by weight of sulfur. It is advantageously derived from the straight distillation (or straight run diesel according to English terminology), a coking unit (coking according to the English terminology), a visbreaking unit (visbreaking according to the English terminology). Saxon), a steam cracking unit, a hydrotreating and / or hydrocracking unit for heavier feedstocks and / or a catalytic cracking unit (Fluid Catalytic Cracking according to the English terminology). Said gasoil fraction preferably has at least 90% of the compounds whose boiling point is between 250 ° C. and 400 ° C. at atmospheric pressure.
• the hydrotreating process of said diesel fuel cutter according to the invention is carried out under the following operating conditions: a temperature of between 200 and 400 ° C., preferably between 300 and 380 ° C., a total pressure of between 2 MPa and 10 ° C. MPa and more preferably between 3 MPa and 8 MPa with a volume ratio of hydrogen per volume of hydrocarbon feedstock, expressed as volume of hydrogen, measured under normal conditions of temperature and pressure, per volume of liquid feed, of between 100 and 600 liters per liter and more preferably between 200 and 400 liters per liter and a hourly volume velocity (WH) of between 1 and 10 h 1 , preferably between 2 and 8 h 1 .
• WH hourly volume velocity
• the WH corresponds to the inverse of the contact time expressed in hours and is defined by the ratio of the volume flow rate of the liquid hydrocarbon feedstock by the volume of catalyst charged to the reaction unit implementing the hydrotreatment process according to the invention.
• the reaction unit implementing the hydrotreating process of said diesel fuel cutter according to the invention is preferably carried out in a fixed bed, in a moving bed or in a bubbling bed, preferably in a fixed bed.
• said hydrotreatment and / or hydrocracking process according to the invention is a hydrotreatment process (in particular hydrodesulfurization, hydrodeaazoation, hydrogenation of aromatics) and / or hydrocracking of a cut of vacuum distillate produced in the presence of at least one catalyst according to the invention.
• Said hydrotreatment and / or hydrocracking process otherwise known as the hydrocracking or hydrocracking pretreatment method according to the invention, is intended, as the case may be, to eliminate the sulfur, nitrogen or aromatic compounds present in said distillate cut so as to effect pretreatment before conversion into catalytic cracking or hydroconversion processes, or hydrocracking the distillate cut which would have been possibly pretreated before if necessary.
• feeds can be processed by the hydrotreatment and / or hydrocracking processes of vacuum distillates described above. Generally they contain at least 20% volume and often at least 80% volume of compounds boiling above 340 ° C at atmospheric pressure.
• the feedstock may be, for example, vacuum distillates as well as feedstocks from aromatic extraction units of lubricating oil bases or from solvent dewaxing of lubricating oil bases, and / or deasphalted oils. or the filler may be a deasphalted oil or paraffins from the Fischer-Tropsch process or any mixture of the aforementioned fillers.
• the feeds have a boiling point T5 greater than 340 ° C. at atmospheric pressure, and more preferably greater than 370 ° C.
• the nitrogen content of the feedstocks treated in the processes according to the invention is usually greater than 200 ppm by weight, preferably between 500 and 10,000 ppm by weight.
• the sulfur content of the feedstocks treated in the processes according to the invention is usually between 0.01 and 5.0% by weight.
• the filler may optionally contain metals (for example nickel and vanadium).
• the asphaltene content is generally less than 3000 ppm by weight.
• the hydrotreatment and / or hydrocracking catalyst is generally brought into contact, in the presence of hydrogen, with the charges described above, at a temperature above 200 ° C., often between 250 ° C. and 480 ° C., advantageously between 320 ° C and 450 ° C, preferably between 330 ° C and 435 ° C, under a pressure greater than 1 MPa, often between 2 and 25 MPa, preferably between 3 and 20 MPa, the volume velocity being between 0.1 and 20.0 h 1 and preferably 0.1 -6.0 h 1 , preferably 0, 2-3.0 h 1 , and the amount of hydrogen introduced is such that the volume ratio liter of hydrogen / liter of hydrocarbon, expressed as volume of hydrogen, measured under normal conditions of temperature and pressure, per volume of liquid charge, ie between 80 and 5000 l / l and most often between 100 and 2,000 l / l.
• the processes for hydrotreatment and / or hydrocracking of vacuum distillates using the catalysts according to the invention cover the pressure and conversion ranges from mild hydrocracking to high pressure hydrocracking.
• Mild hydrocracking is understood to mean hydrocracking leading to moderate conversions, generally less than 40%, and operating at low pressure, generally between 2 MPa and 6 MPa.
• the catalyst according to the invention can be used alone, in one or more fixed bed catalytic beds, in one or more reactors, in a so-called one-step hydrocracking scheme, with or without liquid recycling of the unconverted fraction, or in a two-stage hydrocracking scheme, optionally in combination with a hydrorefining catalyst located upstream of the catalyst of the present invention.
• said hydrotreatment and / or hydrocracking process according to the invention is advantageously used as pretreatment in a fluidized catalytic cracking process (or FCC method for Fluid Catalytic Cracking according to the terminology Anglo-Saxon).
• the operating conditions of the pretreatment in terms of temperature range, pressure, hydrogen recycle rate, hourly space velocity are generally identical to those described above for hydrotreatment and / or hydrocracking processes of vacuum distillates.
• the FCC process can be performed in a conventional manner known to those skilled in the art under suitable cracking conditions to produce lower molecular weight hydrocarbon products.
• a brief description of catalytic cracking can be found in ULLMANS ENCYCLOPEDIA OF INDUSTRIAL CHEMISTRY VOLUME A 18, 1991, pp. 61-64.
• said hydrotreatment and / or hydrocracking process according to the invention is a process for the hydrotreatment (in particular hydrodesulfurization) of a petrol fraction in the presence of at least one catalyst according to the invention. 'invention.
• the hydrotreatment (including hydrodesulfurization) of the species must make it possible to respond to a double antagonistic constraint: to ensure a deep hydrodesulfurization of the species and to limit the hydrogenation of the unsaturated compounds present in order to limit the hydrotreatment. loss of octane number.
• the feed is generally a hydrocarbon cut having a distillation range of between 30 and 260 ° C.
• this hydrocarbon cut is a gasoline type cut.
• the gasoline cut is an olefinic gasoline cut resulting for example from a catalytic cracking unit (Fluid Catalytic Cracking according to the English terminology).
• the hydrotreatment process consists in bringing the hydrocarbon fraction into contact with the catalyst according to the invention and with hydrogen under the following conditions: at a temperature of between 200 and 400 ° C., preferably between 230 and 330 ° C.
• WH Time Volumetric Rate
• the hydrotreatment process of the gasolines can be carried out in one or more reactors in series of the fixed bed type or of the bubbling bed type. If the process is implemented using at least two reactors in series, it is possible to provide a device for removing the H 2 S from the effluent from the first hydrodesulfurization reactor before treating said effluent in the second hydrodesulfurization reactor.
• Example 1 Preparation of CoMoP catalysts on alumina without organic compounds C1 and C2 (not in accordance with the invention).
• alumina support having a BET surface area of 230 m 2 / g, a pore volume measured by mercury porosimetry of 0.78 ml / g and an average pore diameter of 11.5 nm defined as the median diameter by volume by mercury porosimetry and which is in the form "extruded", cobalt, molybdenum and phosphorus are added.
• the impregnating solution is prepared by dissolving molybdenum oxide (21.1 g) and cobalt hydroxide (5.04 g) at 90 ° C. in 11.8 g of an aqueous solution of acid. phosphoric at 85% weight.
• the extrudates are allowed to mature in a saturated water atmosphere for 24 hours at room temperature and then dried at 90 ° C for 16 hours.
• the dried catalyst precursor thus obtained is denoted C1.
• Calcination of the C1 catalyst precursor at 450 ° C for 2 hours leads to calcined catalyst C2.
• Example 2 On the alumina support described above in Example 1 and which is in the "extruded” form, cobalt, molybdenum and phosphorus are added.
• the impregnating solution is prepared by dissolving 90 ° C. of molybdenum oxide (28.28 g) and cobalt hydroxide (6.57 g) in 15.85 g of an aqueous solution of acid. 85% phosphoric acid and water. After homogenization of the above mixture, 38 g of citric acid was added before adjusting the volume of solution to the pore volume of the support by adding water.
• the molar ratio (citric acid) / Mo is equal to 1 mol / mol and that (citric acid) / Co is equal to 2.7 mol / mol.
• the extrudates are allowed to mature in a saturated water atmosphere for 24 hours at room temperature and then dried at 120 ° C for 16 hours.
• the dried catalyst and additive of citric acid thus obtained is noted C3.
• Catalyst C4 is prepared as follows. On the alumina support described in Example 1 and which is in the "extruded" form, cobalt, molybdenum and phosphorus are added. An impregnating solution was prepared by dissolving 90 ° C. of molybdenum oxide (39 g) and cobalt hydroxide (9.3 g) in 21.9 g of an aqueous solution of phosphoric acid. 85% and water. After homogenization of the above mixture, 5- (hydroxymethyl) furfural was added to the 0.8 mole solution per mole of molybdenum, ie 2.2 moles per mole of cobalt to yield the catalyst precursor C4.
• the volume of the solution was adjusted to the pore volume of the support by adding water prior to impregnation. After Dry impregnation, the catalyst precursor extrudates were allowed to mature in a saturated water atmosphere for 24 hours at room temperature, and then dried at 120 ° C for 16 hours.
• Example 3 Preparation of the CoMoP catalyst on C5 alumina (according to the invention) by post-impregnation.
• catalyst precursor C1 18 g of catalyst precursor C1 described above in Example 1 are impregnated and which is in the form "extruded" with an aqueous solution containing 2.5 g of 5- (hydroxymethyl) furfural and whose volume is equal to the volume porous catalyst precursor C1.
• the quantities involved are such that the amount of 5- (hydroxymethyl) furfural is 0.8 mol per mol of molybdenum (corresponding to 2.2 mol per mol of cobalt).
• the extrudates are allowed to mature in a saturated atmosphere with water for 16 hours at room temperature.
• Catalyst precursor C5 is then dried at 120 ° C for 2 hours to give catalyst C5.
• EXAMPLE 4 Preparation of the CoMoP catalyst on C6 alumina (according to the invention) by introducing an organic compound in the vapor phase after impregnation of the metals.
• EXAMPLE 5 Preparation of the COOMP catalyst on C7 alumina (according to the invention) by introducing an organic compound in the vapor phase after the impregnation of the metals.
• a closed enclosure In a closed enclosure are arranged 2.75 g of 5-methyl-2-furaldehyde contained in a crystallizer. 12 g of the catalyst precursor C1 are introduced into the same closed enclosure and arranged on a stainless steel grid so that the liquid 5-methyl-2-furaldehyde is not in physical contact with the catalyst precursor C1. The closed chamber is placed in an oven at 120 ° C for 2 hours. 13.4 g of catalyst C7 are thus obtained after bringing the catalyst precursor C1 into contact with the 5-methyl-2-furaldehyde compound in the liquid state.
• the amount of 5-methyl-2-furaldehyde thus transferred to the catalyst is such that the molar ratio of 5-methyl-2-furaldehyde / Mo is 0.8 mol per mol of molybdenum (corresponding to 2.2 mol per mol of cobalt).
• a closed chamber In a closed chamber are arranged 3.15 g of methyl 2-furoate contained in a crystallizer. 12 g of the catalyst precursor C1 are introduced into the same closed chamber and placed on a stainless steel grid so that the liquid methyl 2-furoate is not in physical contact with the catalyst precursor C1. The closed chamber is placed in an oven at 120 ° C for 2 hours. 13.6 g of catalyst C8 are thus obtained after bringing the catalyst precursor C1 into contact with the methyl 2-furoate compound in the liquid state. The amount of methyl 2-furoate thus transferred to the catalyst is such that the molar ratio of 2-methyl furoate / Mo is 0.8 mol per mol of molybdenum (corresponding to 2.2 mol per mol of cobalt).
• EXAMPLE 7 Preparation of the COOMP catalyst on C 9 alumina (according to the invention) by introducing an organic compound in the vapor phase after the impregnation of the metals.
• the test is conducted in an isothermal pilot reactor fixed bed traversed, flowing fluids from bottom to top.
• the catalyst precursors are previously sulphurized in situ at 350 ° C. in the reactor under pressure using the test gas oil, to which 2% by weight of dimethyl disulphide is added.
• the hydrodesulfurization tests were carried out under the following operating conditions: a total pressure of 7 MPa, a catalyst volume of 30 cm 3 , a temperature of 330 to 360 ° C., with a hydrogen flow rate of 24 l / h and with a flow rate of 60 cm 3 / h.
• the catalytic performances of the catalysts tested are given in Table 1. They are expressed in degrees Celsius with respect to the catalyst C2 (comparative) chosen as reference: they correspond to the temperature difference to be applied to reach 50 ppm of sulfur in the effluent. A negative value means that the target of sulfur content is reached for a lower temperature and that there is a gain in activity. A positive value means that the target of sulfur content is reached for a higher temperature and that there is therefore a loss of activity.
• Table 1 clearly shows the gain on the catalytic effect provided by the organic compounds according to the invention.
• the catalysts C4, C5, C6, C7, C8 and C9 have activities greater than those obtained for all the other catalysts evaluated.
• the furanic compounds thus provide a gain in catalytic activity whatever their mode of introduction: co-impregnation with metals, introduction after impregnation of metals (post-impregnation) in solution and introduction into the gas phase after impregnation of the metals.
• the advantage of the catalysts according to the invention is significant while they have a lower proportion of organic compound than the catalyst C3, with an intrinsic efficiency higher than that of other compounds for which it is necessary to introduce a greater proportion of compound to observe a significant catalytic effect.
• Table 1 Activities relating to iso-volume in hydrodesulphurization of diesel of catalysts C1 and C3 (not in accordance with the invention) and C4, C5, C6, C7, C8 and C9

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