EP4291621A1 - Procede d'hydrotraitement mettant en ouvre un enchainement de catalyseurs avec un catalyseur a base de nickel, molybdene et tungstene - Google Patents

Procede d'hydrotraitement mettant en ouvre un enchainement de catalyseurs avec un catalyseur a base de nickel, molybdene et tungstene

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Publication number
EP4291621A1
EP4291621A1 EP22702739.8A EP22702739A EP4291621A1 EP 4291621 A1 EP4291621 A1 EP 4291621A1 EP 22702739 A EP22702739 A EP 22702739A EP 4291621 A1 EP4291621 A1 EP 4291621A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
weight
vol
hydrotreating
process according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22702739.8A
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German (de)
English (en)
French (fr)
Inventor
Etienne Girard
Anne-Sophie GAY
Isabelle MERDRIGNAC
Antoine Daudin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
IFP Energies Nouvelles IFPEN
Original Assignee
IFP Energies Nouvelles IFPEN
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Application filed by IFP Energies Nouvelles IFPEN filed Critical IFP Energies Nouvelles IFPEN
Publication of EP4291621A1 publication Critical patent/EP4291621A1/fr
Pending legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G45/00Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02Refining 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
    • C10G45/04Refining 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
    • C10G45/06Refining 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
    • C10G45/08Refining 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04Alumina
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts 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
    • B01J23/84Catalysts 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
    • B01J23/85Chromium, molybdenum or tungsten
    • B01J23/88Molybdenum
    • B01J23/883Molybdenum and nickel
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts 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
    • B01J23/84Catalysts 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
    • B01J23/85Chromium, molybdenum or tungsten
    • B01J23/888Tungsten
    • B01J23/8885Tungsten containing also molybdenum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90Regeneration or reactivation
    • B01J23/94Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14Phosphorus; Compounds thereof
    • B01J27/186Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19Molybdenum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/19Catalysts containing parts with different compositions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61Surface area
    • B01J35/615100-500 m2/g
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63Pore volume
    • B01J35/6350.5-1.0 ml/g
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64Pore diameter
    • B01J35/6472-50 nm
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0201Impregnation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0201Impregnation
    • B01J37/0203Impregnation the impregnation liquid containing organic compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0201Impregnation
    • B01J37/0205Impregnation in several steps
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0236Drying, e.g. preparing a suspension, adding a soluble salt and drying
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20Sulfiding
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G65/00Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G65/00Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/12Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1037Hydrocarbon fractions
    • C10G2300/1048Middle distillates
    • C10G2300/1059Gasoil having a boiling range of about 330 - 427 °C

Definitions

  • the invention relates to a process for the hydrotreating of a hydrocarbon feedstock implementing a sequence of at least two catalysts, the second catalyst of which is a catalyst based on nickel, molybdenum and tungsten.
  • the objective of the process is the production of hydrodesulfurized, hydrodenitrogenated and hydrodearomatized hydrocarbon feedstocks.
  • Conventional hydrotreating 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 includes a step of impregnation of 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 sulfurization in order to form the active species.
  • hydrotreating catalyst optimized for hydrodesulfurization is not automatically optimized for aromatics saturation (or HDA hydrodearomatization) or for hydrodenitrogenation (HDN) and vice versa.
  • Catalyst sequences are often used in which each catalyst is optimized for a type of hydrotreatment.
  • Such sequences of supported catalysts are for example described in the documents US2011/0079542, US5068025, CN1176290, FR3013720 or FR3013721.
  • Document CN105435824 discloses a hydrotreating process using a sequence of a CoMoP supported catalyst added to citric acid followed by a supported NiMoWP catalyst.
  • the volume of the first catalyst is between 5 and 95% and the volume of the second catalyst is between 95 and 5%. An increase in HDS and HDN is observed.
  • a sequence of a first hydrotreatment reaction section containing the first catalyst based on an active phase consisting of nickel and molybdenum and a second hydrotreatment reaction section containing the second catalyst based on an active phase consisting of nickel, molybdenum and tungsten in the presence of phosphorus has a synergistic effect in terms of activity and stability in hydrotreatment, in particular in the hydrogenation of aromatics (HDA) but also in hydrodesulphurization (HDS ) and/or in hydrodenitrogenation (HDN) when the respective volumes of the first and second hydrotreatment reaction section observe a certain distribution, in particular between 50% vol/50% vol and 90% vol/10% vol respectively of said first and second hydrotreatment reaction section.
  • HDA hydrogenation of aromatics
  • HDS hydrodesulphurization
  • HDN hydrodenitrogenation
  • the symbiosis of the first bimetallic catalyst based on an active phase made up of nickel and molybdenum, producing in particular the HDS and part of the HDN, followed by the second trimetallic catalyst based on an active phase made up of nickel, molybdenum and tungsten in the presence of phosphorus, notably performing HDA and HDN, in a certain ratio makes it possible to obtain a highly active and stable catalytic sequence in order to obtain hydrocarbon cuts to specifications.
  • the second catalyst is very active, in particular in HDA and HDN, which makes it possible to complete the hydrotreatment reactions, in particular HDS and HDN, of the first catalyst necessary to reach the specifications.
  • the temperature necessary to reach a desired sulfur, nitrogen or aromatics content for example a maximum of 10 ppm of sulfur in the case of a diesel load, in ULSD or Ultra Low mode Sulfur Diesel according to Anglo-Saxon terminology or else a polyaromatic content ⁇ 8% by weight and a cetane number > 46 (summer) and 43-46 (winter)
  • the stability is increased, because the cycle time is extended thanks to the necessary temperature reduction.
  • the trimetallic catalyst deactivates less quickly than a bimetallic catalyst, which makes it possible all the more to increase the cycle time on a standard load or to allow the treatment of loads heavily loaded with sulphur, nitrogen and/or aromatics.
  • the volume distribution of the two catalysts makes it possible to optimize the reactions of HDS, HDN and HDA carried out in the first or second reaction section in order to obtain hydrocarbon cuts to specifications while increasing the activity and the stability of the catalytic system compared to a system containing only one of the catalysts or a system containing the two catalysts with a volume distribution outside the distribution between 50%vol/50%vol and 90 %vol/10%vol.
  • Another advantage of the hydrotreating process according to the invention is the fact that both light feedstocks (diesel) and heavier feedstocks (vacuum distillate) can be treated.
  • the hydrotreating process according to the invention is also particularly suitable for the hydrotreating of feedstocks comprising high nitrogen and aromatics contents, such as feedstocks resulting from catalytic cracking, coker or visbreaking.
  • the process according to the present invention makes it possible to produce a hydrotreated hydrocarbon fraction, that is to say freed from nitrogen compounds, sulfur compounds and aromatic compounds.
  • the conversion to hydrodesulphurization (HDS) is greater than 95%, preferably greater than 98%.
  • the conversion to hydrodenitrogenation (HDN) is greater than 90%, preferably greater than 95%.
  • the conversion into hydrogenation of the aromatics (HDA) is greater than 70%, preferably greater than 80%.
  • the distribution of the volumes V1/V2 is between 70% vol/30% vol and 80% vol/20% vol respectively of said first and second hydrotreatment reaction section.
  • the second catalyst is characterized in that: - the nickel content, measured in NiO form, is between 1 and 4% by weight relative to the total weight of the catalyst, - the molybdenum content, measured in MoO 3 form, is between 2 and 9% by weight relative to the total weight of the catalyst,
  • the tungsten content measured in WO 3 form, is between 18 and 40% by weight relative to the total weight of the catalyst
  • the phosphorus content measured in P 2 O 5 form, is between 0.5 and 4% by weight relative to the total weight of the catalyst.
  • the second catalyst is characterized in that:
  • the nickel content, measured in NiO form, is between 3 and 4% by weight relative to the total weight of the catalyst
  • the molybdenum content, measured in MoO 3 form, is between 2 and 9% by weight relative to the total weight of the catalyst
  • the tungsten content measured in WO 3 form, is between 29 and 40% by weight relative to the total weight of the catalyst
  • the phosphorus content measured in P 2 O 5 form, is between 3 and 4% by weight relative to the total weight of the catalyst.
  • the second catalyst is further characterized in that:
  • the WO 3 /MoO 3 molar ratio is between 2 and 12.4 mol/mol
  • NiO/(WO 3 +MoO 3 ) molar ratio is between 0.20 and 0.33 mol/mol
  • the P 2 O /(WO 3 +MoO 3 ) molar ratio is between 0.21 and 0.34 mol/mol.
  • the first catalyst has a molybdenum content of between 5 and 40% by weight, expressed as MoO 3 , relative to the total weight of the catalyst and a nickel content of between 1 and 10% by weight, expressed as NiO, per relative to the total weight of the catalyst.
  • the first catalyst also comprises phosphorus at a content of between 0.1 and 20% by weight, expressed as P 2 O 5 relative to the total weight of the catalyst.
  • the first and/or the second catalyst additionally contains an organic compound containing oxygen and/or nitrogen and/or sulphur.
  • the organic compound is chosen from a compound comprising one or more chemical functions chosen from a carboxylic, alcohol, thiol, thioether, sulphone, sulphoxide, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, oxime, urea, amide or compounds including a furan ring or a sugar, and preferably it is chosen from ⁇ -valerolactone, 2-acetylbutyrolactone, triethylene glycol, diethylene glycol, ethylene glycol, ethylenediaminetetra- acetic acid (EDTA), maleic acid, malonic acid, citric acid, acetic acid, oxalic acid, gluconic acid, glucose, fructose, sucrose, sorbitol, xylitol, g
  • the content of organic compound is between 1 and 30% by weight relative to the total weight of the catalyst.
  • hydrotreating we mean reactions including in particular hydrodesulphurization (HDS), hydrodenitrogenation (HDN) and the hydrogenation of aromatics (HDA).
  • HDS hydrodesulphurization
  • HDN hydrodenitrogenation
  • HDA hydrogenation of aromatics
  • the hydrocarbon feedstock to be treated according to the hydrotreatment process of the invention has a distillation range of between 150°C and 600°C, preferably between 180°C and 580°C.
  • the feedstocks used in the hydrotreating process are, for example, gas oils, vacuum gas oils, atmospheric residues, vacuum residues, atmospheric distillates, vacuum distillates, heavy fuel oils, oils, waxes and paraffins. , waste oils, residues or deasphalted crudes, fillers from thermal or catalytic conversion processes, lignocellulosic fillers or more generally fillers from biomass such as vegetable oils, taken alone or in a mixture.
  • the fillers which are treated, and in particular those cited above generally contain heteroatoms such as sulphur, oxygen and nitrogen and, for heavy fillers, they most often also contain metals.
  • Said hydrocarbon charge may optionally contain resins.
  • the resin content may be greater than 1% by weight, in particular greater than 5% by weight.
  • the resin content is measured according to the ASTM D 2007-11 standard.
  • the hydrocarbon charge may also contain very few resins (less than 1% by weight).
  • the process according to the invention can be carried out in one, two or more reactors. It is usually performed in a fixed bed.
  • the volume distribution of the two catalysts makes it possible to optimize the reactions of HDS, HDN and HDA carried out in the first or second reaction section. Indeed, a volume of the second catalyst that is too large does not allow the quantitative reduction of nitrogen compounds, thus resulting in an inhibition of the HDA reaction. Conversely, too small a volume of second catalyst does not maximize the HDA reaction.
  • the operating conditions used in steps a) or b) of the hydrotreatment process according to the invention are generally the following: the temperature is advantageously between 180 and 450° C., and preferably between 250 and 440° C., the 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 .
  • the hourly volume velocity (WH) is defined here as the ratio between the hourly volume flow of the hydrocarbon charge by the volume of catalyst(s).
  • the hydrogen/feed ratio expressed as volume of hydrogen, measured under normal temperature and pressure conditions, per volume of liquid feed is advantageously between 50 L/L to 5000 L/L and preferably 80 to 2000 L/L.
  • the operating conditions may be identical or different in steps a) and b). Preferably, they are identical.
  • the hydrogenating function of said first catalyst also called active phase, is ensured by nickel and molybdenum.
  • the molybdenum content, measured in MoO 3 form is between 5 and 40% by weight, preferably between 8 and 39% by weight, and more preferably between 10 and 38% by weight relative to the total weight of the catalyst.
  • the nickel content, measured in NiO form is between 1 and 10% by weight, preferably between 1.5 and 9% by weight, and more preferably between 2 and 8% by weight relative to the total weight of the catalyst.
  • the first catalyst may also include 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 between 0.1 and 20% by weight relative to the total weight of the catalyst, preferably between 0.2 and 15% by weight, and very preferably between 0.3 and 11% by weight expressed as P 2 O 5 .
  • the phosphorus to molybdenum molar ratio in the first 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 0.1 and 0.9 and very preferably between 0.15 and 0.8.
  • the first catalyst may advantageously also contain at least one dopant chosen from boron, fluorine and a mixture of boron and fluorine.
  • the content of boron or fluorine or a mixture of the two is preferably between 0.1 and 10% by weight expressed as boron oxide and/or in fluorine element 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 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 porous volume is measured by mercury porosimetry according to the ASTM D4284 standard with a wetting angle of 140°, as described in the work Rouquerol F.; Rouquerol J.; Singh K. “Adsorption by Powders & Porous Solids: Principle, methodology and applications”, Academy Press, 1999, for example by means of an Autopore IIITM model apparatus from the MicromeriticsTM brand.
  • the specific surface 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 standard ASTM D3663, 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 relative 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, usually 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. Mention may be made, by way of example, 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 is advantageously in the form of beads, extrudates, pellets or irregular and non-spherical agglomerates, the specific shape of which may result from a crushing step.
  • the first catalyst may further comprise an organic compound or a group of organic compounds known for their role as additives.
  • the function of additives is to increase catalytic activity compared to non-additive catalysts.
  • the catalyst may further comprise one or more organic compounds containing oxygen and/or one or more organic compounds containing oxygen. nitrogen and/or one or more sulfur-containing organic compounds.
  • the catalyst may further comprise one or more organic compounds containing oxygen 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, without containing other heteroatoms.
  • the organic compound is chosen from a compound comprising one or more chemical functions chosen from a carboxylic function, alcohol, thiol, thioether, sulphone, sulphoxide, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, oxime, urea and amide or compounds including a furan ring or a sugar.
  • the organic compound containing nitrogen can be one or more chosen from compounds comprising one or more chemical functions chosen from an amine or nitrile function.
  • an organic compound containing nitrogen is understood to mean a compound containing no other heteroatom.
  • the organic compound containing nitrogen can be one or more chosen from the group consisting of ethylenediamine, diethylenetriamine, hexamethylenediamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, acetonitrile , octylamine, guanidine or a carbazole.
  • the organic compound containing oxygen and nitrogen can be one or more chosen from compounds comprising one or more chemical functions chosen from a carboxylic, alcohol, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, amide, urea or oxime.
  • an organic compound containing oxygen and nitrogen is understood to mean a compound not comprising any other heteroatom.
  • the organic compound containing oxygen and nitrogen can be one or more chosen from the group consisting of 1,2-cyclohexanediaminetetraacetic acid, monoethanolamine (MEA), 1- methyl-2-pyrrolidinone, 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, 2-methoxyethyl cyanoacetate, 1-ethyl-2-pyrrolidinone, 1-vinyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 1-(2-hydroxyethyl)-2-pyrrolidinone , 1-(2-hydroxyethy
  • the organic compound containing sulfur can be one or more chosen from compounds comprising one or more chemical functions chosen from a thiol, thioether, sulphone or sulphoxide function.
  • the organic compound containing sulfur can be one or more selected from the group consisting of thioglycolic acid, 2,2'-thiodiethanol, 2-hydroxy-4-methylthiobutanoic acid, a sulfonated derivative of a benzothiophene or a sulfoxide derivative of a benzothiophene, ethyl 2-mercaptopropanoate, methyl 3-(methylthio)propanoate and ethyl 3-(methylthio)propanoate.
  • the organic compound contains oxygen, preferably it is chosen from ⁇ -valerolactone, 2-acetylbutyrolactone, triethylene glycol, diethylene glycol, ethylene glycol, ethylenediaminetetra-acetic acid (EDTA), l maleic acid, malonic acid, citric acid, acetic acid, oxalic acid, gluconic acid, glucose, fructose, sucrose, sorbitol, xylitol, y-ketovaleric acid , a C1-C4 dialkyl succinate and more particularly dimethyl succinate, dimethylformamide, 1-methyl-2-pyrrolidinone, propylene carbonate, 2-methoxyethyl 3-oxobutanoate, bicine, tricine, 2 -furaldehyde (also known as furfural), 5-hydroxymethylfurfural (also known as 5-(hydroxymethyl)-2-furaldehyde or 5-HMF), 2-acetylfuran, 5-methyl-2-f
  • the total content of organic compound(s) containing oxygen and/or nitrogen and/or sulfur present in the catalyst is generally 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 drying step(s) following the introduction of the organic compound is (are) carried out at a temperature below 200° C. so as to retain preferably at least 30%, preferably at least 50%, and very preferably at least 70% of the amount of organic compound introduced calculated on the basis of the carbon remaining on the catalyst.
  • the remaining carbon is measured by elemental analysis according to ASTM D5373.
  • the second catalyst comprises a support based on alumina or silica or silica-alumina and an active phase consisting of nickel, molybdenum and tungsten.
  • the second catalyst according to the invention also comprises phosphorus as a dopant. It may also comprise an organic compound, and/or optionally boron and/or fluorine.
  • the hydrogenating function of said second catalyst, also called active phase consists of nickel, molybdenum and tungsten.
  • the tungsten content measured in WO 3 form, is between 18 and 40% by weight relative to the total weight of the catalyst
  • the phosphorus content measured in P 2 O 5 form, is between 0.5 and 4% by weight relative to the total weight of the catalyst.
  • the second catalyst is characterized in that:
  • the molybdenum content, measured in MoO 3 form is between 2 and 9% by weight relative to the total weight of the catalyst, preferably between 2 and 4% by weight, preferably between
  • the tungsten content measured in WO 3 form, is between 29 and 40% by weight relative to the total weight of the catalyst, preferably between 34 and 40% by weight, preferably between 35 and 39.9% by weight, and more preferably between 36 and 39% by weight,
  • the phosphorus content measured in P 2 O 5 form, is preferably between 3 and 4% by weight relative to the total weight of the catalyst, preferably between 3.1 and 3.9% by weight, and very preferably between 3.2 and 3.8% by weight.
  • the NiO/(WO 3 +MoO 3 ) molar ratio is between 0.20 and 0.33 mol/mol, preferably between 0.21 and 0.31 mol/mol and even more preferably between between 0.22 and 0.30 mol/mol.
  • the P 2 O /(WO 3 +MoO 3 ) molar ratio is between 0.21 and 0.34 mol/mol, preferably between 0.22 and 0.33 mol/mol and even more preferably between 0.23 and 0.32 mol/mol.
  • the catalyst has a density of group VIB metals (Mo+W), expressed as the number of atoms of said metals per unit area of the catalyst, which is between 5 and 12 atoms of group VIB metals per nm 2 of catalyst, preferably between 6 and 11, even more preferably between 7 and 10.
  • Mo+W group VIB metals
  • the total porous volume is measured by mercury porosimetry according to the ASTM D4284 standard with a wetting angle of 140°, as described in the work Rouquerol F.; Rouquerol J.; Singh K. “Adsorption by Powders & Porous Solids: Principle, methodology and applications”, Academy Press, 1999, for example by means of an Autopore IIITM model apparatus from the MicromeriticsTM brand.
  • the support for the second catalyst comprises, and preferably consists of, an alumina or a silica or a silica-alumina.
  • the support is a support as described for the first catalyst. It may also comprise a zeolite as described for the first catalyst. It may be identical to or different from the support of the first catalyst.
  • the first catalyst according to the invention may also comprise an organic compound or a group of organic compounds whose nature and the quantities used are described in the part for the first catalyst.
  • the two catalysts comprise one or more organic compounds, these may be identical or different.
  • a phosphorus content in said catalyst measured in P 2 O 5 form, preferably between 3 and 4% by weight relative to the total weight of the catalyst, preferably between 3.1 and 3.9% by weight, and so very preferably between 3.2 and 3.8% by weight;
  • the first and the second catalysts can be prepared according to any mode of preparation of a supported catalyst known to those skilled in the art.
  • the precursors of the active phase can be introduced simultaneously or successively.
  • the impregnation of each precursor can advantageously be carried out in at least two stages.
  • the different precursors can thus be advantageously impregnated successively with a different impregnation and maturation time.
  • One of the precursors can also be impregnated several times.
  • the preferred phosphorus precursor is orthophosphoric acid H 3 PO 4 , but its salts and esters such as ammonium phosphates are also suitable.
  • the phosphorus can also be introduced at the same time as the element(s) of group VIB in the form of heteropolyanions of Keggin, lacunary Keggin, substituted Keggin or of the Strandberg type.
  • the boron precursors can be boric acid, orthoboric acid H 3 BO 3 , ammonium biborate or pentaborate, boron oxide, boric esters.
  • the boron can be introduced for example by a solution of boric acid in a water/alcohol mixture or else in a water/ethanolamine mixture.
  • the boron precursor, if boron is introduced, is orthoboric acid.
  • the different molar ratios apply for each of the organic compounds present.
  • the first or the second catalyst according to the invention can also be a regenerated and/or rejuvenated catalyst.
  • a regenerated and/or rejuvenated catalyst is understood to mean a catalyst which has been used as a catalyst in a catalytic unit and in particular in hydrotreating and/or hydrocracking and which has been subjected to at least one stage of partial or total removal of the 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 even between 450 and 520°C, lower temperatures at 500° C. being often advantageous.
  • the method for hydrotreating said diesel fraction according to the invention is implemented under the following operating conditions: a temperature between 200°C and 400°C, preferably between 300°C and 380°C, a total pressure between 2 MPa and 10 MPa and more preferably between 3 MPa and 8 MPa with a ratio of volume of hydrogen per volume of hydrocarbon charge, expressed in volume of hydrogen, measured under normal temperature and pressure conditions, per volume of liquid charge, between 100 and 600 liters per liter and more preferably between 200 and 400 liters per liter and an hourly volume rate (WH) between 0.5 and 10 h -1 , preferably between 0.7 and 8 h -1 .
  • WH hourly volume rate
  • the matrix is most often a silica, an alumina, a silica-alumina, a silica-magnesia, a clay or a mixture of two or more of these products.
  • the most commonly used zeolite is zeolite Y.
  • the cracking is carried out in a substantially vertical reactor either in ascending mode (riser) or in descending mode (dropper).
  • the choice of the catalyst and of the operating conditions are functions of the desired products as a function of the feedstock treated, as is for example described in the article by M. MARCILLY pages 990-991 published in the review of the French Petroleum Institute Nov. -dec. 1975 pp. 969-1006.
  • the operation is usually carried out at a temperature of 450 to 600° C. and residence times in the reactor of less than 1 minute, often 0.1 to 50 seconds.
  • Examples 1 to 3 describe the preparation of catalysts C1 to C3.
  • the final metal and phosphorus composition of each catalyst expressed in the form of oxides and related to the weight of the catalyst, as well as the ratios WO 3 /MoO 3 , NiO/(WO 3 +MoO 3 ) and P 2 O 5 / (WO 3 +MoO 3 ) are shown in the table below.
  • Support A1 has a water uptake volume of 0.77 mL/g.
  • the impregnation solution is prepared by dissolution at 90°C of 37.41 grams of molybdenum oxide (MerckTM, purity > 99.5% by weight), 11.96 grams of nickel hydroxycarbonate (MerckTM, purity 99.9% by weight) and 14.53 grams of a solution of orthophosphoric acid (MerckTM, 85 wt% in water) in 67.2 mL of distilled water. After dry impregnation, the extrudates are left to mature in an atmosphere saturated with water for 24 h at room temperature, then they are dried at 90° C. for 16 h.
  • the impregnation solution is prepared by dissolving at 90°C molybdenum oxide (MerckTM, purity > 99.5% by weight, 6.12 g), hydrated ammonium metatungstate (MerckTM, ⁇ 85, 0% by weight WO 3 , 74.74 g), nickel nitrate hexahydrate (MerckTM, purity 99.999% by weight, 26.07 g) and a solution of orthophosphoric acid (MerckTM, 85% by weight in the water, 10.24 grams) in 68.3 mL of distilled water.
  • the extrudates are left to mature in an atmosphere saturated with water for 24 hours at ambient temperature, then they are dried at 90° C. for 16 hours.
  • the dried catalyst thus obtained is denoted C2.
  • Example 3 Preparation of the NiMoWP catalyst on C3 alumina by post-additivation of an organic compound (ascorbic acid).
  • catalyst precursor C2 100 g of catalyst precursor C2 described above in Example 2 and which is in the "extruded” form are impregnated with an aqueous solution containing 28.78 g of ascorbic acid (MerckTM, 100% purity) and whose volume is equal to the pore volume of catalyst precursor C2.
  • the quantities involved are such that the quantity of ascorbic acid is 0.5 mole per mole of molybdenum and tungsten (corresponding to 1.9 moles per mole of nickel).
  • the extrudates are left to mature in an atmosphere saturated with water for 16 h at room temperature.
  • the precursor of catalyst C3 is then dried at 120° C. for 2 hours to give catalyst C3.
  • Table 1 Composition of catalysts C1, C2 and C3.
  • the sequences of catalysts taken from catalysts C1, C2, C3 were tested in the hydrogenation of aromatics (HDA) of diesel fuel.
  • the charge is a mixture of 30% volume of gas oil from atmospheric distillation (also called straight-run according to Anglo-Saxon terminology) and 70% volume of light gas oil from a catalytic cracking unit (also called LCO for light cycle oil according to Anglo-Saxon terminology).
  • the test is carried out in an isothermal pilot reactor with a traversed fixed bed, the fluids circulating from bottom to top.
  • the reactor comprises two catalytic zones making it possible to evaluate different sequences of catalysts C1, C2 and C3.
  • the charge first passes through the first zone charged with the first catalyst, then the second zone charged with the second catalyst.
  • Example 4 the first zone is loaded with catalyst C1 (75% of the volume), then the second with catalyst C2 (25% of the volume).
  • Example 5 the first zone is loaded with catalyst C1 (75% of the volume), then the second with catalyst C3 (25% of the volume).
  • the first zone is loaded with catalyst C1 (40% by volume), then the second with catalyst C2 (60% by volume).
  • the first zone is loaded with catalyst C1 (95% by volume), then the second with catalyst C2 (5% by volume).
  • the catalytic tests were carried out under the following operating conditions: a total pressure of 8 MPa, a total volume of the two catalytic zones of 4 cm 3 , a temperature of 330° C., with a hydrogen flow rate of 3.0 L/ h and with a charge rate of 4.5 cm 3 /h.
  • the characteristics of the effluents are analysed: density at 15°C (NF EN ISO 12185), refractive index at 20°C (ASTM D1218-12), simulated distillation (ASTM D2887), sulfur content and nitrogen content.
  • the residual aromatic carbon contents are calculated by the n-d-M method (ASTM D3238).
  • the rate of hydrogenation of the aromatics is calculated as the ratio of the aromatic carbon content in the feed from which that of the effluents is subtracted, to that of the test feed.
  • the rate of hydrodenitrogenation is calculated as the ratio of the nitrogen content in the load, from which that of the effluents is subtracted, to that of the test load.
  • Table 2 clearly shows the gain in the catalytic effect provided by the specific sequences according to the invention. Indeed, the sequences of catalysts according to the invention make it possible to significantly increase the volume activities in the hydrodearomatization (HDA) and hydrodenitrogenation (HDN) reaction of gas oils. [Table 2]
  • Table 2 Relative activities HDA and HDN for the specific sequences according to the invention (examples 4 and 5) and non-compliant (examples 6 and 7).

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EP22702739.8A 2021-02-09 2022-02-03 Procede d'hydrotraitement mettant en ouvre un enchainement de catalyseurs avec un catalyseur a base de nickel, molybdene et tungstene Pending EP4291621A1 (fr)

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US7816299B2 (en) 2003-11-10 2010-10-19 Exxonmobil Research And Engineering Company Hydrotreating catalyst system suitable for use in hydrotreating hydrocarbonaceous feedstreams
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FR3013721B1 (fr) 2013-11-28 2015-11-13 Ifp Energies Now Procede d'hydrotraitement de gazole mettant en oeuvre un enchainement de catalyseurs
FR3013720B1 (fr) 2013-11-28 2015-11-13 IFP Energies Nouvelles Procede d'hydrotraitement de distillat sous vide mettant en oeuvre un enchainement de catalyseurs
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