Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • 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
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
  • B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • 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
  • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
  • B01J21/08—Silica
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/88—Molybdenum
  • B01J23/882—Molybdenum and cobalt
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/88—Molybdenum
  • B01J23/883—Molybdenum and nickel
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/888—Tungsten
  • B01J23/8885—Tungsten containing also molybdenum
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/14—Phosphorus; Compounds thereof
  • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/14—Phosphorus; Compounds thereof
  • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
  • B01J27/19—Molybdenum
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
  • B01J31/0235—Nitrogen containing compounds
  • B01J31/0237—Amines
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
  • B01J31/0235—Nitrogen containing compounds
  • B01J31/0237—Amines
  • B01J31/0238—Amines with a primary amino group
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
  • B01J31/0255—Phosphorus containing compounds
  • B01J31/0269—Phosphorus containing compounds on mineral substrates
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
  • B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
  • B01J35/51—Spheres
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
  • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
  • B01J37/0205—Impregnation in several steps
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
  • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
  • C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/02—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
  • 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
  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/60—Reduction reactions, e.g. hydrogenation
  • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
  • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
  • B01J2231/646—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of aromatic or heteroaromatic rings
• • 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
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/001—General concepts, e.g. reviews, relating to catalyst systems and methods of making them, the concept being defined by a common material or method/theory
  • B01J2531/002—Materials
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
  • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
  • C07C2521/04—Alumina
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
  • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
  • C07C2521/08—Silica
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
  • C07C2523/74—Iron group metals
  • C07C2523/75—Cobalt
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
  • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
  • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • C07C2527/14—Phosphorus; Compounds thereof
  • C07C2527/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1037—Hydrocarbon fractions
  • C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/201—Impurities
  • C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/02—Gasoline

Definitions

• the invention relates to a catalyst containing a catecholamine, 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 to comply with the specifications in force (sulfur content, aromatic content, etc.) for a given application (automotive fuel , gasoline or diesel, domestic fuel, engine fuel). It may also be pretreated a load to remove impurities or hydrogenate before treating in different processing processes, such as for example reforming processes, hydrocracking of vacuum distillates, catalytic cracking, hydroconversion of atmospheric residues or under vacuum.
• the composition and use of hydrotreatment catalysts are particularly well described in the article by BS Clausen, HT Topsoe, and FE Massoth, from Catalysis Science and Technology, volume 1 (1996), Springer-Verlag .
• the hydrodesulphurization of gasolines obtained by cracking must respond to a double antagonistic constraint: to ensure hydrodesulfurization deep species, while limiting the hydrogenation of unsaturated compounds (olefins) present.
• the hydrogenation of the olefins present in the excracked gasoline causes a very significant drop in the octane number. It is therefore necessary to find catalysts which are very selective for the hydrodesulfurization of sulfur compounds and minimize the hydrogenation of olefins.
• Conventional hydrotreatment catalysts generally comprise an oxide support and an active phase based on Group VI B 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 its oxide form.
• Prior to their use in a hydrotreating and / or hydrocracking reaction these catalysts are generally sulphurized to form the active species which is a transition metal sulfide.
• several axes have been studied. Among them, the addition of an organic compound to the hydrotreatment catalysts to improve their activity has been recommended by those skilled in the art, in particular for catalysts which have been prepared by impregnation followed by drying without subsequent calcination.
• US2014 / 0305842 discloses the use of heterocyclic compounds, containing oxygen or nitrogen in the ring, such as lactams, oxacycloalkanes or lactones.
• US2012 / 0205292 describes the use of oxygen and nitrogen containing compounds, such as aminocarboxylic acids or amino alcohols.
• WO 2014/056846 A1 discloses polymerized additives. Monomers are contacted with the support and polymerized, by means of an initiator and / or by increasing the temperature, before or after the impregnation of the metals of groups VIB and VIII on the support. The use of polymers seems to improve the dispersion of the active phase.
• the invention aims to provide a catalyst having improved catalytic performance.
• the invention relates to a catalyst comprising a support based on alumina or silica or silica-alumina, at least one member selected from group VIII and / or group VIB, and at least one catecholamine.
• a catecholamine on a catalyst containing at least one selected element of group VIII and / or group VIB, allowed to obtain a hydrotreatment catalyst and / or hydrocracking showing improved catalytic performance, in particular an increase in catalytic activity and / or an increase in selectivity.
• 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) can be lowered.
• the process for preparing the catecholamine catalyst has the advantage of not requiring a chemical initiator for the polymerization when it takes place.
• the catecholamine is chosen from dopamine, norepinephrine, adrenaline and isoprenaline, alone or as a mixture. According to a preferred variant, the catecholamine is dopamine.
• 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 catalyst additionally contains phosphorus, the phosphorus content being between 0.01 and 20% by weight expressed as P 2 0 5 relative to the total weight of the catalyst and the phosphorus ratio on the group VIB element. in the catalyst is greater than or equal to 0.01.
• the catecholamine content is between 1 and 40% by weight relative to the weight of the support.
• the catalyst further contains an organic compound other than catecholamine 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 catalyst is at least partially sulphurized.
• the invention also relates to the process for preparing said catalyst comprising the following steps:
• At least one component of a group VIB element and / or at least one component of a group VIII element is contacted with at least one catecholamine and optionally phosphorus with a support based on alumina or silica or silica-alumina, so as to obtain a catalyst precursor
• step b) drying said catalyst precursor from step a) at a temperature below 200 ° C, without subsequently calcining it.
• the catecholamine is dopamine.
• step a) comprises the following steps:
• a1) is prepared a support comprising a catecholamine
• step a2) the support obtained in step a1) is impregnated with an impregnating solution comprising at least one group VIB element and / or at least one group VIII element and optionally phosphorus so as to obtain a catalyst precursor.
• the support comprising a catecholamine is prepared by introducing a catecholamine at any time during the preparation of the support, and preferably during the shaping of the support, or by impregnation on an already formed support .
• step a) comprises the following steps:
• a1 ' a solution containing at least one group VIB element and / or at least one group VIII element, at least one catecholamine and optionally phosphorus with a support based on alumina or silica or silica-alumina so as to obtain a catalyst precursor.
• step a) comprises the following steps:
• a1 is impregnated with a support based on alumina or silica or silica-alumina by at least one solution containing at least one element of group VIB and / or at least one group VIII element and optionally phosphorus to obtain an impregnated support,
• the impregnated support obtained in step a1") is dried at a temperature below 200 ° C to obtain a dried impregnated support, and optionally the dried impregnated support is calcined to obtain a calcined impregnated support,
• a3 is impregnated dried and optionally calcined impregnated support obtained in step a2") by an impregnating solution comprising a catecholamine so as to obtain a catalyst precursor.
• the invention also relates to the use of the catalyst according to the invention or prepared according to the preparation method according to the invention in a hydrotreatment and / or hydrocracking process 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.
• Hydrotreating is understood to mean reactions including, in particular, hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrodeoxygenation (HDO) and aromatic hydrogenation (HDA).
• HDS hydrodesulfurization
• HDN hydrodenitrogenation
• HDO hydrodeoxygenation
• HDA aromatic hydrogenation
• the catalyst according to the invention comprises a support based on alumina or silica or silica-alumina, at least one element chosen from group VIII and / or group VIB, and at least one catecholamine.
• the hydrogenating, desulphurizing and de-nitrogenising function of said catalyst also called the active phase, is provided by at least one group VIB element and / or by at least one element of group VIII.
• the catalyst according to the invention comprises at least one element of group VIB and at least one element of group VIII.
• 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 active phase 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 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 may also comprise 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 0.01 and 20% by weight expressed as P 2 0 5 , preferably between 0.01 and 15% by weight expressed as P 2 0 5 , and very preferably between 0.02 and 10% by weight expressed as P 2 0 5 .
• the phosphorus molar ratio on the group VIB element in the catalyst is greater than or equal to 0.01, preferably greater than or equal to 0.05, preferably of between 0.05 and 1, and very preferably between 0.06 and 0.5.
• the catalyst according to the invention comprises a support based on alumina or silica or silica-alumina.
• the support of said catalyst when the support of said catalyst is based on alumina, it contains more than 50% of alumina relative to the weight of the support and, preferably, it contains only alumina.
• the alumina may be present in a crystallographic form of gamma alumina, delta, theta or alpha type, taken alone or as a mixture.
• the alumina support advantageously has a total pore volume of between 0.1 and 2 cm 3 . g "1 , preferably between 0.4 and 1.5 cm 3 .g -1 .
• the total pore volume is measured by mercury porosimetry according to ASTM 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, using an Autopore III TM model from the Microméritics TM 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 ASTM D3663. method described in the same work cited above.
• the support of said catalyst is a silica-alumina.
• the silica-alumina-based support contains at least 50% by weight of alumina with respect to the weight of the support.
• the silica content in the support is at most 50% by weight relative to the 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 is silica-based. In this case, it contains more than 50% by weight of silica relative to the 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 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 / or VIII, and / or at least a portion of the phosphorus when present and / or at least a portion of catecholamine which have been introduced outside the impregnations (introduced for example during the preparation of the support, for example by co-kneading).
• the support is advantageously in the form of beads, extrudates (cylinders or multilobed, for example trilobed or quadrilobes), pellets, or irregular agglomerates and non-spherical whose specific shape can result from a crushing step.
• the catalyst according to the invention also comprises at least one catecholamine.
• the catecholamine is advantageously chosen from dopamine, norepinephrine, adrenaline and isoprenaline, alone or as a mixture, corresponding to the following formulas:
• the catalyst comprises dopamine.
• dopamine is preferably used in the form of its hydrochloride corresponding to the following formula:
• Catecholamine, and especially dopamine may be present in the catalyst in at least partially polymerized form. Without being bound by any theory, it seems that catecholamine has a tendency to cyclize to an indole-type derivative (through an oxidation reaction, Acc Chem 2010, 43, 1452) when in contact with the support and then to form oligomers and / or polymers, especially during the drying step of the preparation method described below.
• the literature proposes two mechanisms of oligo- or polymerization: an aggregation of the molecules by weak bonds or a true polymerization by the formation of the covalent bonds between two molecules (Adv Funct, Mater 2012, 22, 471 1, Adv Funct Mater 2013, 23, 1331).
• thermogravimetric analysis or TGA for thermogravimetric analysis according to the English terminology
• infra-red spectroscopy or UV spectroscopy or NMR spectroscopy.
• the total content of catecholamine introduced into the catalyst according to the invention is between 1 and 40% by weight, preferably between 3 and 30% by weight relative to the weight of the support.
• the content of catecholamine introduced is expressed relative to the weight of the support, while the metal content is expressed as oxide, based on the weight of the catalyst after loss on ignition, that is to say, after calcination at at least 500 ° C that removes water and organic matter.
• this calcination is carried out in order to determine the metal content, but that the catalyst according to the invention is indeed a dried catalyst containing at least partially the catecholamine introduced after drying and prepared without subsequent calcination. Unless otherwise indicated, and in the case of dopamine, the content refers to the molecule without hydrochloride.
• the drying step (s) consecutive to the introduction of the catecholamine is (are) carried out at a temperature below 200 ° C. so as to preferably retain at least 30% preferably at least 50%, and most preferably at least 70% of the amount of the introduced catecholamine calculated on the basis of the carbon remaining on the catalyst.
• the catalyst according to the invention may comprise, in addition to dopamine, 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 organic compounds 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 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, malic acid, oxalic acid, gluconic acid, tartaric acid, citric acid, gamma ketovaleric, C1-C4 dialkyl succinate, methyl acetoacetate, lactone, di
• the nitrogen-containing organic compound may be one or more of compounds having one or more chemical functions selected from an amino 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 or tricine, or a lactam.
• MEA monoethanolamine
• EDTA ethylenediaminetetraacetic acid
• NDA nitrilotriacetic acid
• HEDTA N- (2-hydroxyethyl) ethylenediamine-N, N ', N'-triacetic acid
• DTPA
• 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 content of organic compound (s) with additive function (s) containing oxygen and / or nitrogen and / or sulfur on the catalyst according to the invention. 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 may be prepared according to any method of preparation of a supported catalyst comprising an organic compound known to those skilled in the art.
• the catalyst according to the invention may be prepared according to a preparation process comprising the following steps:
• the catalyst according to the invention during its preparation process does not undergo calcination after the introduction of catecholamine, or any other organic compound containing oxygen and / or nitrogen and and / or sulfur when present, to preserve at least a portion of the catecholamine or 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 catecholamine (or any other organic compound containing oxygen and / or nitrogen and / or sulfur), especially after impregnation.
• Group VIB and / or VIII elements post-additivation, possibly in the presence of phosphorus.
• the catalytic precursor may be a fresh catalyst precursor or a catalyst precursor after regeneration of a spent catalyst.
• the hydrogenating function comprising the group VIB and / or group VIII elements 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 / or VIII (post-additive), it is simply dried.
• the hydrogenating function comprising the elements of group VIB and / or group VIII of the catalyst according to the invention is then not in an oxide form.
• Group VIB and / or Group VIII elements may be introduced by any method known to those skilled in the art. They are generally introduced by impregnation, preferably by dry impregnation or by impregnation in excess of solution. Dry impregnation means that the volume of the impregnating solution corresponds exactly to the pore volume of the support, this volume is determined beforehand. Preferably, all the elements of group VIB and Group VIII is introduced by impregnation, preferably by dry impregnation and this regardless of the mode of implementation.
• the elements of group VIB and / or group VIII may also be introduced in part at least during the shaping of said support at the time of mixing with at least one alumina chosen as a matrix, the possible remaining elements being then introduced later by impregnation. It is also possible to introduce one of the elements of group VIB or of group VIII during the shaping of said support at the time of mixing, for example the element of group VIB, then to introduce the other element subsequently by impregnation , for example the element of group VIII.
• Molybdenum precursors that can be used are well known to those skilled in the art.
• the sources of molybdenum it is possible to use oxides and hydroxides, molybdic acids and their salts, in particular ammonium salts such as ammonium molybdate, ammonium heptamolybdate, phosphomolybdic acid ( H 3 2 0 4 PMOI o) and salts thereof, and optionally silicomolybdic acid (H 4 SiMoi 2 O 40) and its salts.
• the sources of molybdenum may also be heteropolycomposed Keggin type, Keggin lacunary, Keggin substituted, Dawson, Anderson, Strandberg, for example. Molybdenum trioxide, heteropolyanions of Strandberg, Keggin, Keggin lacunary or substituted Keggin type and phosphomolybdic acid 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 SiWi 2 O 40 ) 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 metatungstate are preferably used. Ammonium or heteropolyanions of Keggin, Keggin lacunary or substituted Keggin type or phosphotungstic acid.
• 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, cobalt carbonate or hydroxide. are used in a preferred manner.
• Phosphorus when present, may advantageously be introduced in whole or in part, alone or in admixture, with at least one of the Group VIB and Group VIII elements, and in any of the impregnation steps of the hydrogenating function if it is introduced in several times. Said phosphorus may also be introduced, in whole or in part, during the impregnation of catecholamine if it is introduced separately from the hydrogenating function (case of the post- and pre-additivation described later) and this in the presence or absence of an organic compound other than catecholamine.
• 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 mixing of the matrix of the chosen support.
• 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.
• Catecholamine is advantageously introduced by impregnation.
• the impregnation solution depending on the method of preparation, may be the same solution or a solution different from that containing the elements of group VIB and / or VIII.
• the impregnation solution is advantageously acidic.
• it has a pH between 1 and 9, and preferably between 5 and 7.
• Catecholamine can also be introduced as soon as the support is synthesized, at any stage of the synthesis thereof. It can thus be introduced before, during or after the mixing of the matrix of the chosen support, optionally in the presence of one or more elements of group VIB and / or VIII and optionally in the presence of phosphorus when it is present.
• 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 polar and protic solvents, in particular from the group formed by methanol, ethanol and water.
• a list of the usual polar solvents as well as their dielectric constant can be found in the book Solvents and Solvent Effects in Organic Chemistry (C. Reichardt, Wiley-VCH, 3rd edition, 2003, pages 472-474.
• the catalyst further comprises an additional additive (in addition to catecholamine) or a further group of additives selected from an organic compound containing oxygen and / or nitrogen and / or sulfur
• the latter may be introduced by an impregnating solution or from the synthesis of the support by mixing.
• the impregnated support is allowed to mature.
• the maturation allows the impregnating solution to disperse homogeneously within the support.
• the ripening step 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 room temperature. Generally a maturation period 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.
• the introduction of catecholamine in step a) can be carried out via several modes of implementation which are distinguished in particular by the mode of introduction of the additive which can be carried out either before the impregnation of the metals (pre- additivation), at the same time as the introduction of metals (co-additivation), or finally after the impregnation of metals (post-additivation).
• the contacting step a) can combine at least two modes of implementation, for example co-additivation and post-additivation. 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 contacting according to step a) of the process for preparing the catalyst according to the invention comprises the following steps:
• a1) is prepared a support comprising a catecholamine
• step a2) the support obtained in step a1) is impregnated with an impregnating solution comprising at least one group VIB element and / or at least one group VIII element and optionally phosphorus so as to obtain a catalyst precursor.
• a support comprising catecholamine is prepared.
• the catecholamine may be introduced at any time during the preparation of the support, and preferably during the shaping of the support (co-kneading) or by impregnation on an already formed support.
• a solution containing catecholamine in a polar solvent preferably water, preferably at room temperature, is prepared. a temperature between 15 and 60 ° C.
• the pH of the solution is between 1 and 9, and preferably between 5 and 7.
• the solution is generally stirred, advantageously for a period of 5 to 10 minutes.
• the solution is then impregnated on the support, preferably by dry impregnation.
• the impregnation step will then be followed by a drying step at a temperature below 200 ° C., preferably between 70 and 120 ° C., preferably between 80 and 100 ° C., under the drying conditions such that described below for step b).
• the carbon content of the dried support is between 2 and 12% by weight.
• a powder of alumina or of silica-alumina or of silica is mixed with a solution, preferably aqueous, containing catecholamine and optionally with a binder and a peptising agent (nitric acid, for example).
• a solution preferably aqueous, containing catecholamine and optionally with a binder and a peptising agent (nitric acid, for example).
• the mixture is homogenized in a kneader.
• the shaping is carried out by extrusion, by pelletizing, by the method of coagulation in drop (oil-drop according to English terminology), by rotating plate granulation or by any other method well known to those skilled in the art. In a very preferred manner, said shaping is carried out by extrusion.
• the shaping step will then be followed by drying at a temperature below 200 ° C., preferably between 70 and 120 ° C., preferably between 80 and 100 ° C., under the drying conditions such that described below in step b).
• the carbon content of the dried support is between 2 and 12% by weight.
• step a2) of the implementation by pre-impregnation the introduction of the elements of group VIB and / or 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, to using solution (s), preferably aqueous (s), containing the metal precursor (s) and optionally the phosphorus precursor.
• step a1) When it is desired to further introduce phosphorus or an additional additive (in addition to catecholamine) or a group of additional additives selected from an organic compound containing oxygen and / or nitrogen and / or sulfur, it may be introduced into the support of step a1) during shaping or by impregnation, and / or in the impregnation solution of step a2) or by an additional impregnation step to any time of the preparation process before the final drying of step b).
• an additional additive in addition to catecholamine
• a group of additional additives selected from an organic compound containing oxygen and / or nitrogen and / or sulfur it may be introduced into the support of step a1) during shaping or by impregnation, and / or in the impregnation solution of step a2) or by an additional impregnation step to any time of the preparation process before the final drying of step b).
• the catecholamine and the components of the group VIB and / or group VIII elements are introduced simultaneously into said support.
• step a) is the following step:
• a1 ' a solution containing at least one group VIB element and / or at least one group VIII element, at least one catecholamine and optionally phosphorus with a support based on alumina or silica or silica-alumina 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 with a maturation period between the impregnation step and the drying step.
• a compound formed from a group VIB element and from catecholamine is prepared beforehand, by contacting a solution containing a Group VIB element, preferably molybdenum, and a solution containing catecholamine under conditions where a precipitate is formed which contains the group VIB element and catecholamine.
• the compound is mixed with alumina powder or silica-alumina or silica, with water and optionally with a binder and a peptizing agent (nitric acid, for example). The mixture is homogenized in a kneader.
• the shaping is carried out by extrusion, by pelletization, by the method of the coagulation in drop (oil-drop according to the English terminology), by granulation with the turntable or by any other method well known to those skilled in the art.
• said shaping is carried out by extrusion.
• the shaping step will then be followed by drying at a temperature below 200 ° C., preferably between 70 and 120 ° C., preferably between 80 and 100 ° C., under the drying conditions such that described below in step b).
• the carbon content of the dried support is between 2 and 12% by weight.
• the group VIII element may be added during the co-kneading step or subsequently by impregnation or by another method known to those skilled in the art.
• step a) of the process for preparing the catalyst according to the invention post-additivation
• at least catecholamine is brought into contact with a dried and optionally calcined impregnated support comprising at least a component of a group VIB element and / or at least one component of a group VIII element, and optionally phosphorus, said support being based on alumina or silica or silica-alumina, so as to obtain a catalyst precursor.
• the contacting according to step a) comprises the following successive steps which will be detailed later: a1 ") is impregnated with a support based on alumina or silica or silica-alumina by at least one solution containing at least one element of group VIB and / or at least one element of group VIII and optionally phosphorus to obtain a impregnated support,
• the impregnated support obtained in step a1") is dried at a temperature below 200 ° C to obtain a dried impregnated support, and optionally the dried impregnated support is calcined to obtain a calcined impregnated support,
• a3 is impregnated dried and optionally calcined impregnated support obtained in step a2") by an impregnating solution comprising a catecholamine so as to obtain a catalyst precursor.
• step a1 ") of the implementation by post-impregnation the introduction of the elements of group VIB and / or group VIII and optionally 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 impregnation, and, preferably, by a single dry impregnation of said support, using solution (s), preferably aqueous (s) containing the or metal precursors and preferably the phosphorus precursor.
• the elements of group VIB and / or group VIII and optionally phosphorus, optionally an organic compound other than catecholamine may be introduced in step a1 ") successively by several impregnation solutions containing a
• each impregnation step is preferably followed by an intermediate drying step at a temperature below 200 ° C, advantageously between 50 and 180 ° C, of 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 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 below in step b ).
• 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 catecholamine so as to obtain a catalyst precursor.
• the catecholamine 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 catecholamine is introduced in dry impregnation, in the presence 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 catalyst precursor obtained by pre-, co-, post-additivation or a mixture of its variants, is then subjected to drying step b).
• drying 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 calcination step higher.
• Any drying step subsequent to the introduction of the catecholamine or any other additive is carried out at a temperature below 200 ° C., preferably between 50 and 180 ° C., preferably between 70 and 150 ° C., and 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. In a very preferred manner, 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 12 hours, preferably between 30 minutes and 6 hours and very preferably between 1 hour and 3 hours.
• 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, n-butyl mercaptan (or 1-butanethiol), polysulfide compounds of the tertiononyl polysulfide type, or any other compound known to those skilled in the art to obtain a good sulphurization of the catalyst.
• DMDS dimethyl disulfide
• alkyl sulphides such as, for example, dimethyl sulphide
• thiols such as, for example, n-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 hydrogenation, hydrodenitrogenation, hydrodearomatization, hydrodesulfurization, hydrodeoxygenation, hydrodemetallation reactions 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 hydrogenation, hydrodenitrogenation, hydrodearomatization, hydrodesulfurization, hydrodeoxygenation, hydrodemetallation reactions or hydroconversion of hydrocarbon feeds.
• 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 charges that are processed, 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., 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 , 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 generally contains from 0.02 to 5.0% by weight of sulfur. It can be derived from the direct distillation of oil (or straight run diesel according to English terminology), a coking unit (coking according to the Anglo-Saxon terminology), a visbreaking unit (visbreaking according to the terminology Anglo-Saxon), a steam cracking unit (steam cracking according to the English terminology), a hydrotreating unit and / or hydrocracking heavier loads and / or a catalytic cracking unit ( Fluid Catalytic Cracking according to the English terminology).
• Said diesel cutter presents preferably at least 90% by weight 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, more preferably between 200 and 400 liters per liter and an hourly space velocity between 1 and 10 h "1, preferably between 2 and 8 h" 1.
• the VVH 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.
• 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.
• the filler may be a deasphalted oil or paraffins from the Fischer-Tropsch process or any mixture of the aforementioned fillers.
• the fillers 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 fillers 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, is between 80 and 5000 l / l and most often between 100 and 2000 l / l
• These operating conditions used in the processes according to the invention generally allow to achieve pass conversions, products with boiling points below 340 ° C
• 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 hydro-refining 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 carried out in a conventional manner known to those skilled in the art under the appropriate 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 hydrotreatment process (in particular hydrodesulfurization) of a petrol fraction containing olefins in the presence of at least one catalyst according to the invention.
• the hydrotreatment (including hydrodesulphurisation) of gasolines must make it possible to respond to a double antagonistic constraint: to ensure a deep hydrodesulphurization of the species and to limit the hydrogenation of the unsaturated compounds (olefins) present in order to to limit the 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. ° C, at a total pressure of between 1 and 3 MPa, preferably between 1.5 and 2.5 MPa, at a Hourly Volumetric Rate (VVH), defined as the volume flow rate of the load relative to the volume of catalyst, between 1 and 10 h -1 , preferably between 2 and 6 h -1 and at a hydrogen / gasoline feedstock ratio of between 100 and 600 Nl / l, preferably between 200 and 400 Nl / l.
• VVH Hourly 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 A Preparation of the Cdopl catalyst (CoMoP / Pdop @ AI P O g ) by pre-additivation of an AI-Og-1 support
• a catalyst is prepared by pre-additivation of dopamine on an Al 2 O 3 -1 support followed by a CoMoP impregnation with a Mo content of 20% by weight expressed in M0O3.
• the support is then dried in an oven at 90 ° C for 20 h which gives a support (Pdop @ AI 2 0 3 -1).
• the additive support contains 5.2% w dopamine (or 6.4% w dopamine hydrochloride).
• a catalyst is prepared by CoMoP impregnation aiming at a content of 20% by weight of Mo expressed in MoO 3 on the Al 2 O 3 -1 support, which is not pre-additivated with dopamine: a) 2.94 g of acid phosphomolybdic acid and 1.86 g of Co (NO 3 ) 2 are dissolved in ethanol to obtain a solution of 8.6 ml.
• CoMoP / Al 2 O 3 -1 (C1) contains 20% by weight of MoO 3 , 4.4% by weight of CoO and 0.8% by weight of P 2 O 5 (expressed as oxide).
• the molar ratio Co / (Co + Mo) is 0.3.
• Example 2A Preparation of the catalyst Cdop2 (CoMoP / Pdop @ Al2O 3 ) by pre-additivation of an Al 2 O 3 support
• a catalyst is prepared by pre-additivation of dopamine on an Al 2 O 3 -1 support followed by a CoMoP impregnation aimed at a Mo content of 10% by weight expressed in MoO 3 .
• the support AI 2 O 3 -1 is prepared by pre-additivation of dopamine according to steps a) to c) of Example 1A. The following steps are then carried out:
• CoMoP / Pdop @ AI 2 O 3 -1 contains 10% by weight of MoO 3 , 2.3% by weight of CoO and 0.4% by weight of P 2 O 5 (relative to oxide mass, that is to say after loss on fire).
• the molar ratio Co / (Co + Mo) is 0.3.
• the dopamine content relative to the support is 5.2% by weight (or 6.4% by weight of dopamine hydrochloride).
• Example 2B (Comparative to Example 2A): Catalyst Preparation C2CoJ JoP / AlsOs
• a catalyst is prepared by impregnation CoMoP targeting a content of 10 wt.% Mo, expressed in MoO 3, on the Al 2 0 3 -1 support, which is not pre-additivated with dopamine:
• the impregnated support is matured in a saturated ethanol atmosphere for 12 hours. It is then dried at 40 ° C. under vacuum for 2 hours.
• CoMoP / Al 2 O 3 -1 (C2) contains 10% by weight of MoO 3 , 2.2% by weight of CoO and 0.4% by weight of P 2 0 5 (expressed as oxide).
• the molar ratio Co / (Co + Mo) is 0.3.
• Example 3A Preparation of the catalyst Cdop3 (CoMoP / Pdop @ AI P O g ) by pre-additivation of a carrier AI? Q 3 -2
• a catalyst is prepared by pre-additivation of dopamine on an Al 2 O 3 -2 support followed by a CoMoP impregnation aimed at a Mo content of 20% by weight expressed in MoO 3 and a high content of dopamine.
• the support is then dried in an oven at 90 ° C for 20 hours to give a support covered by partially polymerized dopamine (Pdop @ AI 2 0 3 -2).
• the support contains 11.2% wt of dopamine (or 13.8 wt% of dopamine hydrochloride).
• CoMoP / Pdop @ AI 2 0 3 -2 contains 20% by weight of MoO 3 , 4.5% by weight of CoO and 0.8% by weight of P 2 0 5 (expressed as oxide) .
• the molar ratio Co / (Co + Mo) is 0.3.
• the dopamine content relative to the support is 1 1, 2% wt (or 13.8% wt dopamine hydrochloride).
• Example 3B (Comparative to Example 3A) Preparation of catalyst C3 (CoMoP / Al O 3?)
• a catalyst is prepared by CoMoP impregnation aiming at a content of 20% by weight of Mo expressed in MoO 3 on the Al 2 O 3 -2 support which is not pre-additivated with dopamine: a) 2.2 g of phosphomolybdic acid and 1.86 g of Co (NO 3 ) 2 are dissolved in ethanol to give a solution of 4.8 mL. b) This solution is impregnated dropwise over 6 g of the support AI 2 0 3 -2. The impregnated support is matured in an ethanol saturated atmosphere for 12 hours. It is then dried at 40 ° C. under vacuum for 2 hours.
• a catalyst is prepared by pre-additivation of dopamine on an SiO 2 support followed by a CoMoP impregnation aimed at a Mo content expressed in MoO 3 of 20% by weight.
• the support is then dried in an oven at 90 ° C for 20 hours.
• the carrier contains 11% w dopamine (or 13.6% w dopamine hydrochloride).
• Example 4B (Comparative to Example 4A): Preparation of C4 CoMoP / SiQp Catalyst
• a catalyst is prepared by CoMoP impregnation aiming at a content of 20% by weight of Mo expressed in M0O3 on the support Si0 2 which is not pre-additivated with dopamine: a) 3.67 g of phosphomolybdic acid and 2.32 g Co (NO 3 ) 2 are dissolved in ethanol to give a solution of 13 mL. b) This solution is impregnated dropwise over 10 g of SiO 2 support. The impregnated support is matured in an ethanol saturated atmosphere for 12 hours. It is then dried at 40 ° C. under vacuum for 2 hours.
• CoMoP / SiO 2 (C4) contains 20% by weight of MoO 3 , 4.5% by weight of CoO and 0.8% by weight of P 2 0 5 (expressed as oxide).
• the molar ratio Co / (Co + Mo) is 0.3.
• a catalyst is prepared by pre-additivation of dopamine on an Al 2 O 3 -3 support by co-mixing followed by a COOMP impregnation aimed at a Mo content of 20% by weight expressed in MoO 3 .
• alumina-3 in powder form, BET surface 279 m 2 / g, pore volume 1, 28 mL / g
• 1.13 g of methyl cellulose and 3.16 g of hydrochloride of dopamine are introduced into a kneader (Brabender®).
• the mixture is homogenized by kneading.
• 0.234 g of nitric acid as a peptizing agent dissolved in 29 ml of water is slowly added to the mixture and kneading is continued until a paste of the right consistency for extrusion is obtained.
• the paste is then introduced into an extruder to produce trilobal extrusions.
• the support is then dried in an oven at 90 ° C for 20 h.
• the carrier contains 8.1% w dopamine (or 10% w dopamine hydrochloride).
• the catalyst Cdop5 is prepared by impregnation on this support Pdop @ AI 2 0 3 -3, according to the following steps:
• CoMoP / Al 2 O 3 -3 (Cdop5) contains 20% by weight of MoO 3 , 4.6% by weight of CoO and 0.8% by weight of P 2 O 5 (expressed as oxide).
• the Co / (Co + Mo) molar ratio is 0.3.
• the dopamine content relative to the support is 8.1% wt (or 10% wt dopamine hydrochloride).
• Example 6 Preparation of a Cdop6 Catalyst (CoMoP / Pdop @ AI TM Q) by co-impregnation
• a catalyst was prepared by co-additive of dopamine, cobalt, molybdenum and phosphorus on a substrate Al 2 0 3 -1 to a Mo content of 10 wt% expressed as Mo0 3.
• CoMoP @ Pdop @ AI 2 0 3 -1 contains 10% by weight of MoO 3 , 2.2% by weight of CoO and 0.4% by weight of P 2 0 5 (expressed as oxide) .
• the molar ratio Co / (Co + Mo) is 0.3.
• the dopamine content relative to the support is 5.2% by weight (or 6.4% by weight of dopamine hydrochloride).
• a catalyst is prepared by precipitation of a Mo-dopamine compound, which is comalaxed with alumina-3 and a cobalt precursor, and then dried.
• This catalyst according to the invention does not contain phosphorus.
• step b) 15 g of Al 2 O 3 -3 (in powder form), 0.71 g of methyl cellulose and 13.15 g of the Mo: dopamine (1: 2) precipitate obtained in step a) are introduced in a mixer (Brabender®). The mixture is homogenized by kneading. 0.159 g of nitric acid as a peptizing agent and 3.68 g of Co (NO 3 ) 2, dissolved in 26.6 ml of water are slowly added to the mixture and the mixing is continued until a paste of good consistency for extrusion.
• CoMoP @ Pdop @ AI 2 0 3 -3 contains 20% by weight of MoO 3 and 4.4% by weight of CoO (expressed as oxide).
• the molar ratio Co / (Co + Mo) is 0.3.
• the dopamine content relative to the Al 2 O 3 support is 38%.
• a catalyst is prepared by post-additivation of dopamine on an Al 2 O 3 -1 alumina catalyst precursor containing cobalt, molybdenum and phosphorus, with a Mo content of 20% by weight expressed in MoO 3 .
• the aim of the toluene hydrogenation test is to evaluate the hydrogenating activity of the catalysts in the presence of H 2 S and under hydrogen pressure.
• the mass of catalyst corresponding to a bed volume of 0.45 cm 3 is charged to a fixed bed reactor through, either before or after prior sulphidation.
• the preliminary sulphurization is carried out in the gas phase with a H 2 S / H 2 mixture in which the amount of H 2 S is 15% by volume at a temperature of 350 ° C. for 2 hours.
• the feed contains 20% toluene, 5.88% dimethyldisulphide (CH 3 -SS-CH 3 , sulfurizing agent) and 74.12% cyclohexane (as solvent).
• This liquid charge is mixed with a flow of hydrogen.
• the hydrogen flow rate on liquid feed rate is 450 LH 2 (at 0 ° C and atmospheric pressure) per L liquid feed (based on density at 15 ° C).
• the reactor is placed under load at a pressure of 60 bar (6 MPa).
• the charge rate corresponds to a hourly volume velocity (VVH) of 4 h "1.
• the temperature is slowly increased to 350 ° C. (2 ° C./min ramp) After 2 h at 350 ° C., the VVH is reduced 2 h "1.
• the catalytic activity is evaluated after a stabilization time of at least 4 hours. Effluent samples are analyzed by gas chromatography. The disappearance of toluene is evaluated. This test was repeated at a temperature of 370 ° C and 390 ° C.
• This catalytic test aims to evaluate the activity and selectivity of a hydrotreatment catalyst for HDS of a cracked gasoline.
• the mass of catalyst corresponding to a bed volume of 0.30 cm 3 is loaded into a fixed-bed reactor, either before or after prior sulphurization.
• the sulphurization step is carried out in the gas phase with a H 2 S / H 2 mixture in which the amount of H 2 S is 15% by volume at a temperature of 350 ° C. for 2 hours.
• the catalyst charged to the reactor is first sulfurized with a feed containing 4% DMDS and 96% by weight n-heptane.
• the liquid charge is mixed with a flow rate of H 2 (300 LH 2 per L of liquid charge).
• the pressure is set at 15 bar (1.5 MPa).
• the temperature is increased with a ramp of 2 ° C / min at 350 ° C and maintained at 350 ° C for 2h.
• the test load contains 10% by weight of 2,3-dimethylbut-2-ene, 0.30% by weight of 3-methylthiophene and 89.7% by weight of n-heptane (as the solvent).
• the liquid charge rate corresponds to a hourly volume velocity (VVH) of 6 hr -1 .
• the temperature is increased from 190 ° C to 220 ° C in 10 ° C intervals.
• the conversion of 3-methylthiophene is calculated via the disappearance of 3-methylthiophene.
• the selectivity of the catalyst is evaluated via the appearance of the products of the reaction.
• x conversion of 3-methyl-thiophene or hydrogenated products of 2,3-dimethylbut-2-ene.
• SiO 2 supported catalyst exhibits improved activity compared to its dopamine-free counterpart.
• the catalysts C1, C2, C1 dop and C2dop were tested in diesel HDS.
• the diesel fuel used is a straight-run diesel fuel mixture and Light Cycle Oil (LCO).
• the sulfur content is 0.6815 wt%.
• the nitrogen content is 488 mg / dm 3 .
• the density at 15 ° C is 0.8795 g / cm 3 .
• the test is conducted in a fixed-bed isothermal reactor. After sulphurization in situ at 350 ° C. in the unit under pressure using the test gas oil, to which 2% by weight of dimethyl disulphide is added, the hydrodesulfurization test was carried out under the following operating conditions: a total pressure of 4 MPa a catalyst volume of 0.48 cm 3 , a temperature of 330 to 340 ° C, a hydrogen flow rate of 2.56 cm 3 / min and a feed rate of 0.48 cm 3 / h.
• the following Table shows the contents of S (in ppm, ie in ⁇ g S / g gas) in the reactor effluent. These contents are measured after a stabilization period of 10 days for the first temperature and 5 days for the following two temperatures. It is clearly seen that the catalyst prepared with dopamine has a better desulfurizing activity than its prepared analogue without dopamine.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Materials Engineering (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• General Chemical & Material Sciences (AREA)
• Inorganic Chemistry (AREA)
• Catalysts (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=56087384

Family Applications (1)

Country Status (6)

Families Citing this family (6)

Family Cites Families (22)

• 2016
  • 2016-03-30 FR FR1652743A patent/FR3049475B1/fr not_active Expired - Fee Related
• 2017
  • 2017-03-01 EP EP17707877.1A patent/EP3436190A1/de not_active Withdrawn
  • 2017-03-01 CN CN201780020626.0A patent/CN108883404A/zh active Pending
  • 2017-03-01 WO PCT/EP2017/054687 patent/WO2017167522A1/fr active Application Filing
  • 2017-03-01 JP JP2018550444A patent/JP2019515781A/ja active Pending
  • 2017-03-01 US US16/089,250 patent/US20190105648A1/en not_active Abandoned

Also Published As

Similar Documents

Legal Events