Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/02—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
• • 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
  • 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
  • B01J31/26—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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/612—Surface area less than 10 m2/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/613—10-100 m2/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/615—100-500 m2/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/63—Pore volume
  • B01J35/633—Pore volume less than 0.5 ml/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/63—Pore volume
  • B01J35/635—0.5-1.0 ml/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/63—Pore volume
  • B01J35/638—Pore volume more than 1.0 ml/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/64—Pore diameter
  • B01J35/643—Pore diameter less than 2 nm
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • 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
  • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/08—Heat treatment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/08—Heat treatment
  • B01J37/082—Decomposition and pyrolysis
  • B01J37/088—Decomposition of a metal salt
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/16—Reducing
  • B01J37/18—Reducing with gases containing free hydrogen
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/20—Sulfiding
• • C—CHEMISTRY; METALLURGY
  • 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
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
  • C10G3/42—Catalytic treatment
  • C10G3/44—Catalytic treatment characterised by the catalyst used
  • C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
  • C10G3/46—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof in combination with chromium, molybdenum, 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
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
  • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/44—Hydrogenation of the aromatic hydrocarbons
  • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
  • C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
  • C10G45/50—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metal, or compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G7/00—Distillation of hydrocarbon oils
  • C10G7/12—Controlling or regulating
• • 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
  • C10G2300/1048—Middle distillates
  • C10G2300/1055—Diesel having a boiling range of about 230 - 330 °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
  • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
• • 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
  • C10G2300/30—Physical properties of feedstocks or products
  • C10G2300/301—Boiling range
• • 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
  • C10G2300/30—Physical properties of feedstocks or products
  • C10G2300/308—Gravity, density, e.g. API
• • 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
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/70—Catalyst aspects
• • 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
  • C10G2400/04—Diesel oil
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry
  • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

• the present invention relates to a process for adding an organic compound to a porous solid, in particular to a porous catalyst support.
• the process according to the invention can be integrated in a process for preparing a heterogeneous catalyst, which is "additive" to an organic compound and comprises a porous support on which at least one Group VI metal is deposited and / or at least one Group VIII metal.
• a heterogeneous catalyst which is "additive" to an organic compound and comprises a porous support on which at least one Group VI metal is deposited and / or at least one Group VIII metal.
• Conventional hydrotreatment catalysts generally comprise a support based on an oxide of a metal (for example aluminum) or a metalloid (for example silicon) and an active phase based on at least one metal group VIB and / or at least one group VIII metal in their oxide forms and optionally phosphorus.
• the preparation of these catalysts generally comprises a step of impregnating the metals and phosphorus on the support, optionally followed by a maturation step, followed by drying or calcination to obtain the active phase in the form of oxides.
• these catalysts are generally subjected to sulphidation in order to form the active species in sulphide form.
• a family of compounds now well known in the literature relates to chelating nitrogen compounds (EP 181035, EP 1043069 and US 6,540,908) with, for example, ethylenediaminetetraacetic acid (EDTA), ethylenediamine, diethylenetriamine or nitrilotriacetic acid (NT A).
• EDTA ethylenediaminetetraacetic acid
• NT A nitrilotriacetic acid
• the processes for preparing the additivated catalysts generally implement an impregnation step in which the organic compound is introduced so as to fill the entire porosity of the support impregnated or not with metal precursors in order to obtain a homogeneous distribution. This leads to using large amounts of organic compound or diluting the organic compound in a solvent. After impregnation, a drying step is then necessary to eliminate the excess of organic compound or the solvent and thus release the porosity necessary for the implementation of the catalyst. The additional cost of the excess of the organic compound or the use of a solvent is added the cost of an additional stage of energy-consuming drying.
• CN 102463151 discloses a method of heat treating a catalyst support comprising a metal phase in a gaseous atmosphere comprising the organic compound which is therefore in the gaseous state.
• the heat treatment is thus performed at a temperature above the boiling temperature of said organic compound.
• the heat treatment is carried out at a temperature of between 150 and 500 ° C. This process is not without risk in its implementation. Indeed, for many organic compounds, such as ethylene glycol cited in this document, the flash point is below the boiling point. There is therefore a risk of fire to work at a temperature above the boiling point.
• a high temperature can also lead to partial or total decomposition of the additive greatly reducing its effect.
• citric acid commonly used as an organic additive (US 2009/0321320) decomposes at 175 ° C while its boiling point is 368 ° C at atmospheric pressure.
• An object of the invention is therefore to propose an alternative method for depositing an organic compound on a porous catalyst support which does not use a step of impregnating the support with a solution containing the organic compound and which is more safe and less expensive in its industrial implementation.
• the present invention relates to a process for adding an organic compound to a porous solid comprising a step a) in which the solid is simultaneously brought into contact with the solid. porous and the organic compound in the liquid state and without physical contact between the solid and the organic compound in the liquid state, at a temperature below the boiling point of the organic compound and under pressure and duration conditions such as a fraction of said organic compound is transferred in the gaseous state to the porous solid.
• the process for adding the organic compound according to the invention does not involve a conventional impregnation step by means of a solution containing a solvent in which the organic compound is diluted. Therefore it is not necessary to proceed to a solid drying step to remove the solvent hence a more economical method in terms of hot utility and raw material.
• the step of adding the organic compound is conducted at a temperature below the boiling temperature of said organic compound, which results in a substantial gain in terms of energy and in terms of safety compared to the setting implemented in CN 102463151.
• the process according to the invention is also characterized in that the addition of the organic compound to the porous solid is carried out without physical contact with the organic compound in the liquid state, that is to say without impregnation of the porous solid by the liquid.
• the method is based on the principle of the existence of a vapor pressure of the organic compound which is generated by its liquid phase at a given temperature and pressure.
• a part of the organic compound molecules in the liquid state passes to the gaseous state (vaporization) and is then transferred (gaseous) to the porous solid.
• This step a) of bringing into contact is carried out for a time sufficient to reach the targeted content of organic compound in the porous solid.
• step a) is carried out by means of an addition unit of said organic compound comprising a first and a second compartments in communication so as to allow the passage of a gaseous fluid between the compartments, the first compartment containing the porous solid and the second compartment containing the organic compound in the liquid state.
• the unit comprises a chamber including the first and second compartments, the two compartments being in communication by gas.
• the unit comprises two enclosures respectively forming the first and second compartments, the two chambers being in gaseous communication.
• step a) bringing the porous solid into contact with the organic compound in the liquid state is carried out in the presence of a flow of a carrier gas flowing from the second compartment into the first compartment.
• step a) is carried out at an absolute pressure of between 0 and 1 MPa.
• the operating temperature of step a) is less than 200 ° C., preferably between 10 ° C. and 150 ° C., more preferably between 25 ° C. and 120 ° C.
• step a) a gaseous effluent containing said organic compound is withdrawn from the first compartment and the effluent is recycled to the first and / or second compartment.
• step a) a gaseous effluent containing said organic compound in the gaseous state is withdrawn from the first compartment, said effluent is condensed so as to recover a liquid fraction containing the organic compound in the liquid state. and said liquid fraction is recycled to the second compartment.
• the porous solid is selected from a catalyst support and a catalyst support further comprising at least one Group VIB metal and / or at least one Group VIII metal.
• the porous support is based on an oxide of a metal and / or a metalloid.
• the porous support is based on alumina and / or silica.
• the organic compound which is used in the process is chosen from organic molecules containing oxygen and / or nitrogen and / or sulfur.
• the invention also relates to a process for preparing a catalyst comprising a porous support, at least one Group VIB metal and / or at least one Group VIII metal and at least one organic compound which comprises at least the following steps:
• step i) being performed before or after steps ii) and iii).
• the solution of step ii) may also comprise at least one additional organic compound different from the organic compound used in step i).
• the process according to the invention for the preparation of a catalyst may also comprise at least one step of impregnating the porous support with a solution comprising an organic compound that is different from the organic compound used in step i).
• the present invention relates to a process for treating a hydrocarbon feedstock in which the hydrocarbon feedstock and a catalyst are brought into contact with hydrogen at a temperature of between 180 and 450 ° C. at a pressure of between 0.degree. 5 and 30 MPa, with a hourly space velocity of between 0.1 and 20 h -1 and with a hydrogen / charge ratio expressed as a volume of hydrogen, measured under normal conditions of temperature and pressure, per volume of liquid charge of between 50 l / l at 5000 l / l, said catalyst having been prepared by a process according to the invention and subjected to at least one sulphurization step.
• the subject of the present invention is a process for adding an organic compound to a porous solid which is, for example, a porous catalyst support or a porous support which already contains at least one Group VIB metal and / or at least one metal Group VIII which will be referred to as "catalyst precursor" in the remainder of the description.
• the porous support is preferably based on at least one oxide of a metal or a metalloid.
• the porous support is based on alumina or silica or silica-alumina.
• the support When the support is based on alumina, it contains more than 50% by weight of alumina.
• the alumina is gamma alumina.
• the support is a silica-alumina that is to say that it contains at least 50% by weight of alumina.
• the silica content in the support is at most 50% by weight, most often less than or equal to 45% by weight, preferably less than or equal to 40% by weight.
• the support of said catalyst is based on silica, it contains more than 50% by weight of silica 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.
• the 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 contain at least one doping element, such as, for example, phosphorus.
• the porous solid preferably has a total pore volume of between 0.1 and 1.5 cm 3 / g, preferably between 0.4 and 1.1 cm 3 / g.
• the total pore volume is measured by mercury porosimetry according to ASTM D4284 with a wetting angle of 140 °, as described in 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 porous solid is advantageously between 5 and 400 m 2 / g, preferably between 10 and 350 m 2 / g, more preferably between 40 and 350 m 2 / g.
• the specific surface is determined in the present invention by the BET method according to ASTM D3663, a method described in the same work cited above.
• the porous solid is generally in the form of balls, extrudates, pellets, or irregular and non-spherical agglomerates whose specific shape can result from a crushing step.
• the process for adding the organic compound can be carried out on a porous solid which is a catalyst precursor, that is to say on a porous support further comprising at least one Group VIB metal and / or or at least one Group VIII metal.
• the groups of chemical elements are given according to the CAS classification (CRC Handbook of Chemistry and Physics, publisher CRC press, editor-in-chief D.R. Lide, 81st edition, 2000-2001).
• group VIII according to the CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IUPAC classification.
• the catalyst precursor may be a fresh catalyst precursor, that is to say which has not been used before in a catalytic unit and in particular in hydrotreatment and / or hydrocracking.
• the catalyst precursor according to the invention may also be a so-called "regenerated” catalyst.
• the term “regenerated catalyst” refers to a catalyst which has been previously used in a catalytic unit and in particular in hydrotreating and / or hydrocracking and which has been subjected to at least one calcination step in order to burn the coke (regeneration).
• the method of adding an organic compound to a porous solid can be carried out in an addition unit of said organic compound.
• the addition unit used comprises first and second compartments in communication so as to allow the passage of a gaseous fluid between the two compartments and in which the first compartment is able to contain the porous solid and the second compartment. is capable of containing the organic compound in liquid form.
• the process comprises a step a) in which the porous solid and the organic compound in liquid form are simultaneously brought into contact without physical contact between the solid and the organic compound in liquid form, at a temperature below the boiling point of the compound.
• the unit of presence comprises a chamber including the first and second compartments, the compartments being in communication by gas.
• the compartments are arranged side by side and separated by a partition, for example substantially vertical, integral with the bottom of the enclosure and extending only over a fraction of the height of the enclosure so as to let the sky spread. gaseous from one compartment to another.
• the compartments are arranged one above the other and are in communication so as to allow the passage of the organic compound in the gaseous state between the two compartments.
• the enclosure is closed.
• the unit comprises two enclosures forming respectively the first and the second compartments, the two enclosures being in communication via gas, for example by means of a pipe.
• the two enclosures are closed.
• the compartment for containing the liquid organic compound comprises means for moving said liquid to facilitate the transfer of the organic compound in a gaseous state from one compartment to another.
• the two compartments comprise means for moving the liquid and the porous solid respectively.
• the compartment containing the organic compound in the liquid state is equipped with internals intended to maximize the surface of the gas / liquid interface. These internals are for example porous monoliths impregnated with capillarities, falling films, packings or any other means known to those skilled in the art.
• step a) of bringing the porous solid into contact with the organic compound is carried out in the presence of a gas (vector) flowing from the second compartment into the first compartment so as to entrain the organic molecules to the gaseous state in the compartment containing the porous solid.
• a gas may be chosen from carbon dioxide, ammonia, air with controlled hygrometry, a rare gas such as argon, nitrogen, hydrogen, natural gas or a refrigerant gas. of the classification published by IUPAC.
• step a) comprises a step in which a gaseous effluent containing said organic compound is withdrawn from the first compartment and the effluent is recycled to the first and / or second compartment.
• a gaseous effluent containing said organic compound in the gaseous state is withdrawn from the first compartment, said effluent is condensed so as to recover a liquid fraction containing the organic compound in the liquid state and said fraction is recycled. liquid in the second compartment.
• the placing step is preferably carried out at an absolute pressure of between 0 and 1 MPa.
• the temperature of the placing step is set at a temperature below the boiling point of the organic compound.
• the temperature of the placing step is generally less than 200 ° C., preferably between 10 ° C. and 150 ° C., more preferably between 25 ° C. and 120 ° C.
• any organic compound may be employed provided that said organic compound is in the liquid state under the temperature and pressure conditions implemented in step a).
• the organic compound may be chosen for example from organic molecules containing oxygen and / or nitrogen and / or sulfur.
• the organic compound is, for example, 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.
• it may be chosen from triethylene glycol, diethylene glycol, ethylene glycol, propylene glycol, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, 1,4-butanediol, 1-butanediol and the like.
• the present invention relates to a process for preparing a catalyst with an organic compound additive comprising a porous support, at least one Group VIB metal and / or at least one Group VI II metal and at least one Group VI II metal. at least one organic compound, the process comprising at least the following steps: i) depositing the organic compound on the porous support by implementing the method according to the invention;
• step i) being performed before or after steps ii) and iii).
• the process for adding the organic compound according to the invention may be carried out one or more times in a production line of an additivated catalyst in order to introduce one or more organic compounds before the impregnation step. of the active metal phase and / or to allow the introduction of one or more organic compounds on a porous support already containing an active metal phase which can be optionally sulphured.
• the porous support is subjected to an impregnation step with a solution comprising at least one Group VIB metal and / or at least one a group VIII metal so as to deposit an active metal phase (step ii).
• the porous support impregnated with the active metal phase is optionally subjected to a maturation step and is then dried (step iii) in order to eliminate the solvent provided by step ii).
• the porous support containing the active and dried metallic phase is treated according to stage i) in the unit of presence with the organic compound in the liquid state so as to provide an additivated catalyst of said organic compound.
• the porous support may in particular already contain an additional organic compound different from that used in step i).
• This additional organic compound may have been incorporated into the support by means of the addition process according to the invention or according to any other method known to those skilled in the art, for example by impregnation of a solution containing the additional organic compound.
• a catalyst support containing no active phase is used.
• the support is first subjected to a step of adding the organic compound according to the invention so as to provide an additive-containing catalyst support of the organic compound (step i), which after an optional phase of maturation, is sent to the step of impregnating the active phase (step ii).
• This step may consist in bringing the additive-containing support into contact with a solution containing at least one precursor of at least one Group VIII metal and / or at least one precursor of at least one Group VIB metal.
• the additive catalyst thus obtained is optionally left to mature and then subjected to a drying step (step iii) in order to remove the solvent provided during the step of impregnating the metal precursors of the active phase.
• the porous support used may optionally already contain an additional organic compound different from that used in step i), the additional organic compound having been incorporated in the catalyst support by means of the process of addition according to the invention or according to any other method known to those skilled in the art.
• the step ii) of deposition of the active metal phase can implement a solution containing at least one precursor of at least one metal of group VIII and or at least one precursor of at least one Group VIB metal and further one or more additional organic compounds different from that of step i).
• the additivated catalyst obtained after steps i) to iii) described above can also be treated by one or more subsequent steps to incorporate one or more additional organic compounds different from that used in step i).
• the incorporation of one or more other additional additional organic compounds can be carried out by means of the addition method according to the invention or according to any other method known to those skilled in the art.
• Said said additional organic compound (s) may, for example, be introduced in one of the modes described in document FR 3 035 008.
• the catalysts according to the invention may contain, as active phase, one or more Group VIB and / or Group VIII metals.
• the preferred Group VIB metals are molybdenum and tungsten and the preferred Group VIII metals are non-noble elements, particularly 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 catalysts generally have a total content of Group VIB metal and / or Group VIII greater than 6% by weight expressed as oxide relative to the total weight of dry catalyst.
• the total content of Group VIB metals is between 5 and 40% by weight, preferably between 8 and 35% by weight, and more preferably between 10 and 32% by weight expressed as Group VIB metal oxide relative to total weight of dry catalyst.
• the total content of metals of group VIII is generally between 1 and 10% by weight, preferably between 1.5 and 9% by weight, and more preferably between 2 and 8% by weight expressed in Group VIII metal oxide relative to to the total weight of dry catalyst.
• the molar ratio of Group VIII metals to Group VIB metals 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 may also include phosphorus as a dopant.
• the phosphorus content in said catalyst is preferably between 0.1 and 20% by weight, expressed as P205, preferably between 0.2 and 15% by weight, expressed as P205, and very preferably between 0.3 and 11% by weight. weight expressed as P205 relative to the total weight of dry catalyst.
• the molar phosphorus ratio on the Group VIB metals in the catalyst is greater than or equal to 0.05, preferably greater than or equal to 0.07, preferably of between 0.08 and 1, preferably of between 0.01 and 0.9 and very preferably between 0.15 and 0.8.
• the catalyst may advantageously also contain at least one dopant chosen from boron, fluorine and a mixture of boron and fluorine.
• the boron content is preferably between 0.1 and 10% by weight expressed as boron oxide, preferably between 0.2 and 7% by weight, and very preferably between 0.2 and 5% by weight relative to the total weight of dry catalyst.
• the fluorine content is preferably between 0.1 and 10% by weight expressed as fluorine, preferably between 0.2 and 7% by weight, and very preferably between 0.2 and 5% by weight. % by weight relative to the total weight of dry catalyst.
• the additivated catalysts thus prepared are especially used for the hydrotreatment reactions of hydrocarbon feeds such as petroleum cuts or for the synthesis of hydrocarbons from synthesis gas.
• hydrotreatment includes, in particular, total or selective hydrogenation reactions, hydrodenitrogenation, hydrodearomatization, hydrodesulphurization, hydrodeoxygenation, hydrodemetallation, and hydrocracking of hydrocarbon feeds.
• the additivated catalyst generally undergoes a sulphurization step before its implementation.
• 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, waxes. and paraffins, waste oils, deasphalted residues or crudes, feeds from thermal or catalytic conversion processes, lignocellulosic feedstocks or biomass feedstocks, alone or as a mixture.
• the operating conditions used in the The processes employing the hydrotreatment reactions of hydrocarbon feedstocks described above 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 , and the ratio Hydrogen / charge 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 between 80 to 2000 l / l.
• Figure 1 is a diagram illustrating the principle of addition of an organic compound according to the common practice known to those skilled in the art
• FIG. 2 is a diagram illustrating the process according to the invention for adding an organic compound according to a first embodiment
• FIG. 3 shows a diagram of the process for adding an organic compound according to a second embodiment
• FIG. 4 is a diagram of the process for adding an organic compound according to a third embodiment.
• FIG. 1 corresponds to a block diagram showing a known method of adding an organic compound to a porous catalyst support or a catalyst precursor as described above, which is hereinafter referred to by the generic term "solid" .
• the solid batch 1 is subjected to optional pretreatment in a solid pretreatment unit 2, intended, if necessary, to condition the solid before the step of impregnating the organic compound.
• This pretreatment step may be, for example and according to the desired effect, a preliminary drying step to adjust the residual moisture.
• This pretreatment can also be an addition by controlled addition of the same solvent, provided by line 3, that which is used during the impregnation of the organic compound in order to avoid a too strong reaction of the solid during the phase of impregnation organic compound.
• the type of reaction that is to be avoided is for example a strong release of heat due to the sudden adsorption of the solvent (such as water for example) on the active sites of the solid.
• the batch of solid 4 resulting from the pretreatment stage is sent to an impregnation unit 5 of the organic compound.
• this step employs a solution containing a solvent, for example water, in which the organic compound to be impregnated is dissolved.
• the impregnation solution is brought via line 6.
• the impregnation is carried out according to any method known to those skilled in the art, for example by dry impregnation.
• the solid in motion is subjected to a jet of the impregnating solution, the volume of spray solution being generally equivalent to the accessible pore volume of the solid to be impregnated.
• the impregnated solid is discharged via line 7 into a drying unit 8 in order to remove the solvent which has been incorporated in the solid together with the organic compound.
• Flow 9 represents the hot utility that is used to dry the solid, which is for example hot air. This results in a dried porous solid comprising the chosen organic compound.
• the amount introduced is not sufficient after a single impregnation step. In which case, it will be possible to use several impregnation and drying steps described above.
• the porous solid may undergo one or more impregnation steps of one or more Group VIB and / or Group VIII metals in order to deposit a metal active phase.
• the step or steps of impregnation of the metal or metals may be followed, after possibly a maturation step, a drying step at a moderate temperature, generally less than 200 ° C.
• FIG. 2 represents a schematic diagram of the method for adding the organic compound according to the invention, which consists in bringing the porous solid to be treated in contact with the organic compound in the liquid state into a unit 1 1, the setting in the presence being performed without physical contact between the porous solid and the liquid phase.
• the porous solid 1 is possibly sent to a pre-treatment unit 2 as mentioned above.
• the pretreatment may consist of a step of drying the solid, for example when said porous solid is a catalyst precursor obtained by impregnating a solution containing at least one Group VIB metal and / or at least one Group VIII metal.
• the porous solid 4 resulting from the pretreatment is fed into a unit 1 1 for bringing the solid into contact with the organic compound in the liquid state.
• the unit 1 1 comprises an enclosure segmented into two compartments A and B separated from one another by a partition means 12, the two compartments being in communication so as to allow the passage of a gaseous flow of organic compound so that compartments A and B share the same gaseous atmosphere.
• the compartment A is able to receive the porous solid 4 while the compartment B is able to contain the liquid organic compound.
• the partition means 2 may be a perforated plate allowing the passage of the gaseous fluid.
• This placing step is done in a controlled manner at a temperature below the boiling temperature of said organic compound. Under these conditions, there is a vapor pressure of the organic compound which is generated by its liquid phase. Thus a part of the organic compound molecules in the liquid state passes in gaseous form (vaporization) and is then transferred (gaseous) to the porous solid. Since the vapor phase of organic compound is gradually consumed by the solid, the liquid continues to vaporize. According to one embodiment, said in "batch" according to the English terminology, the amount of liquid organic compound contained in the compartment B is at least greater than the amount of organic compound that is to be introduced into the porous solid.
• the organic compound can be continuously added in the liquid state as it is consumed by the porous solid or in a semi-continuous manner with a regular point feed so as to maintain a minimum liquid level in the liquid. compartment B.
• the addition of organic compound in the liquid state is provided by a pipe 13.
• the placing step according to the invention can be carried out by maintaining agitation of the liquid in compartment B and / or by moving the solid to be treated in compartment A.
• the placing step is carried out with a forced circulation of a flow of a gas, from the compartment B containing the organic compound in the liquid state to the compartment A containing the porous solid to additiver.
• the flow of a gas may be carbon dioxide, ammonia, air with controlled hygrometry, a rare gas such as argon, nitrogen, hydrogen, gas natural gas or a refrigerant gas under the classification published by IUPAC.
• the gas is either supplied under pressure or pressurized to overcome the pressure drops induced by the circuit by means of a pressure increase equipment of a gas such as a compressor or a fan.
• the gas is injected via line 14 into the liquid so to ensure its agitation to promote the saturation of the gas phase by the organic compound by increasing the gas / liquid exchange surface.
• the placing step is carried out under conditions of controlled duration, temperature and pressure so as to ultimately provide a solid containing the organic compound.
• the introduction of the organic compound into the porous solid may result from adsorption and / or capillary condensation processes.
• the bringing together according to the invention may involve a recycling of the vapor phase extracted from compartment A by line 16 opening into compartment A and / or compartment B or possibly in line 14.
• the gaseous phase 16 extracted from the compartment A is cooled so as to condense the organic compound in liquid form which is thus recycled to the compartment B via the line 12 or possibly via the line 13.
• FIG. 3 is another embodiment of the process for adding the organic compound to a porous solid which differs from that of FIG. 2 in that the unit 1 1 for bringing the solid into contact with the liquid organic compound comprises two chambers 18 and 19 which are able respectively to contain the porous solid 4 possibly pretreated and the organic compound in the liquid state, the two enclosures being in communication by means of a pipe 20 so as to allow only the passage of a phase vapor containing the organic compound in the gaseous state.
• FIG. 4 is a variant of the process for adding an organic compound to a porous solid according to the invention in which the porous additiver solid undergoes heat treatment at a temperature greater than that of the contacting step with the organic compound in the liquid state and wherein a heated entrainment gas is injected into the unit 1 1 bringing together.
• the porous solid 1 undergoes a pretreatment step which consists of a heat treatment at a temperature which is greater than that applied to the placing step in the unit 11.
• the method of Figure 4 includes a thermal integration process of using a carrier gas provided by line 21.
• This carrier gas 21 may be, for example and without limitation, an effluent from another process or a dedicated carrier gas.
• a dedicated carrier gas this may be, for example and without limitation, carbon dioxide, ammonia, air with controlled hygrometry, a rare gas such as argon, nitrogen, hydrogen, natural gas or a refrigerant gas under the classification published by IUPAC.
• the gas is either supplied under pressure, is pressurized to overcome the pressure drops induced by the circuit by means of equipment for increasing the pressure of a gas such as a compressor or a fan. If the temperature of the carrier gas is lower than that applied in the step of bringing the solid into contact with the organic compound in the liquid state, it is advantageous to carry out a heat exchange, for example with a heat exchanger 22 of the type charge-effluent for heating the carrier gas 21 with a gaseous effluent 17 from the unit 1 1 which is described below. As shown in FIG. 4, the stream of warmed carrier gas 21 is sent via line 26 into a heat exchanger 23 in which it exchanges heat with the heat-treated solid 4. This heat exchange can be done by direct contact or indirect between the gas and the solid.
• the heat exchange is done by contacting the carrier gas 21 with the porous solid 4, for example in a fluidized bed.
• a gas / solid exchanger comprising a set of tubes traversed by the carrier gas which pass through the porous solid bed.
• a cooled porous solid stream 24 and a stream of warmed carrier gas 25 are sent which are sent to the unit 1 1 for placing in the presence respectively in compartment A and compartment B.
• the carrier gas feed heated in the compartment containing the liquid organic compound can be done for example by means of a bubbling device.
• this hot carrier gas 25 provides calories in substitution or in addition to the temperature maintenance device for the placing step and it creates a movement of the gas phase from compartment B to compartment A thus participating in the transport of the organic compound in the gaseous state to the porous solid to additiver.
• a gaseous effluent 17 which contains the carrier gas and optionally the organic compound in the gaseous state is removed from the compartment A to supply the heat exchanger 22 in order to heat the carrier gas 21.
• the gaseous effluent 17 cooled at the outlet of the exchanger 22 is either wholly or partly recycled via the line 28 with the carrier gas 21, or is completely discharged from the unit 11 via the line 27.
• the heat exchange 22 optionally allows, when the cooling of the gaseous effluent 17 is sufficient, to condense a fraction of the organic compound which is entrained by the carrier gas. The condensate can then be recycled to the compartment B containing the organic compound in the liquid state.
• Example 1 Preparation of CoMoP catalysts on alumina without organic compounds C1 and C2 (not in accordance with the invention).
• alumina support having a BET surface area of 230 m 2 / g, a pore volume measured by mercury porosimetry of 0.78 ml / g and a mean pore diameter of 1.15 nm defined as the median diameter of volume by mercury porosimetry and which is in the form "extruded” is added cobalt, molybdenum and phosphorus.
• the impregnating solution is prepared by dissolving 90 ° C.
• Example 2 Preparation of the CoMoP catalyst on C3 alumina (not in accordance with the invention) by co-impregnation.
• Example 2 On the alumina support described above in Example 1 and which is in the "extruded” form, cobalt, molybdenum and phosphorus are added.
• the impregnating solution is prepared by dissolving 90 ° C. of molybdenum oxide (28.28 g) and cobalt hydroxide (6.57 g) in 15.85 g of an aqueous solution of acid. phosphoric at 85% weight. After homogenization of the mixture, 38 g of citric acid was added before adjusting the volume of solution to the pore volume of the support by adding water.
• the molar ratio (citric acid) / Mo is equal to 1 mol / mol and that (citric acid) / Co is equal to 2.7 mol / mol.
• the extrudates are allowed to mature in a saturated water atmosphere for 24 hours at room temperature and then dried at 120 ° C for 16 hours.
• the dried catalyst and additive of citric acid thus obtained is noted C3.
• Example 3 Preparation of the CoMoP catalyst on C4 alumina (not in accordance with the invention) by post-impregnation.
• catalyst precursor C1 18 g of catalyst precursor C1 described above in Example 1 are impregnated and which is in the form "extruded" with an aqueous solution containing 3.2 g of 2-methoxyethyl-3-oxobutanoate and whose volume is equal to porous volume of catalyst precursor.
• the quantities involved are such that the amount of 2-methoxyethyl 3-oxobutanoate is 0.8 moles per mole of molybdenum (corresponding to 2.2 moles per mole of cobalt).
• the extrudates are allowed to mature in a saturated atmosphere with water for 16 hours at room temperature.
• Catalyst precursor C4 is then dried at 120 ° C for 2 hours to give catalyst C4.
• EXAMPLE 4 Preparation of the CoMoP catalyst on C5 alumina (according to the invention) by introducing an organic compound in the vapor phase after impregnation of the metals.
• a closed chamber In a closed chamber are placed 4 g of 2-methoxyethyl 3-oxobutanoate contained in a crystallizer. 12 g of the catalyst precursor C1 are introduced into the same closed chamber and placed on a stainless steel grid so that the liquid 2-methoxyethyl 3-oxobutanoate is not in physical contact with the catalyst precursor C1. The closed chamber is placed in an oven at 120 ° C for 6 hours. 14.1 g of catalyst C5 are thus obtained after bringing the catalyst precursor C1 into contact with the 2-methoxyethyl 3-oxobutanoate compound in the gaseous state.
• the amount of 2-methoxyethyl-3-oxobutanoate thus transferred to the catalyst is such that the molar ratio of 2-methoxyethyl-3-oxobutanoate to Mo is 0.8 mol per mol of molybdenum (corresponding to 2.2 mol per mol of cobalt).
• EXAMPLE 5 Preparation of the CoMoP catalyst on C6 alumina (according to the invention) by introducing an organic compound in the vapor phase before the impregnation of the metals.
• a closed chamber In a closed chamber are placed 4 g of 2-methoxyethyl 3-oxobutanoate contained in a crystallizer. 8.4 g of the same support as that used in Example 1 are introduced into the same closed chamber and placed on a stainless steel grid so that liquid 2-methoxyethyl 3-oxobutanoate is not in physical contact. with the support.
• the closed chamber is placed in an oven at 120 ° C for 6 hours. 10.5 g of additive support of 2-methoxyethyl 3-oxobutanoate are thus obtained.
• the amount of 2-methoxyethyl 3-oxobutanoate introduced onto the support is fixed so as to obtain, after impregnation of the metals, a molar ratio of 2-methoxyethyl-3-oxobutanoate / Mo is 0.8 mol per mol of molybdenum (ie still 2.2 moles per mole of cobalt).
• the modified support is then impregnated with an impregnation solution prepared by hot dissolving molybdenum oxide (2.4 g) and cobalt hydroxide (0.6 g) in 1.4 g of a solution. 85% aqueous phosphoric acid being careful to adjust by adding water the volume of the latter solution to the pore volume of the previous modified carrier.
• Catalysts C1, C2, C3 and C4 (not in accordance with the invention) and C5 and C6 (in accordance with the invention) were tested with diesel HDS.
• the test is conducted in an isothermal pilot reactor fixed bed traversed, flowing fluids from bottom to top.
• the catalyst precursors are previously sulphurized in situ at 350 ° C. in the reactor under pressure using the test gas oil, to which 2% by weight of dimethyl disulphide is added.
• the hydrodesulfurization tests were carried out under the following operating conditions: a total pressure of 7 MPa, a catalyst volume of 30 cm 3 , a temperature of 330 to 360 ° C., with a hydrogen flow rate of 24 l / h and with a flow rate of 60 cm 3 / h.
• the catalytic performances of the catalysts tested are given in Table 1. They are expressed in degrees Celsius with respect to the catalyst C2 (comparative) chosen as reference (C2): they correspond to the temperature difference to be applied to reach 50 ppm of sulfur in the effluent. A negative value means that the target of sulfur content is reached for a lower temperature and that there is a gain in activity. A positive value means that the target of sulfur content is reached for a higher temperature and that there is therefore a loss of activity. The results obtained are reported in Table 1.
• Table 1 Activities relating to iso-volume in gas oil hydrodesulphurization of catalysts C1, C2, C3 and C4 (not in accordance with the invention) and C5 and C6 (in accordance with the invention) with respect to catalyst C2 (non-compliant )
• Table 1 clearly shows that the mode of introduction of the organic compound according to the invention makes it possible to avoid the use of a solvent and consequently to avoid a drying step while introducing the appropriate amount of organic compound to a temperature much lower than its boiling point.
• 2-methoxyethyl 3-oxobutanoate is carried out at 120 ° C while its boiling point at atmospheric pressure is 254 ° C.
• the catalysts according to the invention are at least as efficient as those prepared according to the prior art.
• the catalysts C5 and C6 according to the invention are more efficient than all the other comparative catalysts.
• the gain is very important compared to catalysts that do not use an organic molecule (C1 and C2) or citric acid (C3) commonly used by those skilled in the art.
• the catalysts C5 and C6 are more efficient than the catalyst C4 using the same organic molecule introduced according to a protocol well known to those skilled in the art based on a post-additivation in aqueous solution.
• the organic compound can thus be introduced according to the invention both before and after the impregnation of the metals forming the active metal phase.

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