EP3728518B1 - Procédé de conversion de charges lourdes d'hydrocarbures avec recyclage d'une huile désasphaltée - Google Patents

Procédé de conversion de charges lourdes d'hydrocarbures avec recyclage d'une huile désasphaltée Download PDF

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EP3728518B1
EP3728518B1 EP18814904.1A EP18814904A EP3728518B1 EP 3728518 B1 EP3728518 B1 EP 3728518B1 EP 18814904 A EP18814904 A EP 18814904A EP 3728518 B1 EP3728518 B1 EP 3728518B1
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Prior art keywords
hydroconversion
section
dao
fraction
heavy
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German (de)
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EP3728518A1 (fr
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Joao MARQUES
Jan Verstraete
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
    • C10G67/0454—Solvent desasphalting
    • C10G67/0463—The hydrotreatment being a hydrorefining
    • 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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/003—Solvent de-asphalting
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/14—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with moving solid particles
    • C10G45/16—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with moving solid particles suspended in the oil, e.g. slurries
    • 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
    • C10G45/22—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with hydrogen dissolved or suspended in the oil
    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • 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
    • C10G2300/1077—Vacuum residues
    • 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
    • C10G2300/201—Impurities
    • C10G2300/205—Metal content
    • C10G2300/206—Asphaltenes
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
    • 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
    • C10G2300/4012—Pressure
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4081—Recycling 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
    • 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
    • C10G2300/44—Solvents

Definitions

  • the present invention relates to the refining and conversion of heavy hydrocarbon feeds derived either from a crude oil or from the distillation of a crude oil, said feeds comprising a fraction of at least 50% having a boiling point of at least 300°C, and containing inter alia asphaltenes, sulphurous and nitrogenous impurities and metals. It is sought to convert these feedstocks into lighter products that can be used as fuels, for example to produce gasoline or diesel, or raw materials for the petrochemical industry.
  • the invention relates to a method for converting such a heavy load comprising hydroconversion steps in a three-phase reactor operating in an ebullated bed and deasphalting of a fraction of the product resulting from the hydroconversion, in which the oil deasphalted, called DAO for DeAsphalted Oil in English, resulting from deasphalting is recycled during hydroconversion.
  • the feedstocks that it is desired to process in the context of the present invention are either crude oils or heavy hydrocarbon fractions resulting from the distillation of a crude oil, also called petroleum residues, and contain a fraction of at least least 50% having a boiling temperature of at least 300°C, preferably at least 350°C and most preferably at least 375°C. They are preferably vacuum residues containing a fraction of at least 50% have a boiling temperature of at least 450°C, and preferably of at least 500°C.
  • These fillers generally have a sulfur content of at least 0.1%, sometimes at least 1% and even at least 2% by weight, a Conradson carbon content of at least 0.5% by weight and preferably at least 5% by weight, a content of C 7 asphaltenes of at least 1% by weight and preferably at least 3% by weight and a metal content of at least 20 ppm by weight and preferably at least 100 ppm by weight.
  • the conversion of heavy feeds depends on a large number of parameters such as the composition of the feed, the technology of the reactor used, the severity of the operating conditions (temperature, pressure, partial pressure of hydrogen, residence time, etc.) , the type of catalyst used and its activity.
  • the severity of the operating conditions temperature, pressure, partial pressure of hydrogen, residence time, etc.
  • the advanced conversion of heavy feedstocks therefore very often results in the formation of solid, very viscous and/or sticky particles composed of asphaltenes, coke and/or fine particles of catalyst.
  • the excessive presence of these products leads to the coking and deactivation of the catalyst, to the fouling of the process equipment, and in particular the separation and distillation equipment.
  • the refiner is obliged to reduce the conversion of heavy feeds in order to avoid stopping the hydroconversion unit.
  • the international request WO2010/033487A2 describes a "slurry" process for converting a heavy charge of hydrocarbons comprising two stages of hydroconversion (hydrocracking), and an optional deasphalting treatment (SDA) that can be implemented in an intermediate unit positioned after one of the intermediate separation.
  • SDA deasphalting treatment
  • Another configuration according to the direct route consists in carrying out the stage of deasphalting of the heavy cuts after a stage of hydroconversion thus making it possible to minimize the quantity of asphalt produced, then to recycle the DAO at the entrance to the first zone of hydroconversion or in fractionation zones upstream of the first hydroconversion zone, as described in the patent applications FR 2 964 388 and FR 2 999 599 .
  • This configuration requires a significant increase in the volume of the reaction zones as well as the separation zones, increasing the investment required and the operating cost compared to a conversion process without DAO recycling.
  • coke and sediment formation problems may still occur during the hydroconversion step where the DAO is recycled and co-processed with the heavy feed containing asphaltenes.
  • the present invention aims to solve, at least partially, the problems mentioned above in relation to the methods for converting heavy loads of the prior art integrating hydroconversion and deasphalting stages.
  • one of the objectives of the invention is to provide a process for the conversion of heavy loads of hydrocarbons integrating hydroconversion and deasphalting stages in which the stability of the effluents is improved for a given level of conversion of the heavy loads, thus making it possible to push the conversion further in the process, that is to say to carry out the hydroconversion so as to obtain a higher conversion rate.
  • Another object of the invention is to provide such a process in which the formation of coke and sediments is limited during the hydroconversion, thus reducing the problems of deactivation of the catalysts used in the reaction zones and of fouling of the equipment used. implemented in the process.
  • Another object of the invention is also to provide a DAO of good quality, that is to say having a reduced content of nitrogen, sulfur, metals and Conradson carbon.
  • the heavy hydrocarbon charge preferably has a sulfur content of at least 0.1% by weight, a Conradson carbon content of at least 0.5% by weight, a C 7 asphaltenes content of at least 1% weight, and a metal content of at least 20 ppmw.
  • the heavy hydrocarbon feedstock can be a crude oil or consist of atmospheric residues and/or vacuum residues from the atmospheric and/or vacuum distillation of a crude oil, and preferably consists of vacuum residues from vacuum distillation of crude oil.
  • said three-phase reactor containing at least one hydroconversion catalyst is a three-phase reactor operating in an ebullated bed, with an ascending current of liquid and gas, or a three-phase reactor operating in a hybrid bed, said hybrid bed comprising at least one catalyst maintained in said three-phase reactor and at least one catalyst driven out of said three-phase reactor.
  • the initial hydroconversion step ( a 1 ) is carried out under an absolute pressure of between 2 and 38 MPa, at a temperature of between 300° C. and 550° C., at a speed hourly space VVH relative to the volume of each three-phase reactor comprised between 0.05 h -1 and 10 h -1 and under a quantity of hydrogen mixed with the heavy hydrocarbon charge comprised between 50 and 5000 normal cubic meters (Nm 3 ) per cubic meter (m 3 ) of heavy oil load.
  • the additional hydroconversion step(s) ( a n ) are operated at a temperature between 300° C. and 550° C., and higher than the temperature operated in the hydroconversion step initial ( a 1 ), under a quantity of hydrogen mixed with the heavy hydrocarbon charge of between 50 and 5000 normal cubic meters (Nm 3 ) per cubic meter (m 3 ) of heavy hydrocarbon charge and less than the quantity of hydrogen operated in the initial hydroconversion step ( a 1 ), under an absolute pressure of between 2 and 38 MPa, and at an hourly space velocity VVH relative to the volume of each three-phase reactor of between 0.05 h -1 and 10:00 a.m.
  • the intermediate separation section comprises one or more flash drums arranged in series, and/or one or more steam and/or hydrogen stripping columns, and/or a atmospheric distillation column, and/or a vacuum distillation column, and is preferably constituted by a single flash drum.
  • the first fractionation section comprises one or more flash drums arranged in series, and/or one or more steam and/or hydrogen stripping columns, and/or a atmospheric distillation column, and/or a vacuum distillation column, and is preferably constituted by a set of several flash drums in series and atmospheric and vacuum distillation columns.
  • the deasphalting step (d) is carried out in an extraction column at a temperature of between 60° C. and 250° C. with at least one hydrocarbon solvent having from 3 to 7 carbon atoms. of carbon, and a solvent/filler (volume/volume) ratio of between 3/1 and 16/1, and preferably between 4/1 and 8/1.
  • part of the heavy hydrocarbon charge is sent to at least one additional hydroconversion section and/or to at least one intermediate separation section and/or to the first fractionation section and/or in the deasphalter.
  • an external hydrocarbon feed is sent to the process in the initial hydroconversion section and/or in at least one additional hydroconversion section and/or in at least one intermediate separation section and/or in the first fractionation section and/or in the deasphalter.
  • n is equal to 2.
  • the process comprises recycling (f) all of the DAO from step (d) or all of the heavy fraction from the second fractionation step (e) in the last additional hydroconversion step ( a i ), and preferably in the additional hydroconversion step ( a 2 ) when n is equal to 2 and when, in addition, all of the liquid effluent from the step ( a 1 ) is sent to step ( b 1 ), all of the heavy fraction from step ( b 1 ) is sent to step ( a 2 ), all of the hydroconverted liquid effluent from step ( a 2 ) is sent to step (c), and all of the heavy cut from step (c) is sent to step (d).
  • the process comprises recycling (f) all of the DAO from step (d) or all of the heavy fraction from the second fractionation step (e) at an intermediate separation step ( b j ), and preferably at the intermediate separation step ( b 1 ) between the initial hydroconversion step ( a 1 ) and the additional hydroconversion step ( a 2 ) when n is equal to 2 and that in addition all of the liquid effluent from stage ( a 1 ) is sent to stage ( b 1 ), all of the heavy fraction from stage ( b 1 ) is sent to stage ( a 2 ), all of the effluent hydroconverted liquid from step ( a 2 ) is sent to step (c), and all of the heavy cut from step (c) is sent to step (d).
  • the method does not include an intermediate separation step ( b j ) and includes the recycling (f) of all of the DAO from step (d) to the last step additional hydroconversion steps ( a i ), and preferably in the additional hydroconversion step ( a 2 ) when n is equal to 2 and when, in addition, all of the liquid effluent from step ( a 1 ) is sent to stage ( a 2 ), all of the hydroconverted liquid effluent from stage ( a 2 ) is sent to stage (c), and all of the heavy cut from the step (c) is sent to step (d).
  • the hydroconversion catalyst of said at least one three-phase reactor of the initial hydroconversion section and of the additional hydroconversion section(s) contains at least one metal from group VIII not -noble chosen from nickel and cobalt and at least one group VIB metal chosen from molybdenum and tungsten, and preferably comprising an amorphous support.
  • the process for converting heavy hydrocarbon feedstocks according to the invention includes hydroconversion of said feedstocks and deasphalting of at least part of the hydroconverted effluent in the form of a succession of specific steps.
  • figure 1 illustrates the general implementation of the conversion method according to the invention.
  • the present invention it is proposed to simultaneously improve the level of conversion and the stability of the liquid effluents by a sequence comprising at least two successive hydroconversion stages, which can be separated by an intermediate separation stage, and at least one stage deasphalting of a heavy fraction of the effluent from the hydroconversion, with recycling of at least part of the DAO downstream of the first hydroconversion stage.
  • the DAO is either recycled when it leaves the deasphalter, or after having undergone a fractionation step producing a heavy fraction of the DAO which then constitutes the part of the recycled DAO.
  • This configuration makes it possible to achieve a conversion of the heavy charge of hydrocarbons greater than 70%, and preferably greater than 80%, this level of conversion not always being able to be achieved using conventional methods which are limited by the stability of the liquid effluents.
  • the net conversion is defined as being the ratio of (residue flow in the feed - the residue flow in the product) / (residue flow in the feed), for the same feed-product cut point; typically this cut point is between 450°C and 550°C, and often around 540°C; in this definition, the residue being the fraction boiling from this cut point, for example, the 540°C+ fraction.
  • the DAO obtained by the process according to the invention contains no or very little C 7 asphaltenes, compounds known to inhibit the conversion of residual cuts, both by their ability to form heavy hydrocarbon residues, commonly called coke, and by their tendency to produce sediments which severely limit the operability of hydrotreating and hydroconversion units.
  • the DAO obtained by the process according to the invention is also more aromatic than a DAO produced from a heavy petroleum charge resulting from the primary fractionation of the crude (known as "straight run" according to the Anglo-Saxon terminology) because it is derived of an effluent which has previously undergone a high level of hydroconversion.
  • the mixing of at least a part of the DAO and the effluent from the first hydroconversion section(s) in the process according to the invention makes it possible to supply the subsequent hydroconversion stage(s) with a feed having a reduced content of C 7 asphaltenes and a higher content of aromatic compounds both compared to a process comprising a hydroconversion unit without recycling of the DAO, and compared to a process comprising a hydroconversion unit with recycling of the DAO upstream of a first stage of hydroconversion or hydrotreatment.
  • the effluent from the last additional hydroconversion step is separated into several cuts. Deasphalting is then carried out on the heavy cut(s) produced in this separation step. The use of these cuts obtained at the highest level of conversion thus makes it possible to minimize the size required for the deasphalter and to minimize the quantity of asphalt produced.
  • the DAO extracted by deasphalting is always recycled after the initial hydroconversion step, either at the inlet of one of the intermediate separation sections, or at the inlet of one of the additional hydroconversion sections , preferably at the entrance to the section of the last additional hydroconversion step.
  • the size of the reactors of the first hydroconversion sections is not impacted, and according to the second implementation, neither the size of the intermediate separation equipment nor the size of the reactors of the prior hydroconversion stages are impacted.
  • the injection of the DAO downstream of the initial hydroconversion section makes it possible to avoid the prior hydrogenation of the DAO, thus preserving its aromatic character (characterized by the aromatic carbon content measured by the ASTM D 5292 method) which provides a gain in the stability of liquid effluents from areas where the highest conversion levels are reached. An operation to achieve higher conversion rates can therefore thus be envisaged in the process according to the invention.
  • the charge treated in the process according to the invention is a heavy charge of hydrocarbons containing a fraction of at least 50% having a boiling point of at least 300° C., preferably of at least 350° C., and even more preferably at least 375°C.
  • This heavy charge of hydrocarbons can be a crude oil, or come from the refining of a crude oil or from the treatment of another hydrocarbon source in a refinery.
  • the feed is a crude oil or consists of atmospheric residues and/or vacuum residues resulting from the atmospheric and/or vacuum distillation of a crude oil.
  • the heavy hydrocarbon feed may also consist of atmospheric and/or vacuum residues from the atmospheric and/or vacuum distillation of effluents from thermal conversion, hydrotreating, hydrocracking and/or hydro conversion.
  • the charge consists of vacuum residues.
  • vacuum residues generally contain a fraction of at least 50% having a boiling point of at least 450° C., and most often at least 500° C., or even at least 540° C. °C.
  • Vacuum resids can come directly from crude oil, or from other refining units, such as, but not limited to, residing hydrotreating, residing hydrocracking, and residing visbreaking.
  • the vacuum residues are vacuum residues from the vacuum distillation column of the primary fractionation of crude oil (known as “straight run” according to English terminology).
  • the feed may still consist of vacuum distillates, either directly from crude oil or from cuts from other refining units, such as, inter alia, cracking units, such as fluid bed catalytic cracking FCC (for “Fluid Catalytic Cracking” in English) and hydrocracking, and thermal conversion units, such as coking units or visbreaking units.
  • cracking units such as fluid bed catalytic cracking FCC (for “Fluid Catalytic Cracking” in English) and hydrocracking
  • thermal conversion units such as coking units or visbreaking units.
  • It may also consist of aromatic cuts extracted from a lubricant production unit, deasphalted oils from a deasphalting unit (raffinates from the deasphalting unit), asphalts from a deasphalting unit ( residues from the deasphalting unit).
  • the heavy hydrocarbon charge can also be a residual fraction from the direct liquefaction of coal (an atmospheric residue and/or a vacuum residue from, for example, the H-Coal TM process), a vacuum distillate from the direct liquefaction coal, such as for example the H-Coal TM process, or even a residual fraction resulting from the direct liquefaction of the lignocellulosic biomass alone or mixed with coal and/or a petroleum fraction.
  • a residual fraction from the direct liquefaction of coal an atmospheric residue and/or a vacuum residue from, for example, the H-Coal TM process
  • a vacuum distillate from the direct liquefaction coal such as for example the H-Coal TM process
  • even a residual fraction resulting from the direct liquefaction of the lignocellulosic biomass alone or mixed with coal and/or a petroleum fraction can also be a residual fraction from the direct liquefaction of coal (an atmospheric residue and/or a vacuum residue from, for example, the H-Coal
  • feedstocks can be used to form the heavy hydrocarbon feedstock treated according to the invention, alone or as a mixture.
  • the heavy charge of hydrocarbons treated according to the invention contains impurities, such as metals, sulfur, nitrogen, Conradson carbon. It may also contain heptane insolubles, also called C 7 asphaltenes.
  • the metal contents may be greater than or equal to 20 ppm by weight, preferably greater than or equal to 100 ppm by weight.
  • the sulfur content may be greater than or equal to 0.1%, or even greater than or equal to 1%, and may be greater than or equal to 2% by weight.
  • the rate of asphaltenes C 7 (compounds insoluble in heptane according to standard NFT60-115 or standard ASTM D 6560) amounts to at least 1% and is often greater than or equal to 3% by weight.
  • C 7 asphaltenes are compounds known to inhibit the conversion of residual cuts, both by their ability to form heavy hydrocarbon residues, commonly called coke, and by their tendency to produce sediments which severely limit the operability of the units. hydrotreating and hydroconversion.
  • the Conradson carbon content may be greater than or equal to 0.5%, or even at least 5% by weight.
  • the Conradson carbon content is defined by the ASTM D 482 standard and represents, for those skilled in the art, a well-known evaluation of the quantity of carbon residues produced after pyrolysis under standard temperature and pressure conditions.
  • the heavy hydrocarbon charge is treated in the presence of hydrogen in a first hydroconversion stage ( a 1 ), within an initial hydroconversion section A 1 .
  • the initial hydroconversion section comprises one or more three-phase reactors containing at least one hydroconversion catalyst, the reactors possibly being arranged in series and/or in parallel. These reactors can be bubbling bed and/or hybrid bed type reactors, depending on the feed to be treated.
  • the invention is particularly suitable for three-phase reactors operating in an ebullated bed, with an ascending current of liquid and gas.
  • this initial hydroconversion step ( a 1 ) is advantageously implemented in an initial hydroconversion section A 1 comprising one or more three-phase hydroconversion reactors, which can be in series and/or in parallel, operating as a bed bubbling, typically using the technology and under the conditions of the H-Oil TM process as described for example in the patents US 4,521,295 Where US 4,495,060 Where US 4,457,831 Where US 4,354,852 , or in the article AlChE, March 19-23, 1995, Houston, Texas, paper number 46d, "Second generation ebullated bed technology ", or in the chapter 3.5 "Hydroprocessing and Hydroconversion of Residue Fractions" of the book “Catalysis by Transition Metal Sulphides", published by Éditions Technip in 2013 .
  • each three-phase reactor is operated in a fluidized bed called an ebullating bed.
  • Each reactor advantageously comprises a recirculation pump making it possible to maintain the catalyst in an ebullated bed by continuous recycling of at least part of a liquid fraction advantageously drawn off at the top of the reactor and reinjected at the bottom of the reactor.
  • the first hydroconversion stage ( a 1 ) is carried out under conditions making it possible to obtain a liquid effluent with a reduced sulfur, Conradson carbon, metals and nitrogen content.
  • Step ( a 1 ) the feedstock is preferably transformed under specific hydroconversion conditions.
  • Step ( a 1 ) is preferably carried out under an absolute pressure of between 2 MPa and 38 MPa, more preferably between 5 MPa and 25 MPa and even more preferably, between 6 MPa and 20 MPa, at a temperature between 300°C and 550°C, more preferably between 350°C and 500°C and more preferably between 370°C and 450°C.
  • the hourly space velocity (HSV) relative to the volume of each three-phase reactor is preferably between 0.05 h -1 and 10 h -1 .
  • the VVH is between 0.1 h -1 and 10 h -1 , more preferably between 0.1 h -1 and 5 h -1 and even more preferably between 0.15 h -1 and 2 h -1 .
  • the VVH is between 0.05 h -1 and 0.09 h -1 .
  • the amount of hydrogen mixed with the charge is preferably between 50 and 5000 normal cubic meters (Nm 3 ) per cubic meter (m 3 ) of liquid charge, preferably between 100 and 2000 Nm 3 /m 3 and so very preferred between 200 and 1000 Nm 3 /m 3 .
  • the initial hydroconversion step ( a 1 ) being carried out in an ebullated bed and/or in a hybrid bed depending on the feed to be treated, this step therefore contains at least one hydroconversion catalyst which is maintained in the reactor.
  • the hydroconversion catalyst used in the initial hydroconversion step ( a 1 ) of the process according to the invention may contain one or more elements from groups 4 to 12 of the periodic table of elements, which may or may not be deposited on a support.
  • a catalyst comprising a support, preferably amorphous, such as silica, alumina, silica-alumina, titanium dioxide or combinations of these structures, and very preferably alumina.
  • the catalyst may contain at least one non-noble metal from group VIII chosen from nickel and cobalt, and preferably nickel, said element from group VIII preferably being used in combination with at least one metal from group VIB chosen from molybdenum and tungsten, and preferably the Group VIB metal is molybdenum.
  • group VIII according to the CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IUPAC classification.
  • the hydroconversion catalyst used in the initial hydroconversion step ( a 1 ) comprises an alumina support and at least one group VIII metal chosen from nickel and cobalt, preferably nickel, and at least one metal of group VIB chosen from molybdenum and tungsten, preferably molybdenum.
  • the hydroconversion catalyst comprises nickel as a group VIII element and molybdenum as a group VIB element.
  • non-noble group VIII metal in particular nickel
  • metal oxide in particular NiO
  • metal content of the group VIB, in particular in molybdenum is advantageously between 1% and 30% expressed by weight of metal oxide (in particular of molybdenum trioxide MoO 3 ), and preferably between 4% and 20% by weight.
  • the metal contents are expressed as weight percentage of metal oxide relative to the weight of the catalyst.
  • This catalyst is used in the form of extrudates or beads.
  • the balls have for example a diameter of between 0.4 mm and 4.0 mm.
  • the extrudates have for example a cylindrical shape with a diameter between 0.5 and 4.0 mm and a length between 1 and 5 mm.
  • Extrudes can also be objects of a different shape such as trilobes, regular or irregular tetralobes, or other multilobes. Catalysts of other forms can also be used.
  • the size of these different forms of catalysts can be characterized using the equivalent diameter.
  • the equivalent diameter is defined by 6 times the ratio between the volume of the particle and the external surface of the particle.
  • the catalyst used in the form of extrudates, of beads therefore has an equivalent diameter of between 0.4 mm and 4.4 mm.
  • the initial hydroconversion step ( a 1 ) is carried out in a hybrid bed, simultaneously comprising at least one catalyst which is maintained in the reactor and at least one entrained catalyst which enters the reactor with the load and which is drawn outside the reactor with the effluents.
  • a type of entrained catalyst also called "slurry" according to English terminology, is therefore used in addition to the hydroconversion catalyst which is maintained in the reactor in an ebullated bed.
  • the entrained catalyst has, as a difference, a particle size and a density adapted to its entrainment.
  • the entrained catalyst can advantageously be obtained by injecting at least one active phase precursor directly into the hydroconversion reactor(s) and/or into the charge prior to the introduction of said charge into the hydroconversion stage(s).
  • the addition of precursor can be introduced continuously or discontinuously (depending on the operation, the type of feedstock treated, the desired product specifications and the operability).
  • the precursor(s) of entrained catalyst is (are) pre-mixed with a hydrocarbon oil composed for example of hydrocarbons of which at least 50% by weight relative to the total weight of the hydrocarbon oil have a boiling point between 180°C and 540°C, to form a pre-mixture of dilute precursor.
  • the precursor or the dilute precursor pre-mixture is dispersed in the heavy hydrocarbon feedstock, for example by dynamic mixing (for example using a rotor, an agitator, etc. ), by static mixing (e.g. using an injector, by gavage, via a static mixer, etc.), or only added to the charge to obtain a mixture. All the mixing and agitation techniques known to those skilled in the art can be used to disperse the precursor or the mixture of precursors diluted in the charge of one or more hydroconversion stages.
  • the said active phase precursor(s) of the unsupported catalyst may or may be in liquid form such as, for example, precursors of metals soluble in organic media, such as, for example, molybdenum octoates and/or molybdenum naphthenates, or water-soluble compounds, such as for example phosphomolybdic acids and/or ammonium heptamolybdates.
  • Said entrained catalyst can be formed and activated ex situ, outside the reactor under conditions suitable for activation, then be injected with the charge. Said entrained catalyst can also be formed and activated in situ under the reaction conditions of one of the hydroconversion steps.
  • a different hydroconversion catalyst is used in each reactor of this initial hydroconversion stage ( a 1 ), the catalyst offered to each reactor being adapted to the feed sent into this reactor.
  • each reactor contains one or more catalysts suitable for operation in an ebullated bed, and optionally one or more additional entrained catalyst(s).
  • the hydroconversion catalyst when used, can be partly replaced by fresh catalyst, and/or used catalyst but with higher catalytic activity than the used catalyst to be replaced, and/or regenerated catalyst, and/ or rejuvenated catalyst (catalyst from a rejuvenation zone in which most of the metals deposited are removed, before sending the spent and rejuvenated catalyst to a regeneration zone in which the carbon and sulfur that it contains is removed contains thus increasing the activity of the catalyst), by withdrawing the used catalyst preferably at the bottom of the reactor, and by introducing the replacement catalyst either at the top or at the bottom of the reactor.
  • This replacement of used catalyst is preferably carried out at regular time intervals, and preferably in bursts or almost continuously.
  • the replacement of used catalyst can be done entirely or in part by used and/or regenerated and/or rejuvenated catalyst from the same reactor and/or from another reactor of any hydroconversion stage.
  • the catalyst can be added with the metals as metal oxides, with the metals as metal sulfides, or after preconditioning.
  • the rate of replacement of spent hydroconversion catalyst with fresh catalyst is advantageously between 0.01 kg and 10 kg per cubic meter of feedstock treated, and preferably between 0.1 kg and 3 kg per cubic meter load processed. This withdrawal and this replacement are carried out using devices that advantageously allow the continuous operation of this hydroconversion step.
  • the replacement at least in part by regenerated catalyst it is possible to send the spent catalyst withdrawn from the reactor to a regeneration zone in which the carbon and the sulfur which it contains are eliminated and then to return this catalyst regenerated in the hydroconversion step.
  • the replacement at least in part by rejuvenated catalyst it is possible to send the spent catalyst withdrawn from the reactor to a rejuvenation zone in which the major part of the deposited metals is eliminated, before sending the spent catalyst and rejuvenated in an area of regeneration in which the carbon and the sulfur which it contains are eliminated and then this regenerated catalyst is returned to the hydroconversion stage.
  • the liquid effluent from the initial hydroconversion stage ( a 1 ) can then undergo an intermediate separation stage ( b 1 ) in an intermediate separation section B 1 , carried out between the initial hydroconversion stage ( a 1 ) and an additional hydroconversion step following the initial hydroconversion step.
  • This additional hydroconversion step is described below.
  • this intermediate separation step ( b 1 ) is preferred, but it remains optional. Indeed, the liquid effluent from the initial hydroconversion step ( a 1 ) can alternatively be sent directly to the additional hydroconversion step.
  • At least part of the liquid effluent resulting from the initial hydroconversion stage ( a 1 ) is sent to the intermediate separation stage ( b 1 ).
  • the intermediate separation stage ( b 1 ) separates part or all of the liquid effluent from the initial hydroconversion stage ( a 1 ) to produce at least one so-called heavy liquid fraction boiling mainly at a higher temperature or equal to 350°C.
  • This first intermediate separation step therefore produces at least two fractions including the heavy liquid fraction as described above, the other cut(s) being light and intermediate cut(s).
  • the light fraction thus separated contains dissolved light gases (H 2 and C 1 -C 4 ), naphtha (fraction boiling at a temperature below 150°C), kerosene (fraction boiling between 150°C and 250°C) , and at least part of the gas oil (fraction boiling between 250° C. and 375° C.).
  • the light fraction can then be sent at least in part to a fractionation unit (not shown in the figures) where the light gases (H 2 and C 1 -C 4 ) are extracted from said light fraction, for example by passing through a flash balloon.
  • the gaseous hydrogen thus recovered can advantageously be recycled at the inlet of the initial hydroconversion stage ( a 1 ).
  • the fractionation unit where the light fraction can be sent can also include a distillation column.
  • the naphtha, kerosene and gas oil fractions of the light fraction sent to said column are separated.
  • the heavy liquid fraction from the intermediate separation stage ( b 1 ), boiling mainly at a temperature greater than or equal to 350°C, contains at least one fraction boiling at a temperature greater than or equal to 540°C, called residue under void (which is the unconverted fraction).
  • the heavy liquid fraction from the intermediate separation stage ( b 1 ), boiling mainly at a temperature greater than or equal to 350° C. can also contain a fraction boiling between 375 and 540° C., called vacuum distillate. It may optionally also contain part of the gas oil fraction boiling between 250 and 375°C.
  • This heavy liquid fraction is then sent in whole or in part to a second hydroconversion stage ( a 2 ), as described below.
  • the intermediate separation stage ( b 1 ) can therefore separate the liquid effluent from the initial hydroconversion stage ( a 1 ) into more than two liquid fractions, depending on the separation means implemented.
  • the intermediate separation section B 1 comprises any separation means known to those skilled in the art.
  • the intermediate separation section B 1 can thus comprise one or more following separation equipment: one or more flash drums arranged in series, one or more steam and/or hydrogen stripping columns, an atmospheric distillation column , a vacuum distillation column.
  • this intermediate separation step ( b 1 ) is carried out by one or more flash balloons arranged in series.
  • the intermediate separation step ( b 1 ) is carried out by a single flash balloon.
  • the flash drum is at a pressure and a temperature close to the operating conditions of the last reactor of the initial hydroconversion step ( a 1 ). This implementation is preferred in particular because it makes it possible to reduce the number of equipment and therefore the investment cost.
  • the intermediate separation step ( b 1 ) is carried out by a sequence of several flash drums, operating at operating conditions different from those of the last reactor of the initial hydroconversion step ( a 1 ), and leading to the obtaining of at least the light liquid fraction, which can then be sent at least in part to a fractionation unit, and of at least the heavy liquid fraction, which is then sent at least in part to a second hydroconversion step ( a 2 ).
  • the intermediate separation step ( b 1 ) is carried out by one or more steam and/or hydrogen stripping columns.
  • the effluent from the initial hydroconversion step ( a 1 ) is separated into at least the light liquid fraction and at least the heavy liquid fraction.
  • the heavy liquid fraction is then sent at least in part to a second hydroconversion stage ( a 2 ).
  • the intermediate separation stage ( b 1 ) is carried out in an atmospheric distillation column separating the liquid effluent from the initial hydroconversion stage ( a 1 ).
  • the heavy liquid fraction recovered from the atmospheric distillation column is then sent at least in part to a second hydroconversion step ( a 2 ).
  • the intermediate separation step ( b 1 ) is carried out by an atmospheric distillation column separating the liquid effluent from the step initial hydroconversion ( a 1 ), and by a vacuum distillation column receiving the residue from the atmospheric distillation column and producing the heavy liquid fraction which is then sent at least in part to a second hydroconversion stage ( a 2 ).
  • the intermediate separation step ( b 1 ) can also consist of a combination of the different implementations described above, in a different order from that described above.
  • the heavy liquid fraction before being sent to a second hydroconversion stage ( a 2 ) according to the invention, can be subjected to a steam and/or hydrogen stripping stage using one or more stripping columns, in order to eliminate from the heavy fraction the compounds having a boiling point lower than 540°C.
  • the additional effluent can be sent to the inlet of the intermediate separation section, or between two different pieces of equipment of the intermediate separation section, for example between the flash drums, the stripping columns and/or the distillation columns.
  • part or all of the effluent from the initial hydroconversion step ( a 1 ), or preferably part or all of the heavy fraction from the intermediate separation step ( b 1 ), is treated in the presence of hydrogen in an additional hydroconversion step ( a 2 ) carried out in an additional hydroconversion section A 2 , which follows the initial hydroconversion step ( a 1 ) or optionally l intermediate separation step ( b 1 ).
  • the process according to the invention may comprise more than one additional hydroconversion step ( a i ), as well as more than one intermediate separation step ( b j ) between two consecutive additional hydroconversion steps ( a i ).
  • the process according to the invention comprises (n-1) additional hydroconversion step(s) ( a i ) in (n-1) additional hydroconversion section(s) A j , in presence of hydrogen, of at least part or all of the liquid effluent from the preceding hydroconversion step ( a i -1 ) or possibly of a heavy fraction from the optional intermediate separation step ( b j ) between two consecutive hydroconversion stages separating part or all of the liquid effluent from the preceding hydroconversion stage ( a i -1 ) to produce at least one heavy fraction boiling mainly at a higher temperature or equal to 350° C., the (n-1) additional hydroconversion stage(s) ( a i ) being carried out so as to obtain a hydroconverted liquid effluent with a reduced content of sulphur, Conradson carbon, metals , and nitrogen.
  • n is the total number of hydroconversion steps, with n greater than or equal to 2.
  • i and j are indices. i is an integer ranging from 2 to n and j being an integer ranging from 1 to (n-1).
  • the additional hydroconversion section(s) A i each comprise at least one three-phase reactor containing at least one hydroconversion catalyst, as described for the initial hydroconversion section A 1 .
  • the initial hydroconversion step and the additional hydroconversion step(s) are separate steps, carried out in different hydroconversion sections.
  • the (n-1) additional hydroconversion step(s) ( a i ) are advantageously implemented in initial hydroconversion sections A 1 comprising one or more three-phase hydroconversion reactors, which can be in series and/or in parallel, preferably operating in an ebullated bed, as described above for the initial hydroconversion step ( a 1 ).
  • each three-phase reactor is operated in a fluidized bed called an ebullating bed.
  • Each reactor advantageously comprises a recirculation pump making it possible to maintain the catalyst in an ebullated bed by continuous recycling of at least part of a liquid fraction advantageously drawn off at the top of the reactor and reinjected at the bottom of the reactor.
  • the operating conditions can be more severe than in the initial hydroconversion step, in particular by using a higher reaction temperature, remaining in the range between 300° C. and 550° C., preferably between 350°C and 500°C, and more preferably between 370°C and 450°C, or by reducing the quantity of hydrogen introduced into the reactor, remaining in the range between 50 and 5000 Nm 3 /m 3 of liquid filler, preferably between 100 and 2000 Nm 3 /m 3 , and even more preferably between 200 and 1000 Nm 3 /m 3 .
  • the other pressure and VVH parameters are in ranges identical to those described for the initial hydroconversion step.
  • the catalyst used in the reactor(s) of an additional hydroconversion stage may be the same as that used in the reactor(s) of the initial hydroconversion stage, or may also be a catalyst more suitable for hydroconversion of residual cuts containing a DAO.
  • the catalyst may have a porosity of the support or contain metal contents suitable for the hydroconversion of feedstocks containing DAO cuts.
  • the catalyst replacement rate applied in the reactor(s) of an additional hydroconversion stage may be the same as that used for the reactor(s) of the initial hydroconversion stage , or be more suitable for the hydroconversion of residual cuts containing a DAO. In this case, the catalyst replacement rate can be lower, suitable for the hydroconversion of feedstocks containing DAO cuts.
  • the process according to the invention always comprises an intermediate separation step ( b j ) between two consecutive additional hydroconversion steps ( a i ).
  • the effluent from an additional hydroconversion stage ( a i ) is sent directly to another additional hydroconversion stage ( a i + 1 ) following stage ( a i ).
  • the process comprises a single additional hydroconversion step ( a 2 ), and an intermediate separation step ( b 1 ).
  • a 2 the process is a single additional hydroconversion step
  • b 1 an intermediate separation step
  • At least part of the DAO from the deasphalting step (d) detailed below, and/or at least part of the heavy fraction of the DAO from a second fractionation step ( e) also detailed below, is recycled by being sent to an additional hydroconversion stage ( a i ) and/or to an intermediate separation stage ( b j ).
  • the process according to the invention thus excludes recycling of the DAO or of a heavy fraction of the DAO in the initial hydroconversion step.
  • the DAO or the heavy fraction of the DAO thus recycled can then be co-treated in an additional hydroconversion section A i with at least part of the effluent coming from the initial hydroconversion stage ( a 1 ) or d a hydroconversion step additional ( a i ), or more preferably co-treated with at least part of the heavy fraction from an intermediate separation step ( b j ).
  • the additional effluent can be sent to the inlet of the intermediate separation section B j , or between two different pieces of equipment of the intermediate separation section B j , for example between the flash drums, the stripping columns and/or distillation columns.
  • the hydroconverted liquid effluent from the last additional hydroconversion step ( a n ) then undergoes at least part of a fractionation step (c) in a first fractionation section C.
  • This first fractionation stage (c) separates part or all of the effluent from stage ( a n ) into several fractions including at least one heavy liquid fraction boiling mainly at a temperature above 350° C., preferably greater than 500°C and preferably greater than 540°C.
  • the heavy liquid cut contains a fraction boiling at a temperature above 540° C., called vacuum residue (which is the unconverted fraction). It may contain part of the gas oil fraction boiling between 250 and 375°C and a fraction boiling between 375 and 540°C called vacuum distillate.
  • This first fractionation step therefore produces at least two fractions including the heavy liquid fraction as described above, the other cut(s) being light and intermediate cut(s).
  • the first fractionation section C comprises any separation means known to those skilled in the art.
  • the first fractionating section C can thus comprise one or more following separation equipment: one or more flash drums arranged in series, and preferably a sequence of at least two successive flash drums, one or more stripping columns at the steam and/or hydrogen, an atmospheric distillation column, a vacuum distillation column.
  • this first splitting step (c) is performed by linking at least two successive flash balloons.
  • this first fractionation step (c) is carried out by one or more steam and/or hydrogen stripping columns.
  • this first fractionation step (c) is carried out by an atmospheric distillation column, and more preferably by an atmospheric distillation column and a vacuum column receiving the atmospheric residue.
  • this first fractionation step (c) is carried out by one or more flash drums, an atmospheric distillation column and a vacuum column receiving the atmospheric residue.
  • the additional effluent can be sent to the inlet of the intermediate separation section, or between two different pieces of equipment of the intermediate separation section, for example between the flash drums, the stripping columns and/or the distillation columns.
  • the heavy cut from the first fractionation step (c) then undergoes, in accordance with the process according to the invention, in part or in whole, a deasphalting step (d) in a deasphalter D, with at least one hydrocarbon solvent, to extract a DAO and residual asphalt.
  • the deasphalting step (d) using a solvent is carried out under conditions well known to those skilled in the art.
  • a solvent or SDA for Solvent DeAsphalting in English
  • the deasphalting can be carried out in one or more mixer-settlers or in one or more extraction columns.
  • the deasphalter D thus comprises at least one mixer-settler or at least one extraction column.
  • Deasphalting is a liquid-liquid extraction generally carried out at an average temperature between 60°C and 250°C with at least one hydrocarbon solvent.
  • the solvents used for deasphalting are low boiling point solvents, preferably paraffinic solvents, and preferably heavier than propane, and preferably having 3 to 7 carbon atoms.
  • Preferred solvents include propane, butane, isobutane, pentane, isopentane, neopentane, hexane, isohexanes, C 6 hydrocarbons, heptane, C 7 hydrocarbons, light gasolines more or less apolar, as well as the mixtures obtained from the aforementioned solvents.
  • the solvent is butane, pentane or hexane, as well as their mixtures.
  • the solvent or solvents are optionally added with at least one additive.
  • the solvents which can be used and the additives are widely described in the literature.
  • the solvent/feed (volume/volume) ratios entering deasphalter D are generally between 3/1 and 16/1, and preferably between 4/1 and 8/1. It is also possible and advantageous to carry out the recovery of the solvent according to the opticcritical process, that is to say by using a solvent under supercritical conditions in the separation section. This method makes it possible in particular to significantly improve the overall economy of the method.
  • the solvent/feed (volume/volume) ratios entering the deasphalter D are low, typically between 4/1 and 8/1, or even between 4/ 1 and 6/1.
  • the deasphalting is carried out in an extraction column at a temperature between 60° C. and 250° C. with at least one hydrocarbon solvent having from 3 to 7 carbon atoms, and a solvent / charge ratio (volume/volume) between 4/1 and 6/1.
  • the deasphalter D produces a DAO practically free of asphaltenes C 7 and a residual asphalt concentrating the major part of the impurities of the residue, said residual asphalt being withdrawn.
  • the DAO yield is generally between 40% by weight and 95% by weight depending on the operating conditions and the solvent used, and depending on the load sent to the deasphalter D and in particular the quality of the heavy liquid cut resulting from the first fractionation stage (c ).
  • Table 1 gives the ranges of typical operating conditions for deasphalting depending on the solvent: ⁇ b>Table 1 ⁇ /b> Solvent Propane Butane pentane Hexane Heptane Pressure, MPa 3-5 3-4 2-4 2-4 2-4 Temperature, °C 45 - 110 80 - 160 140 - 210 150 - 230 160 - 280 Solvent/Filler Ratio, v/v 6-10 5-8 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6 3-6
  • the deasphalting conditions are adapted to the quality of the DAO to be extracted and to the load entering the deasphalter D.
  • the DAO obtained advantageously has a content of C 7 asphaltenes of less than 2% by weight in general, preferably of less than 0.5% by weight, preferably of less than 0.05% by weight measured of C 7 insolubles.
  • the DAO thus produced is either sent to a second fractionation stage (e) of the process according to the invention, or recycled at least in part to one or more of the intermediate separation stages ( b j ) and/ or directly at the entrance to one or more additional hydroconversion stages ( a i ), and more preferably at the entrance to the last additional hydro conversion stage ( a n ).
  • the DAO from the deasphalting step (d) can undergo, at least in part, a second fractionation in a second fractionation section E, in order to produce at least two fractions.
  • part or all of the DAO from the deasphalting step (d) is sent to this second fractionation step (e).
  • the second fractionation section E comprises any separation means known to those skilled in the art.
  • the second fractionating section E can thus comprise one or more following separation equipment: one or more flash drums arranged in series, and preferably a sequence of at least two successive flash drums, one or more stripping columns at the steam and/or hydrogen, an atmospheric distillation column, a vacuum distillation column.
  • this second splitting step (e) is carried out by linking at least two successive flash balloons.
  • this second fractionation step (e) is carried out by one or more steam and/or hydrogen stripping columns.
  • this second fractionation step (e) is carried out by an atmospheric distillation column, and more preferably by an atmospheric distillation column and a vacuum column receiving the atmospheric residue.
  • this second fractionation stage (e) is carried out by one or more flash drums, an atmospheric distillation column and a vacuum column receiving the atmospheric residue.
  • this second fractionation step (e) is carried out by a vacuum column.
  • the choice of the equipment of the splitting section E preferably depends on the choice of the equipment of the first splitting section C and of the loads introduced into the deasphalter D.
  • the heavy fraction of the DAO thus produced in the second fractionation section E is then recycled at least in part to one or more intermediate separation stages and/or directly to the inlet of one or several additional hydroconversion steps ( a i ), and more preferably at the inlet of the last additional hydroconversion step ( a n ).
  • the heavy cut resulting from the first fractionation section C of the process according to the invention is an atmospheric residue which leaves an atmospheric distillation column.
  • the absence of a vacuum distillation column avoids the concentration of sediments and rapid fouling of the vacuum distillation column.
  • the atmospheric residue thus produced is then sent to the deasphalter D to operate the deasphalting stage (d), producing a residual asphalt and a DAO practically free of C 7 asphaltenes and sediments, but containing both a fraction of distillate under vacuum and a residue fraction under vacuum.
  • This DAO thus obtained can then be sent to the second fractionation section E of the process according to the invention, consisting of a vacuum distillation column and having the objective of separating the DAO into at least one light fraction of the DAO whose boiling point is predominantly below 500°C and at least one heavy fraction of the DAO whose boiling point is predominantly above 500°C.
  • the vacuum distillation column will only foul very slowly, thus avoiding frequent shutdowns and shutdowns for cleaning of the vacuum distillation column.
  • the heavy fraction of the DAO thus produced is then advantageously recycled at least in part at the inlet of the last additional hydroconversion stage ( a n ).
  • the process according to the invention therefore improves the stability of the liquid effluents treated during the hydroconversion, and more particularly during the additional hydroconversion stages receiving at least a part of the DAO and/or of the heavy fraction of the DAO, while by considerably increasing the conversion of the heavy hydrocarbon feedstock.
  • the process according to the invention comprises the recycling of at least part of the DAO resulting from stage (d) and/or of at least a part of the heavy fraction of the DAO resulting from stage (e) to an additional hydroconversion step ( a i ) and/or to an intermediate separation step ( b j ).
  • the process according to the invention may comprise other recyclings, the recycled effluents possibly coming from the second fractionation stage (e), from the deasphalting stage (d), from an additional hydroconversion stage ( a i ), or an intermediate separation step ( b j ).
  • the method comprises the recycling ( r 1 ) of part or all of the light fraction of the DAO from step (e) in the initial hydroconversion section A 1 and/or in at least one additional hydroconversion section A i and/or in at least one intermediate separation section B j and/or in the first fractionation section C.
  • the method comprises the recycling ( r 2 ) of part of the heavy fraction of the DAO resulting from step (e) in the first fractionation section C.
  • the method comprises the recycling ( r 3 ) of part of the DAO resulting from step (d) in the first fractionation section C.
  • the method comprises the recycling ( r 4 ) of part or all of the residual asphalt resulting from step (d) in the initial hydroconversion section A 1 and/or in at least one additional hydroconversion section A i .
  • the residual asphalt is recycled in a hydroconversion section different from that which receives the DAO or the heavy fraction of the DAO.
  • the figure 1 schematically represents the general case of the method according to the invention, including different options corresponding to different embodiments.
  • the heavy hydrocarbon charge 1 is sent via a pipe to an initial hydroconversion section A 1 composed of one or more three-phase reactors, which can be in series and/or in parallel.
  • These hydroconversion reactors can be reactors of the bubbling bed and/or hybrid bed type, depending on the feed to be treated, and are preferably reactors operating in a bubbling bed.
  • the initial hydroconversion step carried out in section A 1 represents the first hydroconversion step of the heavy hydrocarbon feedstock 1, and may include the co-treatment of one or more external feedstocks 2 and/or one or more recycle effluents from other stages of the process.
  • the liquid effluent 3 from the initial hydroconversion section A 1 can be sent either directly to the additional hydroconversion section A 2 , or to the intermediate separation section B 1 via a pipe.
  • This line offers the possibility of purging a fraction of this effluent 3 and therefore of sending either all or only part of the liquid effluent from A 1 to the intermediate separation section B 1 .
  • the heavy fraction 5 from the first intermediate separation section B 1 is then sent at least in part to the additional hydroconversion section A 2 via a pipe, while the light fraction 4 from the section B 1 is purged via a other conduct.
  • a purge of the heavy fraction 5 can be carried out; it is either part or all of the heavy fraction 5 which is sent to the additional hydroconversion section A 2 .
  • Part of the effluent 5 can also be recycled to the initial hydroconversion section A 1 .
  • Section A 2 represents the second hydroconversion section where an additional hydroconversion step ( a 2 ) is carried out.
  • Section A 2 is made up of one or more three-phase reactors, which can be in series and/or in parallel. These hydroconversion reactors can be reactors of the bubbling bed and/or hybrid bed type, depending on the feed to be treated, and are preferably reactors operating in a bubbling bed.
  • the liquid effluent 6 from the second hydroconversion section A 2 can be sent to a third hydroconversion section, or to a second intermediate separation section via a pipe which offers the possibility of purging a fraction of said effluent and therefore of sending either all or only part of said effluent from section A 2 to second intermediate separation section B 2 (not shown), as well as recycling part of said effluent to one or more hydroconversion sections upstream from section A 2 or towards the intermediate separation section B 1 situated between sections A 1 and A 2 .
  • the process according to the invention can thus comprise n hydroconversion steps and (n-1) intermediate separation steps.
  • Section A n represents the last hydroconversion step where the additional hydroconversion step ( a n ) is carried out.
  • Section A n is made up of one or more three-phase reactors, which can be in series and/or in parallel. These hydroconversion reactors can be boiling bed and/or hybrid bed reactors, depending on the feed to be treated, and are preferably reactors operating in a boiling bed.
  • Section C represents the first fractionation section in which all or at least part of the hydroconverted liquid effluent 10 from the last hydroconversion section A n is sent via a pipe to be split into several cuts.
  • the figure 1 represents three cuts, a light cut 11, which comes out of the process according to the invention and which is optionally sent to post-processing, an intermediate cut 12 and a heavy cut 13. These last two cuts can be partially or totally sent to d other processes and/or recycled to one or more hydroconversion stages of the process according to the invention and/or recycled to one or more intermediate separation sections of the process according to the invention.
  • the DAO produced in the deasphalter D can either be sent, in part or totally, to the second fractionation section E, or recycled, in part or totally, to one or more of the additional hydroconversion sections A i and/or to one or more of the intermediate separation sections B j .
  • Section E represents a second splitting section of the method according to the invention in which step (e) of splitting all or at least part of the DAO into at least two sections is carried out.
  • the process illustrated in figure 1 shows two cuts, a light cut 16, which can come out of the process according to the invention and/or be recycled in different sections of the process as previously described, and a heavy cut 17. The latter can then be partially or totally recycled in one or more several additional hydroconversion sections A i and/or recycled on one or on several intermediate separation sections B j .
  • the light cut 16 can for example, in part or in whole, be used to produce heavy fuel oils, such as bunker fuel oils.
  • the light cut 16 can also, in part or in whole, be sent to a conversion stage operating with a process chosen from the group formed by fixed-bed hydrocracking, fluidized-bed catalytic cracking, bubbling-bed hydroconversion , these processes possibly comprising a prior hydrotreatment.
  • part or all of the light cut 16 of the deasphalted DAO fraction is subjected to fixed-bed hydrocracking, in the presence of hydrogen, under an absolute pressure of between 5 MPa and 35 MPa, at a temperature advantageously comprised between 300 and 500° C., a WH comprised between 0.1 h -1 and 5 h -1 , and a quantity of hydrogen comprised between 100 Nm 3 /m 3 and 1000 Nm 3 /m 3 (normal cubic meters (Nm 3 ) per cubic meter (m 3 ) of liquid charge), and in the presence of a catalyst containing at least one element from non-noble group VIII and at least one element from group VIB and comprising a support containing at minus one zeolite.
  • part or all of the light cut 16 of the deasphalted fraction DAO is subjected to catalytic cracking in an FCC fluidized bed in the presence of a catalyst, preferably devoid of metals, comprising alumina, silica, silica-alumina, and preferably comprising at least one zeolite.
  • a catalyst preferably devoid of metals, comprising alumina, silica, silica-alumina, and preferably comprising at least one zeolite.
  • part or all of the light cut 16 of the deasphalted fraction DAO is subjected to bubbling bed hydroconversion, carried out in the presence of hydrogen, under an absolute pressure of between 2 MPa and 35 MPa, at a temperature between 300°C and 550°C, a quantity of hydrogen between 50 Nm 3 /m 3 and 5000 Nm 3 /m 3 (normal cubic meters (Nm 3 ) per cubic meter (m 3 ) of liquid load), a WH between 0.1 h -1 and 10 h -1 and in presence of a catalyst containing a support and at least one metal from group VIII chosen from nickel and cobalt and at least one metal from group VIB chosen from molybdenum and tungsten.
  • Circuit 18 dotted on the figure 1 represents the multiple possible catalyst exchanges between the different hydroconversion steps, as well as the purging and addition of fresh and spent catalysts.
  • the figure 2 illustrates the invention in a preferred implementation comprising the recycling of the heavy fraction of the DAO at the inlet of the last hydroconversion step.
  • the method comprises the following successive steps: the initial hydroconversion step ( a 1 ), the intermediate separation step ( b 1 ), a second hydroconversion step ( a 2 ) which is the only additional hydroconversion step, the first fractionation step (c), the deasphalting step (d) and the second fractionation step (e).
  • the heavy hydrocarbon charge 1 is sent via a pipe into the initial hydroconversion section A 1 at high hydrogen pressure 19.
  • the section A 1 is identical to that described in relation to the figure 1 .
  • the liquid effluent 3 from section A 1 is separated in intermediate separation section B 1 .
  • the conditions are generally chosen so as to obtain two liquid fractions, a light fraction 4 and a heavy fraction 5.
  • the section can comprise any means of separation known to those skilled in the art, and preferably does not comprise either an atmospheric distillation column or a vacuum distillation column, but a vapor or hydrogen stripping column, and is constituted more preferably by a sequence of flash drums, and even more preferably by a single flash balloon.
  • the heavy liquid fraction 5 at the outlet of the intermediate separation section B 1 is then sent via a pipe to the second hydroconversion stage A 2 at high hydrogen pressure 20.
  • This section A 2 conforms to the description of the section of initial hydroconversion A 1 of the figure 1 .
  • the hydroconverted liquid effluent 6 obtained at the end of this second hydroconversion stage is separated in the first fractionation section C.
  • the conditions are chosen so as to obtain at least two liquid fractions, a light cut 11 and a heavy cut 13.
  • the section preferably includes a set of flash drums and an atmospheric distillation column.
  • the heavy cut 13 is then sent via a pipe into the deasphalter D to obtain a DAO 15 which is sent to the second fractionating section E via a pipe and a residual asphalt 14 which is purged via another pipe.
  • Section E comprises preferably a set of flash flasks and a vacuum distillation column.
  • the heavy fraction of the DAO 17 is then mixed, in part or in whole as shown, with the heavy liquid fraction 5 from the intermediate separation section B 1 and the mixture is then sent to the second hydroconversion section A 2 .
  • the picture 3 illustrates the invention in another implementation involving the recycling of the DAO in the intermediate separation section.
  • the method comprises the following successive steps: the initial hydroconversion step ( a 1 ), the intermediate separation step ( b 1 ), a second hydroconversion step ( a 2 ) which is the one additional hydroconversion step, the first fractionation step (c), and the deasphalting step (d). There is no second splitting step (e).
  • the heavy hydrocarbon charge 1 is sent via a pipe to an initial hydroconversion section A 1 at high hydrogen pressure 19.
  • Section A 1 is identical to that described in relation to the figure 1 .
  • Section B 1 may include any means of separation known to those skilled in the art, and preferably does not include either an atmospheric distillation column or a vacuum distillation column, but a steam or hydrogen stripping column, and is more preferred by a sequence of flash balloons, and even more preferably by a single flash balloon.
  • the heavy liquid fraction 5 at the outlet of the intermediate separation section B 1 is then sent to the second hydroconversion section A 2 at high hydrogen pressure 20.
  • This section A 2 conforms to the description of the hydroconversion section initial A 1 of the figure 1 .
  • the hydroconverted liquid effluent 6 obtained at the end of this second hydroconversion stage is separated in the first fractionation section C.
  • the conditions are chosen so as to obtain at least two liquid fractions, a light cut 11 and a heavy cut 13.
  • the section preferably involves using a set of flash flasks and an atmospheric distillation column.
  • the heavy cut 13 is then sent via a pipe to the deasphalter D to obtain a DAO which is recycled to the intermediate separation section B 1 and a residual asphalt 14 which is purged via another pipe.
  • the DAO is then mixed, in part or in whole as shown, with the liquid effluent 3 from the initial hydroconversion section A 1 and the mixture is then sent to the intermediate separation section B 1 .
  • the figure 4 illustrates the invention in another preferred implementation comprising the recycling of the DAO at the inlet of the last hydroconversion step.
  • the method comprises the following successive steps: the initial hydroconversion step ( a 1 ), the intermediate separation step ( b 1 ), a second hydroconversion step ( a 2 ) which is the one additional hydroconversion step, the first fractionation step (c), and the deasphalting step (d). There is no second splitting step (e).
  • the heavy hydrocarbon charge 1 is sent via a pipe to an initial hydroconversion section A 1 at high hydrogen pressure 19.
  • Section A 1 is identical to that described in relation to the figure 1 .
  • the liquid effluent 3 from section A 1 is separated in intermediate separation section B 1 .
  • the conditions are chosen so as to obtain two liquid fractions, a light fraction 4 and a heavy fraction 5.
  • the section can comprise any means of separation known to those skilled in the art, and preferably not has neither an atmospheric distillation column nor a vacuum distillation column, but a steam or hydrogen stripping column, and is more preferred by a sequence of flash balloons, and even more preferably by a single flash balloon.
  • the heavy liquid fraction 5 at the outlet of the intermediate separation section B 1 is then sent via a pipe to the second hydroconversion stage A 2 at high hydrogen pressure 20.
  • This section A 2 conforms to the description of the section of initial hydroconversion A 1 of the figure 1 .
  • the hydroconverted liquid effluent 6 obtained at the end of this second hydroconversion stage is separated in the first fractionation section C.
  • the conditions are chosen so as to obtain at least two liquid fractions, a light cut 11 and a heavy cut 13.
  • the section preferably comprises a set of flash drums and atmospheric and vacuum distillation columns.
  • the heavy cut 13 is then sent via a pipe to the deasphalter D to obtain a DAO 15 which is recycled via a pipe to the second hydroconversion section A 2 and a residual asphalt 14 which is purged via another pipe.
  • the DAO is then mixed, in part or in whole as shown, with the heavy liquid fraction 5 coming from the intermediate separation section B 1 and the mixture is then sent to the second hydroconversion section A 2 .
  • the figure 5 illustrates the invention in another implementation not comprising any intermediate separation step.
  • the method comprises the following successive steps: the initial hydroconversion step ( a 1 ), a second hydroconversion step ( a 2 ) which is the only additional hydroconversion step, the first step of fractionation (c), and the deasphalting step (d). There is no second splitting step (e).
  • the heavy hydrocarbon charge 1 is sent via a pipe to an initial hydroconversion section A 1 at high hydrogen pressure 19.
  • Section A 1 is identical to that described in relation to the figure 1 .
  • the liquid effluent 3 from section A 1 is then sent via a pipe to the second hydroconversion section A 2 at high hydrogen pressure 20.
  • This section A 2 conforms to the description of the initial hydroconversion section At 1 of the figure 1 .
  • the hydroconverted liquid effluent 6 obtained at the end of this second hydroconversion step is separated in the first fractionation section C.
  • the conditions are chosen so as to obtain at least two liquid fractions, a light cut 11 and a heavy cut 13.
  • the section preferably comprises using a set of flash drums and atmospheric and vacuum distillation columns.
  • the heavy cut 13 is then sent via a pipe to the deasphalter D to obtain the DAO 15 which is recycled via a pipe to the second hydroconversion section A 2 and a residual asphalt 14 which is purged via another pipe.
  • the DAO 15 is mixed, in part or in whole as shown, with the liquid effluent 3 from the initial hydroconversion section A 1 , and the mixture is sent to the second hydroconversion section A 2 .
  • Examples 1, 2 and 6 are not in accordance with the invention.
  • Examples 3, 4, 5 and 7 are in accordance with the invention.
  • the heavy hydrocarbon charge is a vacuum residue (RSV) originating from a Ural crude oil, the main characteristics of which are presented in Table 2 below.
  • RSV vacuum residue
  • Table 2 Charge of the first stage of hydroconversion ( a 1 ) / (a' 1 ) / (a" 1 ) Charge RSV Urals Content at 540°C+ %weight 84.7 Viscosity at 100°C cSt 880 Density 1.0090 Carbon Conradson %weight 17.0 C 7 Asphaltenes %weight 5.5 Nickel + Vanadium ppm weight 254 Nitrogen %weight 0.615 Sulfur %weight 2,715
  • This RSV heavy load is the same fresh load for the different examples.
  • Example. 1 Method of. reference without recycling of / a DAO. (not according to the invention)
  • This example illustrates a process for the hydroconversion of a heavy charge of hydrocarbons according to the state of the art comprising two successive hydroconversion stages each comprising a reactor operating in an ebullated bed, followed by a deasphalting stage without recycling of the DAO.
  • the fresh feed from Table 2 is sent in its entirety to a first hydroconversion section A′ 1 in the presence of hydrogen to undergo a first hydroconversion step ( a′ 1 ), said section comprising a three-phase reactor containing a catalyst of NiMo/alumina hydroconversion having a NiO content of 4% by weight and a MoO 3 content of 10% by weight, the percentages being expressed relative to the total mass of the catalyst.
  • the reactor operates in an ebullated bed operating with an ascending current of liquid and gas.
  • the hydroconverted liquid effluent from the first hydroconversion stage ( a′ 1 ) is then sent to an intermediate separation section B′ 1 composed of a single gas/liquid separator operating at the pressure and temperature of the reactor of the first stage of hydroconversion.
  • a light fraction and a so-called heavy fraction are thus separated.
  • the light fraction is mainly composed of molecules with a boiling point lower than 350°C and the heavy fraction is mainly composed of molecules of hydrocarbons boiling at a temperature higher than or equal to 350°C.
  • the heavy fraction is sent to a second hydroconversion section A ′ 2 in the presence of hydrogen to undergo a second hydroconversion stage ( a ′ 2 ).
  • the second hydroconversion section A ′ 2 comprises a three-phase reactor A ′ 2 containing a NiMo/alumina hydroconversion catalyst having a NiO content of 4% by weight and a MoO 3 content of 10% by weight, the percentages being expressed by relative to the total mass of the catalyst.
  • the section operates as a bubbling bed operating with an ascending current of liquid and gas.
  • the hydroconverted liquid effluent from the hydroconversion step ( a′ 2 ) is sent to a fractionation step (c′) carried out in a fractionation section C′ composed of an atmospheric distillation column and a distillation column under vacuum following which a distillate fraction is recovered under vacuum boiling at a temperature between essentially between 350°C and 500°C (DSV) and an unconverted vacuum residue fraction boiling at a temperature greater than or equal to 500°C (RSV) whose yields relative to the fresh load and product qualities are given in Table 6 below.
  • a fractionation section C′ composed of an atmospheric distillation column and a distillation column under vacuum following which a distillate fraction is recovered under vacuum boiling at a temperature between essentially between 350°C and 500°C (DSV) and an unconverted vacuum residue fraction boiling at a temperature greater than or equal to 500°C (RSV) whose yields relative to the fresh load and product qualities are given in Table 6 below.
  • the RSV from the distillation zone of the fractionation section C′ is then advantageously sent to a deasphalting stage (d′) in a deasphalter D′ in which it is treated in an extractor using butane solvent in deasphalting conditions to obtain a DAO and a residual asphalt.
  • the overall conversion of the 540° C.+ fraction of the fresh charge is 64.0% by weight.
  • the unconverted vacuum residue fraction contains 0.20% by weight of sediments, 150 ppm by weight of metals and a Conradson Carbon content greater than 30% by weight. This cut is therefore very difficult to value.
  • the deasphalting of the unconverted vacuum residue makes it possible to extract a recoverable fraction by separating the RSV into a DAO fraction (which represents almost 70% of the RSV) and an asphalt fraction.
  • the DAO fraction contains almost no more metals or asphaltenes and its Conradson Carbon content is less than 8% by weight.
  • This DAO cut can therefore be sent, in part or in whole, to another conversion stage such as fixed bed hydrocracking, fixed bed hydrotreating, fluidized bed catalytic cracking, or bubbling bed hydroconversion .
  • Example 2 Reference process. with recycling of the DAO at the inlet of the first, hydroconversion stage (not in accordance with the invention)
  • the state of the art is illustrated in a process for the hydroconversion of a heavy charge of hydrocarbons comprising two successive hydroconversion stages each comprising a reactor operating in an ebullated bed, followed by a stage of deasphalting with recycling of the DAO at the entrance to the first hydroconversion stage.
  • the fresh load from Table 2 is first mixed with the DAO from the deasphalting stage ( d" ) in a fresh load/DAO volume ratio equal to 75/25. This mixture is then sent in its entirety to a first section of hydroconversion A “ 1 in the presence of hydrogen to undergo a first hydroconversion step ( a " 1 ).
  • This section A " 1 is identical to that described in example 1.
  • the conversion per pass of the 540° C.+ fraction at the outlet of the first hydroconversion stage is 33.4% by weight.
  • the hydroconverted liquid effluent from the first hydroconversion stage (a" 1 ) is then sent to an intermediate separation section B" 1 composed of a single gas/liquid separator operating at the pressure and temperature of the reactor of the first hydroconversion step.
  • a light fraction and a heavy fraction are thus separated.
  • the light fraction is mainly composed of molecules with a boiling point below 350°C and the so-called heavy fraction is mainly composed of hydrocarbon molecules bubbling at a temperature greater than or equal to 350°C.
  • the heavy fraction is sent in its entirety to a second hydroconversion section A′′ 2 in the presence of hydrogen to undergo a second hydroconversion stage (a′′ 2 ).
  • This section A" 2 is identical to that described in example 1.
  • the hydroconverted liquid effluent from the hydroconversion stage (a" 2 ) is sent to a fractionation stage (c") carried out in a fractionation section C" composed of an atmospheric distillation column and a distillation column under vacuum following which a distillate fraction under vacuum boiling at a temperature essentially between 350°C and 500°C (DSV) and an unconverted residue fraction under vacuum boiling mainly at a temperature greater than or equal to 500°C are recovered (RSV) whose yields in relation to the fresh load and product qualities are given in Table 11 below.
  • the RSV from the first fractionation section C ′′ is then advantageously sent to a deasphalting stage (d′′) in a deasphalting device D ′′, in which it is treated as described in example 1 (same equipment and same conditions).
  • the conversion by pass of the 540° C.+ fraction of the fresh feed in the section of hydroconversion is 55.9% by weight.
  • the unconverted vacuum residue fraction contains 0.34% by weight of sediment, 74 ppm by weight of metals and a Conradson Carbon content of 21% by weight. This cut is therefore very difficult to value.
  • the deasphalting of the unconverted vacuum residue makes it possible to extract a recoverable fraction by separating the RSV into a DAO fraction (which represents almost 74% of the RSV) and an asphalt fraction.
  • the DAO fraction contains almost no more metals or asphaltenes and its Conradson Carbon content is less than 5% by weight.
  • a large fraction of this DAO cut (74%) is recycled at the inlet of the first reactor of the hydroconversion section. Thanks to recycling, the overall conversion of the 540° C.+ fraction of the fresh feed is 69.7% by weight.
  • Example 3 Process according to the invention, aimed at reducing the sediment content of the unconverted vacuum residue
  • the process according to the invention is illustrated in an implementation comprising two successive hydroconversion stages each comprising a reactor operating in an ebullated bed followed by a deasphalting stage with recycling of the DAO at the inlet of the last hydroconversion reactor.
  • the fresh feed from Table 2 is sent in its entirety to a first hydroconversion section A 1 in the presence of hydrogen to undergo a first hydroconversion step ( a 1 ).
  • This section A 1 is identical to that described in example 1.
  • the hydroconverted liquid effluent is then sent to an intermediate separation section B 1 composed of a single gas/liquid separator operating at the pressure and temperature of the reactor of the first hydroconversion stage.
  • a light fraction and a heavy fraction are thus separated.
  • the light fraction is mainly composed of molecules with a boiling point below 350°C and the so-called heavy fraction is mainly composed of hydrocarbon molecules bubbling at a temperature greater than or equal to 350°C.
  • the heavy effluent from the intermediate separation section B 1 is completely mixed with the DAO from the deasphalting step ( d ) in a heavy effluent/DAO volume ratio of 75 /25.
  • the composition of this filler is shown in Table 15. ⁇ b>Table 15 ⁇ /b> Stage load (a 2 ) Density 0.9854 Carbon Conradson %weight 10.4 C 7 Asphaltenes %weight 3.7 Nickel + Vanadium ppm weight 60 Nitrogen %weight 0.54 Sulfur %weight 1.2186
  • this mixture is sent entirely to a second hydroconversion section A 2 in the presence of hydrogen to undergo a second hydroconversion stage ( a 2 ).
  • Said section A 2 is identical to that described in example 1.
  • the hydroconverted liquid effluent from the hydroconversion stage ( a 2 ) is sent to a fractionation stage ( c ) carried out in a fractionation section C composed of an atmospheric distillation column and a vacuum distillation column at the following which a vacuum distillate fraction boiling at a temperature essentially between 350° C. and 500° C. (DSV) and an unconverted vacuum residue fraction boiling at a temperature greater than or equal to 500° C. (RSV) are recovered.
  • DSV vacuum distillate fraction boiling at a temperature essentially between 350° C. and 500° C.
  • RSV unconverted vacuum residue fraction boiling at a temperature greater than or equal to 500° C.
  • Example 2 Comparing with Example 1, a higher level of hydrotreating is observed with a lower density, lower sulfur, nitrogen, metals, asphaltenes and Conradson carbon contents.
  • RSV contains less sediment and is therefore more stable, in particular thanks to the presence of heavy aromatics from the recycled DAO upstream of the second hydroconversion step.
  • Example 2 By comparing with Example 2, it is noted that the level of hydrotreatment is slightly lower, but that the RSV contains much less sediment. This cut is therefore more stable, in particular thanks to the presence of heavy aromatics from the DAO cut recycled upstream of the second hydroconversion step.
  • the DAO is recycled upstream of the first hydroconversion stage and the heavy aromatics are hydrogenated more compared to the process according to the invention.
  • the RSV from the first fractionation section is then advantageously sent to a deasphalting stage ( d ) in a deasphalting device, in which it is treated as described in example 1 (same equipment and same conditions).
  • the conversion per pass of the 540° C.+ fraction of the fresh feed from the hydroconversion section is 61.5% by weight.
  • the unconverted vacuum residue fraction contains 0.07% by weight of sediment, 63 ppm by weight of metals and a Conradson Carbon content of 24% by weight. This cut is therefore very difficult to value.
  • the deasphalting of the unconverted vacuum residue makes it possible to extract a recoverable fraction by separating the RSV into a DAO fraction (which represents almost 74% of the RSV) and an asphalt fraction.
  • the DAO fraction contains almost no more metals or asphaltenes and its Conradson Carbon content is less than 5% by weight.
  • the conversion is stronger (5.5 conversion points more) and that the RSV which leaves the vacuum distillation column at the first fractionation stage is more stable. (0.07% by weight instead of 0.20% by weight), because it contains less sediment, thus limiting the fouling of the columns of the first fractionation section.
  • the overall conversion is identical, but the residual RSV contains 5 times less sediment (0.07% by weight instead of 0.34% by weight). As a result, the fouling of the columns of the first fractionation section is greatly reduced allowing a longer operation before stopping for their cleaning.
  • Example 4 Process according to the invention , aimed at increasing the overall conversion of the 540° C.+ fraction
  • the process according to the invention is illustrated in an implementation comprising two successive hydroconversion stages each comprising a reactor operating in an ebullated bed followed by a deasphalting stage with recycling of the DAO at the inlet of the last hydroconversion reactor.
  • this latter reactor will be operated under more severe conditions in order to increase the overall conversion of the process.
  • the fresh feed from Table 2 is sent in its entirety to a first hydroconversion section A 1 in the presence of hydrogen to undergo a first hydroconversion step ( a 1 ).
  • This section A 1 is identical to that described in example 1.
  • the hydroconverted liquid effluent is then sent to an intermediate separation section B 1 composed of a single gas/liquid separator operating at the pressure and temperature of the reactor of the first hydroconversion stage.
  • a light fraction and a heavy fraction are thus separated.
  • the light fraction is mainly composed of molecules with a boiling point below 350°C and the so-called heavy fraction is mainly composed of hydrocarbon molecules bubbling at a temperature greater than or equal to 350°C.
  • the heavy effluent from the intermediate separation section B 1 is completely mixed with the DAO from the deasphalting step ( d ) in a heavy effluent/DAO volume ratio of 75 /25.
  • the composition of this filler is shown in Table 21. ⁇ b>Table 21 ⁇ /b> Stage load (a 2 ) Density 0.9865 Carbon Conradson %weight 10.6 C 7 Asphaltenes %weight 3.7 Nickel + Vanadium ppm weight 60 Nitrogen %weight 0.55 Sulfur %weight 1.2324
  • this mixture is sent entirely to a second hydroconversion section A 2 in the presence of hydrogen to undergo a second hydroconversion stage ( a 2 ).
  • Said section A 2 is identical to that described in example 1.
  • the hydroconverted liquid effluent from the hydroconversion stage (a 2 ) is sent to a fractionation stage ( c ) carried out in a fractionation section C composed of an atmospheric distillation column and a vacuum distillation column at the following which a vacuum distillate fraction boiling at a temperature essentially between 350° C. and 500° C. (DSV) and an unconverted vacuum residue fraction boiling at a temperature greater than or equal to 500° C. (RSV) are recovered.
  • DSV vacuum distillate fraction boiling at a temperature essentially between 350° C. and 500° C.
  • RSV unconverted vacuum residue fraction boiling at a temperature greater than or equal to 500° C.
  • Example 2 Comparing with Example 1, a higher level of hydrotreating is observed with a lower density, lower sulfur, nitrogen, metals, asphaltenes and Conradson carbon contents. Despite the higher severity, the RSV contains the same sediment content and therefore remains stable, in particular thanks to the presence of heavy aromatics from the DAO recycled upstream of the second hydroconversion step.
  • Example 2 By comparing with Example 2, it is noted that the level of hydrotreatment is very similar, but that the RSV contains less sediment. This cut is therefore more stable, in particular thanks to the presence of heavy aromatics from the DAO cut recycled upstream of the second hydroconversion step.
  • the DAO is recycled upstream of the first hydroconversion stage and the heavy aromatics are hydrogenated more compared to the process according to the invention.
  • the RSV from the first fractionation section is then advantageously sent to a deasphalting stage ( d ) in a deasphalting device, in which it is treated as described in example 1 (same equipment and same conditions).
  • a conversion is achieved per pass of the 540° C.+ fraction of the fresh charge of 64 .6% by weight in the hydroconversion section for identical operating conditions.
  • the unconverted fraction, the vacuum residue contains 0.19 wt% sediment, 61 wppm metals and a Conradson Carbon content of 27 wt%. This cut is therefore very difficult to value.
  • the deasphalting of the unconverted vacuum residue makes it possible to extract a recoverable fraction by separating the RSV into a DAO fraction (which represents almost 73% of the RSV) and an asphalt fraction.
  • the DAO fraction contains almost no more metals or asphaltenes and its Conradson Carbon content is less than 6% by weight.
  • a large fraction of this DAO cut (83%) is recycled at the inlet of the last reactor of the hydroconversion section. Thanks to recycling, the overall conversion of the 540° C.+ fraction of the fresh feed is 73.9% by weight.
  • the conversion is much stronger (+10 conversion points), but that the RSV which leaves the vacuum distillation column at the first fractionation stage remains stable, because it contains approximately the same sediment content (0.19% by weight instead of 0.20% by weight).
  • the conversion is greater (+4 conversion points), but the residual RSV still contains much less sediment (0.19% by weight instead of 0.34% by weight) and remains therefore stable under these more severe conditions. Therefore, in the scheme according to the invention, the fouling of the columns of the first fractionation section is greatly reduced compared to diagram 2 not in accordance with the invention, allowing a longer operation before stopping for their cleaning.
  • Example 5 Method according to the invention, aiming to recycle the DAO cut until extinguished
  • the process according to the invention is illustrated in an implementation comprising two successive hydroconversion stages each comprising a reactor operating in an ebullated bed followed by a deasphalting stage with recycling of the DAO at the inlet of the last hydroconversion reactor.
  • the DAO cut will be recycled until extinguished in order to increase the overall conversion of the process.
  • the fresh feed from Table 2 is sent in its entirety to a first hydroconversion section A 1 in the presence of hydrogen to undergo a first hydroconversion step ( a 1 ).
  • This section A 1 is identical to that described in example 1.
  • the hydroconverted liquid effluent is then sent to an intermediate separation section B 1 composed of a single gas/liquid separator operating at the pressure and temperature of the reactor of the first hydroconversion stage.
  • a light fraction and a heavy fraction are thus separated.
  • the light fraction is mainly composed of molecules with a boiling point below 350°C and the so-called heavy fraction is mainly composed of hydrocarbon molecules bubbling at a temperature greater than or equal to 350°C.
  • the heavy effluent from the intermediate separation section B 1 is mixed in its entirety with the entire DAO cut resulting from the deasphalting stage ( d ).
  • the composition of this filler is shown in Table 27. ⁇ b>Table 27 ⁇ /b> Stage load (a 2 ) Density 0.9857 Carbon Conradson %weight 9.8 C 7 Asphaltenes %weight 3.2 Nickel + Vanadium ppm weight 52 Nitrogen %weight 0.52 Sulfur %weight 1.1591
  • this mixture is sent entirely to a second hydroconversion section A 2 in the presence of hydrogen to undergo a second hydroconversion stage ( a 2 ).
  • Said section A 2 is identical to that described in example 1.
  • the hydroconverted liquid effluent from the hydroconversion stage ( a 2 ) is sent to a fractionation stage ( c ) carried out in a fractionation section C composed of an atmospheric distillation column and a vacuum distillation column at the following which a vacuum distillate fraction boiling at a temperature essentially between 350° C. and 500° C. (DSV) and an unconverted vacuum residue fraction boiling at a temperature greater than or equal to 500° C. (RSV) are recovered.
  • DSV vacuum distillate fraction boiling at a temperature essentially between 350° C. and 500° C.
  • RSV unconverted vacuum residue fraction boiling at a temperature greater than or equal to 500° C.
  • Example 1 Comparing with Example 1, a higher level of hydrotreating is observed with a lower density, lower sulfur, nitrogen, metals, asphaltenes and Conradson carbon contents. Despite the higher severity, the RSV contains a similar sediment content (0.25% by weight compared to 0.20% by weight in Example 1) and therefore remains stable, in particular thanks to the presence of heavy aromatics from the DAO recycled upstream of the second hydroconversion stage.
  • Example 2 By comparing with Example 2, it is noted that the level of hydrotreatment is very similar, but that the RSV contains less sediment. This cut is therefore more stable, in particular thanks to the presence of heavy aromatics from the DAO cut recycled upstream of the second hydroconversion step.
  • the DAO is recycled upstream of the first hydroconversion stage and the heavy aromatics are hydrogenated more compared to the process according to the invention.
  • the RSV from the first fractionation section is then advantageously sent to a deasphalting stage ( d ) in a deasphalting device, in which it is treated as described in example 1 (same equipment and same conditions).
  • the DAO cut is sent in its entirety upstream of the last hydroconversion step.
  • a conversion is achieved per pass of the 540° C.+ fraction of the fresh charge of 64 .6% by weight in the hydroconversion section for identical operating conditions.
  • the unconverted fraction, the vacuum residue contains 0.25 wt% sediment, 66 wppm metals and a Conradson Carbon content of 25 wt%. This cut is therefore very difficult to value.
  • the deasphalting of the unconverted vacuum residue makes it possible to extract a recoverable fraction by separating the RSV into a DAO fraction (which represents 73.3% of the RSV) and an asphalt fraction.
  • the DAO fraction contains almost no more metals or asphaltenes and its Conradson Carbon content is only 5.2% by weight.
  • all of this DAO cut is recycled at the inlet of the last reactor of the hydroconversion section. Thanks to quenching recycling of the DAO cut, the overall conversion of the 540°C+ fraction of the fresh feed is 76.1% by weight.
  • Example 2 the conversion is much stronger (+12 conversion points), but that the RSV which leaves the vacuum distillation column at the first fractionation stage remains stable, because it contains about the same sediment content (0.25% weight instead of 0.20% weight). Compared to Example 2, the conversion is greater (more than 6 additional conversion points), but the residual RSV contains less sediment (0.25% by weight instead of 0.34% by weight) and therefore remains rather stable under these more severe conditions. Therefore, in the diagram according to the invention, the fouling of the columns of the first fractionation section is greatly reduced compared to diagram 2 not according to the invention, allowing a longer operation before stopping for their cleaning. .
  • Example 6 Process according to the invention, aimed at reducing the sediment content of the unconverted vacuum residue
  • the process according to the invention is illustrated in an implementation comprising two successive hydroconversion stages each comprising a reactor operating in an ebullated bed followed by a deasphalting stage and a fractionation stage, with recycling of the heavy DAO at the inlet of the last hydroconversion reactor and conversion of the light DAO in an FCC unit.
  • the fresh feed from Table 2 is sent in its entirety to a first hydroconversion section A 1 in the presence of hydrogen to undergo a first hydroconversion stage ( a 1 ).
  • This section A 1 is identical to that described in example 1.
  • the hydroconverted liquid effluent is then sent to an intermediate separation section B 1 composed of a single gas/liquid separator operating at the pressure and temperature of the reactor of the first hydroconversion stage.
  • a light fraction and a heavy fraction are thus separated.
  • the light fraction is mainly composed of molecules with a boiling point below 350°C and the so-called heavy fraction is mainly composed of hydrocarbon molecules bubbling at a temperature greater than or equal to 350°C.
  • the heavy effluent from the intermediate separation section B 1 is completely mixed with the heavy DAO from the second fractionation section ( e ) in a heavy effluent/DAO volume ratio of 75/25.
  • the composition of this filler is shown in Table 33. ⁇ b>Table 33 ⁇ /b> Stage load (a 2 ) Density 1.0005 Carbon Conradson %weight 12.2 C 7 Asphaltenes %weight 3.6 Nickel + Vanadium ppm weight 59 Nitrogen %weight 0.57 Sulfur %weight 1.2706
  • this mixture is sent entirely to a second hydroconversion section A 2 in the presence of hydrogen to undergo a second hydroconversion stage ( a 2 ).
  • Said section A 2 is identical to that described in example 1.
  • the hydroconverted liquid effluent from the hydroconversion stage ( a 2 ) is sent to a fractionation stage ( c ) carried out in a fractionation section C composed of an atmospheric distillation column and a vacuum distillation column at the following which a vacuum distillate fraction boiling at a temperature essentially between 350° C. and 500° C. (DSV) and an unconverted vacuum residue fraction boiling at a temperature greater than or equal to 500° C. (RSV) are recovered.
  • DSV vacuum distillate fraction boiling at a temperature essentially between 350° C. and 500° C.
  • RSV unconverted vacuum residue fraction boiling at a temperature greater than or equal to 500° C.
  • Example 2 Comparing with Example 1, a higher level of hydrotreating is observed with a lower density, lower sulfur, nitrogen, metals, asphaltenes and Conradson carbon contents.
  • RSV contains less sediment and is therefore more stable, in particular thanks to the presence of heavy aromatics from the recycled DAO upstream of the second hydroconversion step.
  • Example 2 By comparing with Example 2, it is noted that the level of hydrotreatment is lower, but that the RSV contains much less sediment. This cut is therefore more stable, in particular thanks to the presence of heavy aromatics from the heavy DAO cut recycled upstream of the second hydroconversion step.
  • the total DAO is recycled upstream of the first hydroconversion step and the heavy aromatics are hydrogenated more compared to the process according to the invention.
  • the RSV from the first fractionation section is then advantageously sent to a deasphalting stage ( d ) in a deasphalting device, in which it is treated as described in example 1 (same equipment and same conditions).
  • the DAO cut produced is sent to a second fractionation section ( e ) carried out in a fractionation section E composed by a series of flashes, an atmospheric distillation column and a vacuum distillation column following which a light DAO cut (DAO-) boiling at a temperature essentially comprised below 580° C. and a heavy DAO cut (DAO+) boiling mainly at a temperature greater than or equal to 580° C. are recovered.
  • DAO- light DAO cut
  • DAO+ heavy DAO cut
  • the heavy DAO cut (DAO+) from the fraction stage ( e ) is sent in full to the second hydroconversion stage, while the light DAO fraction (DAO-) is sent to an FCC catalytic cracking unit for a additional conversion.
  • the light DAO cut (DAO-) from the second fractionation section ( e ) carried out in the fractionation section E is then sent to a fluidized bed catalytic cracking unit, also called FCC.
  • FCC fluidized bed catalytic cracking unit
  • This conversion unit makes it possible to transform the DAO fraction, which is a 540°C+ cut, into lighter fractions. This therefore makes it possible to increase the overall conversion of the starting charge.
  • the liquid fraction from the FCC unit still contains an unconverted 540°C+ fraction, the yield of which is only 0.4% by weight relative to the FCC charge, as indicated in Table 38.
  • the conversion per pass of the 540° C.+ fraction of the fresh feed from the hydroconversion section is 60.9% by weight.
  • the unconverted vacuum residue fraction contains 0.12% by weight of sediment, 67 ppm by weight of metals and a Conradson Carbon content of 28% by weight. This cut is therefore very difficult to value.
  • Deasphalting of unconverted vacuum residue makes it possible to extract a recoverable fraction by separating the RSV into a DAO fraction (which represents approximately 72% of the RSV) and an asphalt fraction.
  • the DAO fraction contains almost no more metals or asphaltenes and its Conradson Carbon content is less than 6% by weight.
  • the DAO cut is sent to a second fractionation section in order to produce a light DAO cut, which is sent to an FCC catalytic cracking unit for further conversion, and a heavy DAO cut, which is recycled in full at the inlet of the last hydroconversion step. Thanks to the recycling of the heavy DAO cut, the overall conversion of the 540°C+ fraction of the fresh feed is 73.4% by weight in the hydrotreating section. Thanks to the conversion of the light DAO in the FCC unit, an additional conversion of 4.1% by weight is obtained, leading to an overall conversion of the scheme according to the invention of 77.5% by weight of the 540° C.+ fraction of the fresh load.
  • the conversion is much higher (+13.5 conversion points), while keeping a stable RSV which leaves the vacuum distillation column at the first fractionation section , because it contains less sediment (0.12% by weight instead of 0.20% by weight), thus limiting the fouling of the columns of the first fractionation section.
  • the conversion is not only greater (almost 8 additional conversion points), but the residual RSV contains much less sediment (0.12% by weight instead of 0.34% by weight) and remains therefore stable under these more severe conditions. Therefore, in the scheme according to the invention, the fouling of the columns of the first fractionation section is greatly reduced compared to the scheme of example 2 not in accordance with the invention, allowing a longer operation before the stop for their cleaning.
  • the use of an FCC unit for the conversion of the light DAO cut makes it possible to produce more gasoline and less diesel.
  • Example 7 Process according to the invention, aimed at increasing the overall conversion of the 540° C.+ fraction
  • the process according to the invention is illustrated in an implementation comprising two successive hydroconversion stages each comprising a reactor operating in an ebullated bed followed by a deasphalting stage and a fractionation stage, with recycling of the heavy DAO at the inlet of the last hydroconversion reactor and conversion of the light DAO in an FCC unit.
  • this latter reactor will be operated under more severe conditions in order to increase the overall conversion of the process.
  • the fresh feed from Table 2 is sent in its entirety to a first hydroconversion section A 1 in the presence of hydrogen to undergo a first hydroconversion stage ( a 1 ).
  • This section A 1 is identical to that described in example 1.
  • the hydroconverted liquid effluent is then sent to an intermediate separation section B 1 composed of a single gas/liquid separator operating at the pressure and temperature of the reactor of the first hydroconversion stage.
  • a light fraction and a heavy fraction are thus separated.
  • the light fraction is mainly composed of molecules with a boiling point below 350°C and the so-called heavy fraction is mainly composed of hydrocarbon molecules bubbling at a temperature greater than or equal to 350°C.
  • the heavy effluent from the intermediate separation section B 1 is completely mixed with the heavy DAO from the second fractionation section ( e ) in a heavy effluent/DAO volume ratio of 75/25.
  • the composition of this filler is shown in Table 41. ⁇ b>Table 41 ⁇ /b> Stage load (a 2 ) Density 0.9964 Carbon Conradson %weight 11.6 C 7 Asphaltenes %weight 3.6 Nickel + Vanadium ppm weight 59 Nitrogen %weight 0.55 Sulfur %weight 1.2671
  • this mixture is sent entirely to a second hydroconversion section A 2 in the presence of hydrogen to undergo a second hydroconversion stage ( a 2 ).
  • Said section A 2 is identical to that described in example 1.
  • the hydroconverted liquid effluent from the hydroconversion stage ( a 2 ) is sent to a fractionation stage ( c ) carried out in a fractionation section C composed of an atmospheric distillation column and a vacuum distillation column at the following which a vacuum distillate fraction boiling at a temperature essentially between 350° C. and 500° C. (DSV) and an unconverted vacuum residue fraction boiling at a temperature greater than or equal to 500° C. (RSV) are recovered.
  • DSV vacuum distillate fraction boiling at a temperature essentially between 350° C. and 500° C.
  • RSV unconverted vacuum residue fraction boiling at a temperature greater than or equal to 500° C.
  • Example 2 Comparing with Example 1, a higher level of hydrotreating is observed with lower density, lower sulfur, nitrogen, metals, asphaltenes and Conradson carbon contents.
  • RSV contains less sediment and is therefore more stable, in particular thanks to the presence of heavy aromatics from the recycled DAO upstream of the second hydroconversion step.
  • Example 2 By comparing with Example 2, it is noted that the level of hydrotreatment is lower, but that the RSV contains less sediment. This cut is therefore more stable, in particular thanks to the presence of heavy aromatics from the heavy DAO cut recycled upstream of the second hydroconversion step.
  • the total DAO is recycled upstream of the first hydroconversion step and the heavy aromatics are hydrogenated more compared to the process according to the invention.
  • the RSV from the first fractionation section is then advantageously sent to a deasphalting stage ( d ) in a deasphalting device, in which it is treated as described in example 1 (same equipment and same conditions).
  • the DAO cut produced is sent to a second fractionation section ( e ) carried out in a fractionation section E composed by a series of flashes, an atmospheric distillation column and a vacuum distillation column following which a light DAO cut (DAO-) boiling at a temperature essentially comprised below 580° C. and a heavy DAO cut (DAO+) boiling mainly at a temperature greater than or equal to 580° C. are recovered.
  • DAO- light DAO cut
  • DAO+ heavy DAO cut
  • the heavy DAO cut (DAO+) from fraction stage (e) is sent in full to the second hydroconversion stage, while the light DAO fraction (DAO-) is sent to an FCC catalytic cracking unit for additional conversion.
  • the light DAO cut (DAO-) from the second fractionation section (e) produced in the fractionation section E is then sent to a fluidized bed catalytic cracking unit, also called FCC.
  • FCC fluidized bed catalytic cracking unit
  • This conversion unit makes it possible to transform the DAO fraction, which is a 540°C+ cut, into lighter fractions. This therefore increases the overall conversion of the starting charge.
  • the liquid fraction from the FCC unit still contains an unconverted 540°C+ fraction, the yield of which is only 0.4% by weight relative to the FCC charge, as indicated in Table 46.
  • the conversion per pass of the 540° C.+ fraction of the fresh feed from the hydroconversion section is 64.6% by weight.
  • the unconverted vacuum residue fraction contains 0.23% by weight of sediment, 65 ppm by weight of metals and a Conradson Carbon content of 29% by weight. This cut is therefore very difficult to value.
  • the deasphalting of the unconverted vacuum residue makes it possible to extract a recoverable fraction by separating the RSV into a DAO fraction (which represents approximately 72% of the RSV) and an asphalt fraction.
  • the DAO fraction contains almost no more metals or asphaltenes and its Conradson Carbon content is less than 6% by weight.
  • the DAO cut is sent to a second fractionation section in order to produce a light DAO cut, which is sent to an FCC catalytic cracking unit for further conversion, and a heavy DAO cut, which is recycled in full at the inlet of the last hydroconversion stage. Thanks to the recycling of the heavy DAO cut, the overall conversion of the 540°C+ fraction of the fresh feed is 79.2% by weight in the hydrotreating section. Thanks to the conversion of the light DAO in the FCC unit, an additional conversion of 4.0% by weight is obtained, leading to an overall conversion of the scheme according to the invention of 83.2% by weight of the 540°C+ fraction of the fresh load.
  • the conversion is much higher (+19 conversion points), while keeping a stable RSV which leaves the vacuum distillation column at the first fractionation section, because it has a similar sediment content (0.23 wt% instead of 0.20 wt%).
  • the conversion is not only greater (more than 12 additional conversion points), but the Residual RSV contains less sediment (0.23% by weight instead of 0.34% by weight) and therefore remains more stable despite the more severe conditions. Therefore, in the scheme according to the invention, the fouling of the columns of the first fractionation section is greatly reduced compared to the scheme of example 2 not in accordance with the invention, allowing a longer operation before the stop for their cleaning.
  • the use of an FCC unit for the conversion of the light DAO cut makes it possible to produce more gasoline and less diesel.

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CN111819268A (zh) 2020-10-23
PL3728518T3 (pl) 2022-09-26
RU2020123948A3 (zh) 2022-01-21
PT3728518T (pt) 2022-07-22
FR3075809B1 (fr) 2020-09-11
US11149217B2 (en) 2021-10-19
EP3728518A1 (fr) 2020-10-28
FR3075809A1 (fr) 2019-06-28
US20200339894A1 (en) 2020-10-29
SA520412257B1 (ar) 2023-03-05

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