EP3728519B1 - Verbessertes verfahren zur umwandlung von rückständen mit tiefen hydrokonversionsschritten und einem entasphaltierungsschritt - Google Patents

Verbessertes verfahren zur umwandlung von rückständen mit tiefen hydrokonversionsschritten und einem entasphaltierungsschritt Download PDF

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EP3728519B1
EP3728519B1 EP18814905.8A EP18814905A EP3728519B1 EP 3728519 B1 EP3728519 B1 EP 3728519B1 EP 18814905 A EP18814905 A EP 18814905A EP 3728519 B1 EP3728519 B1 EP 3728519B1
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weight
hydroconversion
fraction
section
stage
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EP3728519A1 (de
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Joao MARQUES
Matthieu DREILLARD
Frédéric Feugnet
Jean-François Le Coz
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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
    • C10G67/049—The hydrotreatment being a hydrocracking
    • 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
    • C10G65/14—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only
    • C10G65/18—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only including only cracking 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
    • C10G47/30—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles according to the "fluidised-bed" technique
    • 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
    • C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
    • C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
    • C10G55/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one catalytic cracking step
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
    • 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
    • C10G2300/40—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

Definitions

  • the present invention relates to the conversion of heavy hydrocarbon feedstocks including at least 50% by weight of a fraction having a boiling point of at least 300°C.
  • These are crude oil or feeds resulting, directly or after treatment, from the atmospheric and/or vacuum distillation of a crude oil, such as atmospheric or vacuum residues.
  • the patent FR 2.906.814 of the applicant describes a process comprising the successive sequence of a step of deasphalting producing a deasphalted oil, a step of hydroconversion of said deasphalted oil to produce an effluent, and a step of distilling said effluent to produce a residue which is returned with the load at the deasphalting stage.
  • This patent describes a sequence of processes in which the hydroconversion step is carried out at conventional space velocities (VVH) of 0.1 h -1 to 5 h -1 and the SDA step is carried out upstream of the step. of hydroconversion.
  • VVH space velocities
  • the patent FR-2964386 of the applicant describes the sequence of a process for the treatment of feedstocks derived from crude oil, or for the atmospheric or vacuum distillation of crude oil.
  • the process comprises a bubbling bed hydroconversion step (known as the H-Oil ® or LC-Fining process) followed by a light fraction separation step (boiling point below 300°C, preferably below 375°C), and the resulting heavy fraction is directly subjected to a deasphalting step to produce a deasphalted oil (DAO).
  • DAO can be hydrocracked or hydrotreated or fractionated.
  • the bubbling bed hydroconversion step is carried out at space velocities (VVH) of 0.1 h -1 to 10 h -1 .
  • the patent FR-3033797 of the applicant describes a process for the treatment of feedstocks derived from crude oil, or for the atmospheric or vacuum distillation of crude oil, of which at least 80% by weight has a boiling point of at least 300°C.
  • the process comprises a hydroconversion step (first hydroconversion), followed by separation of the light fraction (boiling point below 350°C) and the resulting heavy fraction is subjected to hydroconversion (second hydroconversion) separated from the first, the effluent obtained is then fractionated by distillation.
  • This hydroconversion process is carried out at a low overall VVH, preferably from 0.05 h -1 to 0.09 h -1 .
  • the advantage provided by the low overall VVH is significant purification which makes it possible to obtain a residue with a low content of asphaltenes and Conradson carbon, for a high level of conversion of the residue (>75%).
  • the stability of liquid effluents is improved.
  • the sediment content at the hydroconversion outlet is reduced, which induces better operability of the process.
  • the overall conversion of this process is limited by the unconverted heavy effluent.
  • 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
  • a process has now been sought with improved performance, in particular with a high fuel conversion (naphtha, kerosene, gas oil) to adapt to the market.
  • the applicant has demonstrated that a better solution is to add a deasphalting step to the process of the most recent art, which makes it possible to obtain a high level of yield and quality of the DAO, and to treat the DAO in at least one conversion step, the latter preferably operating at high VVH, and thus increasing the conversion while providing markedly improved operability and a substantial saving on the capital invested and a better return on the investment.
  • the present invention also makes it possible to further reduce the amount of resulting asphalt compared to processes with a higher overall VVH.
  • the method comprises a step f) of converting part or all of said deasphalted DAO fraction, optionally distilled.
  • Part or all of the DAO fraction is sent, preferably directly, to conversion stage f) 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, and the bubbling bed hydroconversion catalyst of step f) being used in the form of extrudates or beads.
  • the overall hourly space velocity for stages a) to c) is less than 0.1h -1 , the overall velocity being the liquid feed rate of stage a) of hydroconversion taken under standard temperature and pressure conditions , based on the total volume of the reactors of stages a) and c), and the hydroconversion catalyst of stage a) and the hydroconversion catalyst of stage c) are used in the form of extrudates or beads.
  • the DAO is distilled before step f) of conversion so as to separate a heavy fraction of which at least 80% by weight has a boiling point of at least 375° C., or of at least 400° C. , or at least 450° C. or at least 500° C., and preferably at least 540° C., and said heavy fraction sent in part or in whole to stage f) of conversion.
  • part or all 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 between 300 and 500°C, a VVH between 0.1 h -1 and 5h -1 , and a quantity of hydrogen 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 non-noble group VIII element and at least one group VIB element and comprising a support containing at least one zeolite.
  • hydrogen under an absolute pressure of between 5 MPa and 35 MPa, at a temperature advantageously between 300 and 500°C, a VVH between 0.1 h -1 and 5h -1 , and a quantity of hydrogen between 100 Nm 3 /m 3 and 1000 Nm 3 /m 3 (normal cubic meters (Nm 3 ) per cubic
  • part or all 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 deasphalted DAO fraction is subjected to bubbling bed hydroconversion, carried out in the presence of hydrogen, under an absolute pressure 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 charge), a VVH of between 0.1 h -1 and 10 h -1 and in the presence of a catalyst containing a support and at least one group VIII metal chosen from nickel and cobalt and at least one group VIB metal selected from molybdenum and tungsten.
  • step d) of separation the effluent from said second hydroconversion is separated into at least one light fraction and at least one heavy fraction of which at least 80% by weight has a boiling point of at least 375 °C, or at least 400°C, or at least 450°C or at least 500°C, and preferably at least 540°C.
  • steps a) and c) are carried out under an absolute pressure of between 5 MPa and 25 MPa and preferably between 6 MPa and 20 MPa, at a temperature of between 350° C. and 500° C. and at a preferably between 370°C and 430°C, and more preferably between 380°C and 430°C, with a quantity of hydrogen between 100 Nm 3 /m 3 and 2000 Nm 3 /m 3 and very preferably between 200 Nm 3 /m 3 and 1000 Nm 3 /m 3 , the hourly space velocity (HSV) being at least 0.05 h -1 , preferably between 0.05 h -1 and 0.09 h -1
  • crude oils or heavy hydrocarbon fractions resulting from the atmospheric and/or vacuum distillation of a crude oil. It can also be residue atmospheric and/or vacuum residues, and in particular atmospheric and/or vacuum residues from hydrotreating, hydrocracking and/or hydroconversion. It can also be vacuum distillates, cuts from a catalytic cracking unit such as FCC (fluidized bed catalytic cracking), a coking or visbreaking unit.
  • FCC fluidized bed catalytic cracking
  • these residues are vacuum residues.
  • these residues are fractions of which at least 80% by weight boils at a boiling point of at least 450°C or more, and most often at least 500°C or 540°C.
  • Aromatic cuts extracted from a lubricant production unit may also be suitable as fillers.
  • the charge can also be a residual fraction from the direct liquefaction of coal (an atmospheric residue and/or a vacuum residue from the H-Coal ® process, for example), a vacuum distillate from the direct liquefaction of coal (by example of the H-Coal ® process), coal pyrolysis residues or shale oils, or a residual fraction from the direct liquefaction of 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 the H-Coal ® process, for example
  • a vacuum distillate from the direct liquefaction of coal by example of the H-Coal ® process
  • coal pyrolysis residues or shale oils or a residual fraction from the direct liquefaction of lignocellulosic biomass alone or mixed with coal and / or a petroleum fraction.
  • the fillers mentioned above contain impurities, such as metals, sulphur, nitrogen, Conradson carbon and heptane insolubles, also called C 7 asphaltenes.
  • the metal contents are generally greater than 20 ppm by weight, most often greater than 100 ppm by weight.
  • the sulfur content is above 0.1%, often above 1% by weight or 2% by weight.
  • the content of C 7 -asphaltenes (asphaltenes insoluble in heptane according to standard NFT60-115) amounts to at least 0.1% by weight and is often greater than 3% by weight.
  • the Conradson carbon content is at least 3%, often at least 5% by weight.
  • 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 residue produced after pyrolysis under standard temperature and pressure conditions. These contents are expressed in % by weight relative to the total weight of the filler.
  • step a The first step of deep hydroconversion (step a))
  • the feed is treated in a hydroconversion step a) comprising at least one or more three-phase reactors arranged in series and/or in parallel.
  • reactors hydroconversion can, inter alia, be reactors of the fixed bed, moving bed, bubbling bed, and/or hybrid bed type, depending on the feed to be treated.
  • hybrid bed refers to a mixed bed of catalysts of very different particle size, simultaneously comprising at least one catalyst which is maintained in the reactor (typical operation of an ebullated bed) and at least one catalyst entrained (known as "slurry" according to Anglo-Saxon terminology) which enters the reactor with the load and which is entrained outside the reactor with the effluents (typical operation of an entrained bed).
  • the invention is particularly suitable for boiling bed reactors.
  • this step is advantageously implemented using the technology and under the conditions of the H-Oil ® process as described for example in the patents US-4521295 Where US-4495060 Where US-4457831 or in the article Aiche, March 19-23, 1995, Houston, Texas, paper number 46d, "Second generation ebullated bed technology".
  • Each reactor advantageously comprises a recirculation pump allowing the catalyst to be maintained in an ebullated bed by continuous recycling of at least a part of the liquid fraction advantageously drawn off at the top of the reactor and reinjected at the bottom of the reactor.
  • Step a) said feedstock is transformed under specific hydroconversion conditions.
  • Step a) is carried out under an absolute pressure between 2 MPa and 35 MPa, preferably between 5 MPa and 25 MPa and preferably between 6 MPa and 20 MPa, at a temperature between 300° C. and 550° C. and preferably comprised between 350°C and 500°C and more preferably comprised between 370°C and 430°C, and more preferably comprised between 380°C and 430°C.
  • the quantity of hydrogen, advantageously mixed with the charge is preferably between 50 Nm 3 /m 3 and 5000 Nm 3 /m 3 of liquid charge taken under standard temperature and pressure conditions, preferably between 100 Nm 3 /m 3 and 2000 Nm 3 /m 3 and very preferably between 200 Nm 3 /m 3 and 1000 Nm 3 /m 3 .
  • the hydroconversion catalyst used in step a) contains one or more elements from groups 4 to 12 of the periodic table of elements, which are 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 contains at least one non-noble group VIII metal chosen from nickel and cobalt and preferably nickel, and at least one group VIB metal chosen from molybdenum and tungsten and preferably the group VIB metal is molybdenum.
  • the hydroconversion catalyst of step a) is a catalyst comprising an alumina support and at least one metal from group VIII chosen from nickel and cobalt, preferably nickel, and at least one metal from group VIB chosen of molybdenum and tungsten, preferably the Group VIB metal is molybdenum.
  • the hydroconversion catalyst comprises nickel and molybdenum.
  • non-noble group VIII metal in particular nickel
  • metal oxide in particular NiO
  • metal content of group VIB in particular molybdenum
  • metal oxide in particular MoO 3
  • This catalyst is used in the form of extrudates or beads.
  • the balls have for example a diameter between 0.4 mm and 4.0 mm
  • the extrudates have for example a cylindrical shape with a diameter comprised between 0.5 mm and 4.0 mm and a length comprised between 1 mm 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, beads or other shapes therefore has an equivalent diameter of between 0.4 mm and 4.4 mm.
  • the deep hydroconversion step a) 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 entrained outside the reactor with the effluents.
  • the entrained catalyst also called slurry catalyst, is used in addition to the catalyst maintained in the ebullated bed reactor in the process according to the invention.
  • Said entrained catalyst has, as a difference with the catalyst maintained in the reactor, a particle size and a density adapted to its entrainment.
  • entrainment of the catalyst is meant its circulation in the three-phase reactor or reactors by the liquid flows, said catalyst circulating from the bottom upwards, with the charge, in the said three-phase reactor(s), and being withdrawn of said three-phase reactor(s) with the liquid effluent produced. Due to its small size, which can vary between a few nanometers up to a hundred micrometers (typically from 0.001 ⁇ m to 100 ⁇ m), the entrained catalyst is very well dispersed in the charge to be converted, thus greatly improving the reactions of hydrogenation and hydroconversion throughout a reactor, reducing coke formation and increasing the conversion of the heavy end of the feed. These entrained catalysts are well known to those skilled in the art.
  • the entrained catalyst can be formed and activated ex situ, outside the reactor under conditions suitable for activation, then injected with the charge.
  • the entrained catalyst can also be formed and activated in situ under the reaction conditions of one of the hydroconversion steps.
  • the entrained catalyst, or its precursor, is injected with the charge to be converted at the inlet of the reactor.
  • the catalyst passes through the reactor with the charges and the products being converted, then it is entrained with the reaction products out of the reactor.
  • Entrained catalysts exist either in powder form (patent US 4,303,634 ), which is the case of the supported entrained catalysts described below, either in the form of a so-called soluble catalyst (patent US 5,288,681 ).
  • the entrained catalyst is in the form of dispersed solid particles, colloids or molecular species dissolved in the charge, depending on the nature of the catalyst.
  • Such precursors and entrained catalysts that can be used in the process according to the invention are widely described in the literature.
  • the entrained catalysts used can be powders of heterogeneous solids (such as natural ores, iron sulphate, etc.), dispersed catalysts from water-soluble precursors, such as phosphomolybdic acid, molybdate of ammonium, or a mixture of Mo or Ni oxide with aqueous ammonia, or derived from precursors soluble in an organic phase.
  • the entrained catalysts used come from precursors soluble in an organic phase.
  • the precursors soluble in an organic phase are preferably chosen from the group of organometallic compounds consisting of naphthenates of Mo, of Co, of Fe, or of Ni, or multi-carbonyl compounds of these metals, for example 2-ethyl hexanoates of Mo or Ni, acetylacetonates of Mo or Ni, C 7 -C 12 fatty acid salts of Mo or W, etc.
  • the precursor is Mo naphthenate.
  • the entrained catalysts can be used in the presence of a surfactant to improve the dispersion of the metals, in particular when the catalyst is bimetallic.
  • entrained so-called oil-soluble catalysts are used, and the precursor is mixed with a carbonaceous filler (which may be part of the filler to be treated, an external filler, etc.), the mixture is optionally dried at least in part, then or simultaneously is sulfurized by adding a sulfur compound and heated. Preparations of these entrained catalysts are described in the prior art.
  • Additives can be added during the preparation of the entrained catalyst or to the entrained catalyst before it is injected into the reactor. These are, for example, a gas oil, an aromatic additive, solid particles whose size is preferably less than 1 mm, etc.
  • Preferred additives are mineral oxides such as alumina, silica, mixed Al/Si oxides, spent catalysts supported (for example, on alumina and/or silica) containing at least one group VIII element (such as Ni, Co) and/or at least one element of group VIB (such as Mo, W). Mention may be made, for example, of the catalysts described in the patent US 2008/177124 . Coke, optionally pretreated, can also be used. These additives are widely described in the literature.
  • 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 step or steps.
  • 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 entrained catalyst precursor(s) are premixed 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 of 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, among others.
  • 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.
  • Said supported entrained catalyst preferably comprises a support, such as silica, alumina, silica-alumina, titanium dioxide, clays, carbon, coal, coke, carbon black, lignite, or combinations of these structures, and very preferably alumina.
  • the active phase of said supported entrained catalyst contains one or more elements from groups 4 to 12 of the periodic table of elements, which may or may not be supported.
  • the active phase of said entrained catalyst advantageously contains at least one metal from group VIB chosen from molybdenum and tungsten, and preferably the metal from group VIB is molybdenum.
  • Said group VIB metal can be in combination with at least one non-noble group VIII metal chosen from nickel, cobalt, iron, ruthenium and preferably nickel.
  • the groups of chemical elements are given according to the CAS classification (CRC Handbook of Chemistry and Physics, publisher CRC press, editor-in-chief DR Lide, 81st edition, 2000-2001).
  • metals in group VIII according to the CAS classification correspond to metals in columns 8, 9 and 10 according to the new IUPAC classification.
  • the content of non-noble group VIII metal, in particular nickel is advantageously between 0.5% and 10% expressed by weight of metal oxide (in particular NiO), and preferably between 1% to 6% by weight.
  • the metal content of group VIB, in particular 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% weight.
  • the metal contents are expressed as weight percentage of metal oxide relative to the weight of the supported catalyst entrained.
  • the supported entrained catalyst may also contain at least one doping element chosen from phosphorus, boron and the halogens (group VIIA or group 17 of the new notation of the periodic table of the elements), preferably phosphorus.
  • each reactor of step a) of hydroconversion can use a different catalyst adapted to the feed which is sent to this reactor.
  • each reactor of stage a) can contain one or more catalysts suitable for operation in an ebullated bed, and optionally one or more additional entrained catalyst(s).
  • the used hydroconversion catalyst can be partly replaced by fresh catalyst by drawing off, the latter being preferably drawn off at the bottom of the reactor, and the fresh catalyst being introduced into the reactor.
  • the fresh catalyst can be replaced in whole or in part by spent catalyst and/or regenerated catalyst (without coke) and/or rejuvenated catalyst (regenerated catalyst added with a compound increasing the activity of the catalyst) and/or catalyst reactivated via the extraction of poisons and inhibitors such as deposited metals from hydrodemetallization reactions and elimination of the coke formed.
  • the method preferably operates with step b).
  • At least part, and preferably all of the effluent from stage a) of hydroconversion can undergo one or more separation stages.
  • This separation step is carried out with the objective of separating from the effluent at least one light fraction (known as the first light fraction) and thus obtaining at least one heavy liquid fraction of which at least 80% by weight has a boiling point of at least 250°C, and preferably at least 300°C.
  • the light fraction can then be sent at least in part to a fractionation section where it is then advantageously separated from the light gases (H 2 and C 1 -C 4 ), for example by passing through a flash drum.
  • the gaseous hydrogen is recovered then is then advantageously recycled at the inlet to step a) of deep hydroconversion or sent to step c) of deep hydroconversion and/or to other units of the refinery.
  • the light liquid fraction separated from the light gases can then advantageously be sent to stage d) of fractionation.
  • This light liquid fraction thus separated contains dissolved light gases, naphtha (fraction boiling at a temperature below 150°C), kerosene (fraction boiling between 150°C and 250°C) and at least part of the diesel fuel boiling between 250°C and 375°C.
  • the heavy liquid fraction from step b) contains the compounds boiling at 250°C, preferably at 300°C, or more, and in particular those boiling at 375°C and down to less than 540°C (distillate vacuum) and those boiling at a temperature of 540°C and above which correspond to the vacuum residue (which is the unconverted fraction). It can therefore contain part of the gas oil fraction, that is to say compounds boiling between 250°C and 375°C.
  • This heavy liquid fraction is sent in whole or in part to stage c) of hydroconversion.
  • step b) of separation is carried out by one or more flash balloons in series, and preferably by a single flash balloon.
  • the flash drum is operated at a pressure and a temperature close to the operating conditions of the last reactor of step a) of hydroconversion.
  • the separation step is carried out by a sequence of several flash drums, operating at operating conditions different from those of the last reactor of step a) of hydroconversion and making it possible to obtain several fractions light liquids. These can then be sent in whole or in part to a splitting section.
  • the separation step is carried out by one or more steam and/or hydrogen stripping (stripping) columns.
  • the effluent from stage a) of hydroconversion will be separated into a light fraction and a heavy liquid fraction.
  • the separation step is carried out by an atmospheric distillation column alone or followed by a vacuum distillation column.
  • the separation step can also be a combination of these different implementations.
  • the heavy liquid fraction before being sent to stage c) of hydroconversion according to the invention, can be subjected to a stage of separation of compounds with a boiling point of 540° C. or less. At least 80% by weight of the heavy fraction which is obtained has a boiling point of at least 540°C.
  • This separation can be carried out by stripping with steam and/or with hydrogen, using one or more stripping columns.
  • stage a) or the heavy fraction from separation stage b) is subjected to deep hydroconversion in stage c). Said effluent or said fractions may or may not be recycled to stage a). Steps a) and c) are different steps performed in separate areas.
  • step c) The operating conditions of step c) are identical to or different from those of step a).
  • the global hourly space velocity (WH), that is to say the liquid feed rate of stage a) of hydroconversion taken under standard conditions of temperature and pressure, relative to the volume total of the reactors of stages a) and c), is less than 0.1 h -1 , generally at least 0.05 h -1 , preferably between 0.05 h -1 and 0.09 h -1 .
  • stage d) of fractionation The effluent resulting from stage c) of hydroconversion is then subjected, in whole or in part, to a stage d) of fractionation.
  • This fractionation can be carried out by one or more flash drums in series, preferably by a sequence of at least two successive flash drums, preferably by one or more steam and/or hydrogen stripping columns , more preferably by an atmospheric distillation column, more preferably by an atmospheric distillation column and a vacuum column on the atmospheric residue, even more preferably by one or more flash drums, an atmospheric distillation column and a vacuum column on the atmospheric residue.
  • This fractionation can also be carried out by a combination of the various separation means described above.
  • the fractionation step is carried out with the aim of separating the light gases and the recoverable distillates (gasoline, diesel) and so as to obtain at least one heavy liquid fraction of which at least 80% by weight boils at at least 300°C, or at least 350°C, advantageously at least 375°C, or at least 400°C, or at least 450°C or at least 500°C and preferably a residue fraction of which 80% is obtained weight boils at at least 540°C or more.
  • a vacuum residue is separated (by atmospheric distillation then vacuum distillation of the atmospheric residue) having an initial boiling point of 540°C.
  • step d Said heavy liquid fraction obtained in step d), and in said residue fraction, then undergoes, in accordance with the process according to the invention, a step e) of deasphalting, to obtain a deasphalted hydrocarbon fraction called DAO and asphalt.
  • the deasphalting is generally carried out at a temperature between 60° C. and 250° C. with at least one hydrocarbon solvent having from 3 to 7 carbon atoms, the solvent being chosen from the group formed by butane, pentane or hexane , as well as mixtures thereof, optionally containing at least one additive.
  • the solvent/feed (volume/volume) ratios during deasphalting are generally between 4/1 and 9/1, often between 4/1 and 8/1.
  • the solvents which can be used and the additives are widely described. It is also possible and advantageous to carry out the recovery of the solvent according to the optical-critical method, 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.
  • This deasphalting can be done in one or more mixer-settlers or in one or more extraction columns.
  • the deasphalting unit produces a deasphalted DAO hydrocarbon cut (also called deasphalted oil or deasphalting raffinate) practically free of C 7 asphaltenes and a residual asphalt concentrating most of the impurities of the residue and which is withdrawn.
  • a deasphalted DAO hydrocarbon cut also called deasphalted oil or deasphalting raffinate
  • the DAO yield is generally between 40% and 90% by weight depending on the quality of the heavy liquid fraction sent, the operating conditions and the solvent used.
  • the deasphalting conditions are adapted to the quality of the DAO to be obtained and to the load entering the deasphalting.
  • the DAO deasphalted hydrocarbon cut obtained advantageously has a C 7 asphaltene content of less than 0.5% by weight, preferably less than 0.1% by weight, and better still less than 0.08% or 0.07% by weight, relative to the total weight of said cut.
  • all or preferably part of said deasphalted DAO fraction is recycled to step a) and/or to step c).
  • the DAO fraction is sent in whole or in part to an additional conversion step f).
  • the DAO is sent directly to the conversion step.
  • the entire DAO fraction is sent directly to the stage of conversion, that is to say that it does not undergo any treatment except possibly one or more fractionation steps.
  • This step makes it possible to bring the conversion of the process to a very high level (compared to the 540°C+ cut), and most often to more than 90%.
  • the conversion processes targeted in this stage are fixed bed hydrocracking, FCC fluidized bed catalytic cracking, bubbling bed hydroconversion (H-Oil DC), these conversion processes can be preceded by hydrotreating.
  • said deasphalted DAO hydrocarbon cut can be subjected to atmospheric distillation, optionally followed by vacuum distillation, in particular when step c) does not include distillation.
  • the recoverable product cuts obtained are the gasoline cut (150°C-), one or more middle distillate cut(s) (150-375°C) and one or more fraction(s) heavier at point of boiling point of 375°C or more.
  • This/these heavier fraction(s) is preferably sent to stage f) of conversion.
  • the deasphalted DAO hydrocarbon cut is advantageously distilled as a mixture with at least part and preferably all of the light liquid fraction from step b.
  • said mixture can be sent to step f) conversion without prior fractionation (distillation).
  • the DAO may also have been mixed with a feed external to the process, such as, for example, vacuum distillate cuts, atmospheric residue or vacuum residue from the primary fractionation (of the crude) from the refinery.
  • the process preferably operates without distillation.
  • the DAO fraction, in part or in whole, is then sent as in step f).
  • the conversion step may be fixed bed hydrocracking. It can advantageously take place in one or more reactors or in a single reactor comprising one or more catalytic beds.
  • Fixed-bed hydrocracking uses acid catalysis in the presence of hydrogen.
  • At least one fixed bed of hydrotreating catalyst is generally used, followed by at least one fixed bed of a hydrocracking catalyst.
  • These catalysts are well known to those skilled in the art.
  • the catalysts contain at least one non-noble group VIII element (Ni and/or Co) and at least one group VIB element (Mo and/or W).
  • the content of group VIII elements is advantageously between 1% and 10% by weight of oxides relative to the total catalyst mass, preferably between 1.5% and 9% by weight and very preferably between 2% and 8 % weight.
  • the contents of the elements of group VIB are advantageously between 5% and 40% by weight of oxides relative to the total mass of the catalyst, preferably between 8% and 37% by weight and very preferably between 10% and 35% by weight. .
  • the contents are expressed relative to the total weight of the catalyst.
  • the support for hydrotreating catalysts is generally alumina; that of the hydrocracking catalysts contains one or more zeolites (usually Y or ⁇ zeolites) generally mixed with alumina and/or silica-alumina.
  • zeolites usually Y or ⁇ zeolites
  • the weight contents of zeolite are generally less than 80% by weight.
  • the hydrotreating and hydrocracking catalysts can also contain at least one organic additive.
  • the operation is preferably carried out under an absolute pressure of between 5 MPa and 35 MPa and preferably between 10 MPa and 20 MPa, at a temperature advantageously between 300° C. and 500° C. and preferably between 350° C. and 450° C. .
  • the VVH and the partial pressure of hydrogen are chosen according to the characteristics of the feed to be treated and the desired conversion.
  • the WH is between 0.1 h -1 and 5 h -1 and more preferably between 0.15 h -1 and 2 h -1 .
  • the quantity of hydrogen, advantageously mixed with the charge is preferably between 100 Nm 3 /m 3 and 1000 Nm 3 /m 3 of liquid charge and preferably between 500 Nm 3 /m 3 and 3000 Nm 3 /m 3 .
  • the bubbling bed hydroconversion step treating the DAO (H-Oil ® DC) fraction can advantageously be carried out under an absolute pressure of between 2 MPa and 35 MPa, preferably between 5 MPa and 25 MPa and preferably between 6 MPa and 20 MPa, at a temperature between 300°C and 550°C and preferably between 350°C and 500°C and preferably between 380°C and 470°C, and more preferably between 400°C and 450°C.
  • the quantity of hydrogen, advantageously mixed with the charge is preferably between 50 Nm 3 /m 3 and 5000 Nm 3 /m 3 of liquid charge taken under standard temperature and pressure conditions, preferably between 100 Nm 3 /m 3 and 2000 Nm 3 /m 3 and very preferably between 200 Nm 3 /m 3 and 1000 Nm 3 /m 3 .
  • the VVH of this step is between 0.1 h -1 and 10 h -1 and more preferably between 0.15 h and 5 h.
  • the hydroconversion catalyst used in an ebullated bed contains one or more elements from groups 4 to 12 of the periodic table of elements, which are 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 contains at least one metal from group VIII chosen from nickel and cobalt and preferably nickel, and at least one metal from group VIB chosen from molybdenum and tungsten and preferably the metal from group VIB is molybdenum .
  • the hydroconversion catalyst is a catalyst comprising an alumina support and at least one group VIII metal chosen from nickel and cobalt, preferably nickel, and at least one group VIB metal chosen from molybdenum and tungsten. preferably, the Group VIB metal is molybdenum.
  • the hydroconversion catalyst comprises nickel and molybdenum.
  • the nickel content is advantageously between 0.5% by weight to 10% by weight expressed by weight of nickel oxide (NiO) and preferably between 1% by weight and 6% by weight
  • the molybdenum content is advantageously between 1 % by weight and 30% by weight expressed by weight of molybdenum trioxide (MoO 3 ) and preferably between 4% and 20% by weight.
  • the contents are expressed relative to the total weight of the catalyst.
  • This catalyst is advantageously used in the form of extrudates or beads.
  • the extrudates have for example a diameter comprised between 0.5 mm and 2.0 mm and a length comprised between 1 mm and 5 mm. These catalysts are well known to those skilled in the art.
  • the used hydroconversion catalyst can be partly replaced by fresh catalyst by drawing off, the latter being preferably drawn off at the bottom of the reactor, and the fresh catalyst being introduced into the reactor.
  • the fresh catalyst can be replaced in whole or in part by used catalyst and/or regenerated catalyst (without coke) and/or rejuvenated catalyst (regenerated catalyst added with a compound increasing the activity of the catalyst) and/or catalyst reactivated via the extraction of poisons and inhibitors such as the deposited metals resulting from the reactions of hydrodemetallization and elimination of the coke formed.
  • the effluent resulting from step f) conversion is then generally distilled so as to recover the recoverable gasoline and gas oil cuts.
  • the residual unconverted fraction can be recycled to one of the process steps.
  • step f) of conversion can be carried out through a fluidized bed catalytic cracking unit.
  • the DAO can be processed in coprocessing with one or more heavy loads such as VGO, HDT VGO, residue or alone.
  • the fluidized bed catalytic cracking unit can comprise a single reactor treating both the heavy load and the DAO or only the DAO, or two separate reactors, one treating the heavy load, the other the DAO. Additionally, each of the reactors can be either upflow or downflow. Most often, the two reactors will have the same flow mode.
  • the spent catalyst streams from the two FCC reactors are separated from the cracking effluents by any gas-solid separation system known to those skilled in the art and regenerated in a common regeneration zone.
  • This separation unit generally includes a primary separation of effluents allowing, among other things, the production of recoverable cuts such as gasoline, middle distillate and heavy distillate cuts.
  • recoverable cuts such as gasoline, middle distillate and heavy distillate cuts.
  • the residual unconverted fraction can be recycled to one of the process steps.
  • the catalyst for the fluidized bed catalytic cracking step typically consists of particles with an average diameter generally between 40 micrometers and 140 micrometers, and most often between 50 micrometers and 120 micrometers.
  • the catalytic cracking catalyst contains at least one appropriate matrix such as alumina, silica or silica-alumina with or without the presence of a type Y zeolite dispersed in this matrix.
  • the catalyst may further comprise at least one zeolite having a shape selectivity of one of the following structural types: MEL (for example ZSM-11), MFI (for example ZSM-5), NES, EUO, FER, CHA (for example SAPO-34), MFS, MWW. It may also include one of the following zeolites: NU-85, NU-86, NU-88 and IM-5, which also exhibit shape selectivity.
  • the proportion of zeolite exhibiting shape selectivity relative to the total amount of zeolite can vary depending on the fillers used and the structure of the desired products. Often, 0.1% to 60%, preferably 0.1% to 40%, and in particular 0.1% to 30% by weight of zeolite exhibiting shape selectivity are used.
  • the zeolite(s) can be dispersed in a matrix based on silica, alumina or silica alumina, the proportion of zeolite (all zeolites combined) relative to the weight of the catalyst often being between 0.7% and 80% by weight , preferably between 1% and 50% by weight, and more preferably between 5% and 40% by weight.
  • zeolites In the case where several zeolites are used, they can be incorporated into a single matrix or into several different matrices.
  • the content of zeolite exhibiting shape selectivity in the total inventory is less than 30% by weight.
  • the catalyst used in the catalytic cracking reactor may consist of an ultra-stable Y-type zeolite dispersed in an alumina, silica or silica-alumina matrix, to which an additive based on ZSM5 zeolite, the amount in crystals of ZSM5 in the total inventory being less than 30% by weight.
  • the figure 1 illustrates the invention.
  • Step a) of deep hydroconversion It comprises a deep hydroconversion section A in which step a) of deep hydroconversion is carried out.
  • Charge 1 is converted in the presence of hydrogen 2 and the resulting effluent 3 is separated (step b, optionally followed by step b') in separation section B.
  • a light fraction 4 and a heavy fraction are obtained 5.
  • the latter is sent to the deep hydroconversion section C where it undergoes step c) of deep hydroconversion in the presence of hydrogen 6.
  • From the resulting effluent 7 is separated a light fraction 8 and a heavy fraction 9 which is directed to the deasphalting section E where the deasphalting step e) is carried out using a solvent 12.
  • the deasphalted oil DAO 10 is sent to a conversion section F where the conversion step f) takes place and the asphalt 11 is recovered.
  • the effluent 13 from step f) conversion is then generally sent to a separation step so as to recover the recoverable cuts, for example gasoline and diesel.
  • Examples 1 and 2 are compared at iso-conversion (75% of 540° C.+ in 540° C-) and examples 3 and 4 are made at iso-temperature.
  • Examples 5 and 6 are compared at iso-conversion (75% of 540° C.+ in 540° C.-) and examples 7 and 8 are carried out at iso-temperature. Examples 1 to 5 and 7 do not fall within the scope of the invention, and are given by way of illustration.
  • the heavy load is a vacuum residue (RSV) originating from an Ural crude oil, the main characteristics of which are presented in table 1 below.
  • This RSV heavy load is the same fresh load for the different examples.
  • Table 1 composition of the process feed Stage load AT Charged RSV Urals Density 1,000 Content 540°C+ %weight 77.9 Viscosity at 100°C cSt 880 Carbon Conradson %weight 17.0 C 7 Asphaltenes %weight 6.8 Nickel + Vanadium ppm 233 Nitrogen ppm 6010 Sulfur %weight 2,715
  • two ebullated bed reactors (first and second deep hydroconversion section) are arranged in series, operated at high hourly space velocity (WH) and high temperature with an interstage separation section and a downstream deasphalting process.
  • WH hourly space velocity
  • the fresh feed from Table 1 is sent in its entirety to the first bubbling bed hydroconversion section A, in the presence of hydrogen, which comprises a three-phase reactor, a NiMo/alumina hydroconversion catalyst having a NiO content of 4% by weight and a MoO 3 content of 9% by weight, the percentages being expressed relative to the total mass of the catalyst.
  • the section operates as an updraft bubbling bed of liquid and gas.
  • Table 2 operating conditions of hydroconversion section A Section AT P total MPa 16 Temperature °C 431 Hydrogen quantity Nm 3 /m 3 500
  • the liquid effluent from section A is then sent to a separation section B composed of a single gas/liquid separator operating at the pressure and temperature of the reactor of the first hydroconversion section A.
  • a so-called light and a so-called heavy fraction are thus separated.
  • the so-called light fraction is mainly composed of molecules with a boiling point below 350°C and the so-called heavy fraction is mainly composed of molecules of hydrocarbons boiling at a temperature of at least 350°C.
  • the heavy fraction from separation section B is sent alone and in its entirety to a second hydroconversion section C in the presence of hydrogen.
  • Said section comprises a three-phase reactor containing a NiMo/alumina hydroconversion catalyst having a NiO content of 4% by weight and a MoO 3 content of 9% by weight, the percentages being expressed relative to the total mass of the catalyst.
  • the section operates as an updraft bubbling bed of liquid and gas.
  • Table 4 operating conditions of hydroconversion section C Section VS P total MPa 15.6 Temperature °C 431 Hydrogen quantity Nm 3 /m 3 300
  • the effluent from the hydroconversion section C is sent to a fractionation section D consisting of atmospheric distillation followed by vacuum distillation from which an unconverted heavy vacuum residue fraction (RSV) boiling at a temperature of at least 540° C., the yields of which with respect to the fresh load and the quality are given in Table 5 below.
  • RSV unconverted heavy vacuum residue fraction
  • Table 5 Yield and quality of RSV from fractionation section D Fraction Unconverted vacuum residue Efficiency relative to fresh load (A) %weight 19.42 Content 540°C+ %weight 100 Density g/ cm3 1.0157 Carbon Conradson %weight 22.2 Nickel + Vanadium ppm 91.4 Nitrogen ppm 8870 Sulfur %weight 1,028 Saturated %weight 15.5 Aromatics %weight 36.2 Resins %weight 38.9 C 7 Asphaltenes %weight 9.4
  • Table 7 Yields and qualities of effluents from deasphalting section E Fraction CAD Asphalt Yield relative to unconverted RSV (D) %weight 49.9 50.1 Efficiency relative to fresh load (A) %weight 9.7 9.7 Density g/ cm3 0.9474 1.0942 Carbon Conradson %weight 7.42 36.9 C 7 Asphaltenes %weight 0.09 18.7 Nickel + Vanadium ppm ⁇ 2 181 Nitrogen ppm 4520 13210 Sulfur %weight 0.836 1,220
  • the fresh feed from Table 1 is sent in its entirety to the first bubbling bed hydroconversion section A, in the presence of hydrogen, which comprises a three-phase reactor containing a NiMo/alumina hydroconversion catalyst having a NiO content of 4% by weight and a MoO 3 content of 9% by weight, the percentages being expressed relative to the total mass of the catalyst.
  • the section operates as an updraft bubbling bed of liquid and gas.
  • Table 8 operating conditions of hydroconversion section A Section AT P total MPa 16 Temperature °C 411 Hydrogen quantity Nm 3 /m 3 600
  • the liquid effluent from section A is then sent to a separation section B composed of a single gas/liquid separator operating at the pressure and temperature of the reactors of the first hydroconversion section A.
  • a so-called light and a so-called heavy fraction are thus separated.
  • the so-called light fraction is mainly composed of molecules with a boiling point below 350°C and the so-called heavy fraction is mainly composed of molecules of hydrocarbons boiling at a temperature of at least 350°C.
  • the heavy fraction from the separation section B is sent alone and in its entirety to a second hydroconversion section C in an ebullated bed, in the presence of hydrogen.
  • Said section comprises a three-phase reactor containing a NiMo/alumina hydroconversion catalyst having a NiO content of 4% by weight and a MoO 3 content of 9% by weight, the percentages being expressed relative to the total mass of the catalyst.
  • the section operates as an updraft bubbling bed of liquid and gas.
  • Table 9 operating conditions of hydroconversion section C Section VS P total MPa 15.6 Temperature °C 411 Hydrogen quantity Nm 3 /m 3 250
  • the effluent from the hydroconversion section C is sent to a fractionation section D consisting of atmospheric distillation followed by vacuum distillation from which an unconverted heavy vacuum residue fraction (RSV) boiling at a temperature of at least 540° C., the yields of which with respect to the fresh load and the quality are given in table 10 below.
  • RSV unconverted heavy vacuum residue fraction
  • Table 10 Yield and quality of RSV from fractionation section D Fraction Unconverted vacuum residue Efficiency relative to fresh load (A) %weight 19.33 Content at 540°C+ %weight 100 Density g/ cm3 0.9924 Carbon Conradson %weight 16.4 Nickel + Vanadium ppm 21.7 Nitrogen ppm 7120 Sulfur %weight 0.687 Saturated %weight 19.0 Aromatics %weight 41.6 Resins %weight 34.9 C 7 Asphaltenes %weight 4.6
  • Table 12 Yields and qualities of effluents from deasphalting section E Fraction CAD Asphalt Yield relative to unconverted RSV (D) %weight 68.2 31.8 Efficiency compared to fresh load (A) %weight 13.2 6.1 Density g/ cm3 0.9495 1.0988 Carbon Conradson %weight 8.1 34.1 C 7 Asphaltenes %weight 0.07 14.2 Nickel + Vanadium ppm ⁇ 2 67.4 Nitrogen ppm 4590 12530 Sulfur %weight 0.610 0.849
  • one operates with two ebullated bed reactors arranged in series (first and second deep hydroconversions), operated at high hourly space velocity (WH) and at moderate temperature (420°C) with an interstage separation section and a downstream deasphalting process.
  • WH hourly space velocity
  • 420°C moderate temperature
  • the three-phase reactor contains a NiMo/alumina hydroconversion catalyst having a NiO content of 4% by weight and a MoO 3 content of 9% by weight, the percentages being expressed relative to the total mass of the catalyst.
  • the section operates as an updraft bubbling bed of liquid and gas.
  • Table 13 operating conditions of hydroconversion section A Section AT P total MPa 16 Temperature °C 420 Hydrogen quantity Nm 3 /m 3 350
  • the liquid effluent from section A is then sent to a separation section B composed of a single gas/liquid separator operating at the pressure and temperature of the reactors of the first hydroconversion section A.
  • a so-called light and a so-called heavy fraction are thus separated.
  • the so-called light fraction is mainly composed of molecules with a boiling point below 350°C and the so-called heavy fraction is mainly composed of molecules of hydrocarbons boiling at a temperature of at least 350°C.
  • the heavy fraction from the separation section B is sent alone and in its entirety to a second hydroconversion section C in an ebullated bed, in the presence of hydrogen.
  • Said section comprises a three-phase reactor containing a NiMo/alumina hydroconversion catalyst having a NiO content of 4% by weight and a MoO 3 content of 9% by weight, the percentages being expressed relative to the total mass of the catalyst.
  • the section operates as an updraft bubbling bed of liquid and gas.
  • Table 14 operating conditions of hydroconversion section C Section VS P total MPa 15.6 Temperature °C 420 Hydrogen quantity Nm 3 /m 3 200
  • the effluent from the hydroconversion section C is sent to a fractionation section D consisting of atmospheric distillation followed by vacuum distillation from which an unconverted heavy vacuum residue fraction (RSV) boiling at a temperature of at least 540° C., the yields of which with respect to the fresh load and the quality are given in table 15 below.
  • RSV unconverted heavy vacuum residue fraction
  • Table 15 Yield and quality of RSV from fractionation section D Fraction Unconverted vacuum residue Efficiency relative to fresh load (A) %weight 31.75 Content 540°C+ %weight 100 Density g/ cm3 1.0098 Carbon Conradson %weight 20.7 Nickel + Vanadium ppm 98.0 Nitrogen ppm 8230 Sulfur %weight 1,246 Saturated %weight 16.4 Aromatics %weight 37.5 Resins %weight 37.9 C7 Asphaltenes %weight 8.2
  • Table 17 Yields and qualities of effluents from deasphalting section E Fraction CAD Asphalt Yield versus unconverted RSV %weight 54.1 45.9 Efficiency compared to fresh load (A) %weight 17.2 14.6 Density g/ cm3 0.9478 1.0943 Carbon Conradson %weight 7.53 36.3 C 7 Asphaltenes %weight 0.08 17.8 Nickel + Vanadium ppm ⁇ 2 212.4 Nitrogen ppm 4420 12730 Sulfur %weight 1,036 1,493
  • All of the fresh feed from Table 1 is sent to a bubbling bed hydroconversion section A, in the presence of hydrogen.
  • Said section comprises a three-phase reactor containing a NiMo/alumina hydroconversion catalyst having a NiO content of 4% by weight and a MoO 3 content of 9% by weight, the percentages being expressed relative to the total mass of the catalyst.
  • the section operates as an updraft bubbling bed of liquid and gas.
  • Table 18 operating conditions of hydroconversion section A Section AT P total MPa 16 Temperature °C 420 Hydrogen quantity Nm 3 /m 3 700
  • the liquid effluent from section A is then sent to a separation section B composed of a single gas/liquid separator operating at the pressure and temperature of the reactors of the first hydroconversion section A.
  • a so-called light and a so-called heavy fraction are thus separated.
  • the so-called light fraction is mainly composed of molecules with a boiling point below 350°C and the so-called heavy fraction is composed of molecules of hydrocarbons boiling at a temperature of at least 350°C.
  • the heavy fraction) from the separation section B is sent alone and in its entirety to a second hydroconversion section C in an ebullated bed, in the presence of hydrogen.
  • Said section comprises a three-phase reactor containing a NiMo/alumina hydroconversion catalyst having a NiO content of 4% by weight and a MoO 3 content of 9% by weight, the percentages being expressed relative to the total mass of the catalyst.
  • the section operates as an updraft bubbling bed of liquid and gas.
  • Table 19 operating conditions of hydroconversion section C Section VS P total MPa 15.6 Temperature °C 420 Hydrogen quantity Nm 3 /m 3 350
  • the effluent from the hydroconversion section C is sent to a fractionation section D consisting of atmospheric distillation followed by vacuum distillation from which an unconverted heavy vacuum residue fraction (RSV) boiling at a temperature of at least 540° C., the yields of which with respect to the fresh load and the quality are given in table 20 below.
  • RSV unconverted heavy vacuum residue fraction
  • Table 20 Yield and quality of RSV from fractionation section D Fraction Unconverted vacuum residue Efficiency relative to fresh load (A) %weight 10.8 Content at 540°C+ %weight 100 Density g/ cm3 0.9952 Carbon Conradson %weight 17.05 Nickel + Vanadium ppm 19.4 Nitrogen ppm 7350 Sulfur %weight 0.582 Saturated %weight 18.5 Aromatics %weight 41.4 Resins %weight 35.4 C7 Asphaltenes %weight 4.8
  • Table 22 Yields and qualities of effluents from deasphalting section E Fraction CAD Asphalt Yield versus unconverted RSV %weight 66.8 33.2 Efficiency compared to fresh load (A) %weight 7.2 3.6 Density g/ cm3 0.9505 1.0995 Carbon Conradson %weight 8.3 34.6 C 7 Asphaltenes %weight 0.07 14.2 Nickel + Vanadium ppm ⁇ 2 57.9 Nitrogen ppm 4670 12750 Sulfur %weight 0.515 0.716
  • the conversion of the heavy cut 540°C+ is 86.1% by weight before the deasphalting step, is greater by 26.9% by weight compared to Example 3 at the same temperature level.
  • the amount of unconverted RSV recovered in Example 4 is thus approximately 3 times lower.
  • the unconverted RSV of example 4 contains lower contents of Conradson carbon and C 7 asphaltenes in comparison with example 3, which makes it possible to recover a greater quantity of DAO from the unconverted RSV (66.8% recoverable weight in this example against 54.1% weight in example 3).
  • this scheme according to the invention is accompanied by a lower generation of asphalt corresponding to only 3.6% by weight relative to the fresh starting load. If all of the DAO is converted in a hydrocracking unit, a very high conversion of the starting 540° C.+ heavy cut of 95.4% by weight can thus be obtained thanks to this scheme according to the invention.
  • two ebullated bed reactors (first and second deep hydroconversion section) are arranged in series, operated at high hourly space velocity (WH) and high temperature with an interstage separation section and a deasphalting process in downstream.
  • WH hourly space velocity
  • the CAD cut is then converted into an FCC unit.
  • the fresh feed from Table 1 is sent in its entirety to the first bubbling bed hydroconversion section A, in the presence of hydrogen, which comprises a three-phase reactor, a NiMo/alumina hydroconversion catalyst having a NiO content of 4% by weight and a MoO 3 content of 9% by weight, the percentages being expressed relative to the total mass of the catalyst.
  • the section operates as an updraft bubbling bed of liquid and gas.
  • the conditions applied in the hydroconversion section A are presented in table 2. These operating conditions make it possible to obtain a liquid effluent with a reduced content of Conradson carbon, metals and sulphur.
  • the liquid effluent from section A is then sent to a separation section B composed of a single gas/liquid separator operating at the pressure and temperature of the reactor of the first hydroconversion section A.
  • a so-called light and a so-called heavy fraction are thus separated.
  • the so-called light fraction is mainly composed of molecules with a boiling point below 350°C and the so-called heavy fraction is mainly composed of molecules of hydrocarbons boiling at a temperature of at least 350°C.
  • the heavy fraction from separation section B is sent alone and in its entirety to a second hydroconversion section C in the presence of hydrogen.
  • Said section comprises a three-phase reactor containing a NiMo/alumina hydroconversion catalyst having a NiO content of 4% by weight and a MoO 3 content of 9% by weight, the percentages being expressed relative to the total mass of the catalyst.
  • the section operates as an updraft bubbling bed of liquid and gas.
  • the conditions applied in the hydroconversion section C are shown in Table 4.
  • the effluent from the hydroconversion section C is sent to a fractionation section D consisting of atmospheric distillation followed by vacuum distillation from which an unconverted heavy vacuum residue fraction (RSV) boiling at a temperature of at least 540°C, the yields of which with respect to the fresh load and the quality are given in table 5.
  • RSV unconverted heavy vacuum residue fraction
  • the vacuum residue from section D is sent to deasphalting section E.
  • the conditions applied in the deasphalting unit are described in Table 6.
  • a DAO fraction and a fraction known as “asphalt” which is difficult to recover.
  • the yields and qualities of these two products are given in Table 7.
  • the DAO fraction from the deasphalting 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 vacuum residue (RSV) originating from an Ural crude whose characteristics are presented in table 1).
  • the liquid fraction from the FCC unit still contains a small non-converted 540°C+ fraction, the yield of which is 1.1% by weight relative to the FCC charge, as indicated in Table 23.
  • the conversion of the DAO is not total here.
  • Table 23 Yields and qualities of effluents from the FCC F unit Unity FCC Gasoline yield (C5 - 220°C) %weight 40.9 Diesel efficiency (220 - 360°C) %weight 14.2 Yield Distillate Under Vacuum (360 - 540°C) %weight 14.2 Vacuum Residue Yield (540°C+) %weight 1.1
  • VVH 0.089h -1
  • 411/411°C low temperature
  • the CAD cut is then converted into an FCC unit.
  • the fresh feed from Table 1 is sent in its entirety to the first bubbling bed hydroconversion section A, in the presence of hydrogen, which comprises a three-phase reactor containing a NiMo/alumina hydroconversion catalyst having a NiO content of 4% by weight and a MoO 3 content of 9% by weight, the percentages being expressed relative to the total mass of the catalyst.
  • the section operates as an updraft bubbling bed of liquid and gas.
  • the conditions applied in the hydroconversion section A are shown in Table 8.
  • the liquid effluent from section A is then sent to a separation section B composed of a single gas/liquid separator operating at the pressure and temperature of the reactors of the first hydroconversion section A.
  • a so-called light and a so-called heavy fraction are thus separated.
  • the so-called light fraction is mainly composed of molecules with a boiling point below 350°C and the so-called heavy fraction is mainly composed of molecules of hydrocarbons boiling at a temperature of at least 350°C.
  • the heavy fraction from the separation section B is sent alone and in its entirety to a second hydroconversion section C in an ebullated bed, in the presence of hydrogen.
  • Said section comprises a three-phase reactor containing a NiMo/alumina hydroconversion catalyst having a NiO content of 4% by weight and a MoO 3 content of 9% by weight, the percentages being expressed relative to the total mass of the catalyst.
  • the section operates as an updraft bubbling bed of liquid and gas. Those operating conditions make it possible to obtain a liquid effluent with a reduced content of Conradson carbon, metals and sulphur.
  • the conditions applied in the hydroconversion section C are shown in Table 9.
  • the effluent from the hydroconversion section C is sent to a fractionation section D consisting of atmospheric distillation followed by vacuum distillation from which an unconverted heavy vacuum residue fraction (RSV) boiling at a temperature of at least 540°C, the yields of which with respect to the fresh load and the quality are given in table 10.
  • RSV unconverted heavy vacuum residue fraction
  • the vacuum residue from section D is sent to the deasphalting section E.
  • a DAO fraction and a fraction called "asphalt" difficult to recover.
  • the yields and qualities of these two products are given in Table 12.
  • the DAO fraction from the deasphalting 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 vacuum residue (RSV) originating from an Ural crude whose characteristics are presented in table 1).
  • the liquid fraction from the FCC unit still contains a small non-converted fraction at 540°C+, the yield of which is 1.2% by weight relative to the FCC charge, as indicated in table 24.
  • the conversion of the DAO is not total here.
  • Table 24 Yields and qualities of effluents from the FCC F unit Unity FCC Gasoline yield (C5 - 220°C) %weight 41.6 Diesel efficiency (220 - 360°C) %weight 14.3 Yield Distillate Under Vacuum (360 - 540°C) %weight 15.2 Vacuum Residue Yield (540°C+) %weight 1.2
  • one operates with two ebullated bed reactors arranged in series (first and second deep hydroconversions), operated at high hourly space velocity (WH) and at moderate temperature (420°C) with an interstage separation section and a downstream deasphalting process.
  • the CAD cut is then converted into an FCC unit.
  • the three-phase reactor contains a NiMo/alumina hydroconversion catalyst having a NiO content of 4% by weight and a MoO 3 content of 9% by weight, the percentages being expressed relative to the total mass of the catalyst.
  • the section operates as an updraft bubbling bed of liquid and gas.
  • the liquid effluent from section A is then sent to a separation section B composed of a single gas/liquid separator operating at the pressure and temperature of the reactors of the first hydroconversion section A.
  • a so-called light and a so-called heavy fraction are thus separated.
  • the so-called light fraction is mainly composed of molecules with a boiling point below 350°C and the so-called heavy fraction is mainly composed of molecules of hydrocarbons boiling at a temperature of at least 350°C.
  • the heavy fraction from the separation section B is sent alone and in its entirety to a second hydroconversion section C in an ebullated bed, in the presence of hydrogen.
  • Said section comprises a three-phase reactor containing a NiMo/alumina hydroconversion catalyst having a NiO content of 4% by weight and a MoO 3 content of 9% by weight, the percentages being expressed relative to the total mass of the catalyst.
  • the section operates as an updraft bubbling bed of liquid and gas.
  • the conditions applied in the hydroconversion section C are shown in Table 14.
  • the effluent from the hydroconversion section C is sent to a fractionation section D consisting of atmospheric distillation followed by vacuum distillation from which an unconverted heavy vacuum residue fraction (RSV) boiling at a temperature of at least 540°C, the yields of which with respect to the fresh load and the quality are given in table 15.
  • RSV unconverted heavy vacuum residue fraction
  • the vacuum residue from section D is sent to the deasphalting section E.
  • a DAO fraction and a fraction called "asphalt" difficult to recover.
  • the yields and qualities of these two products are given in Table 17.
  • the DAO fraction from the deasphalting 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 vacuum residue (RSV) originating from an Ural crude whose characteristics are presented in table 1).
  • the liquid fraction from the FCC unit still contains a small unconverted 540°C+ fraction, the yield of which is 1.9% by weight relative to the FCC charge, as indicated in Table 25.
  • the conversion of the DAO is not total here.
  • Table 25 Yields and qualities of effluents from the FCC F unit Unity FCC Gasoline yield (C5 - 220°C) %weight 30.9 Diesel efficiency (220 - 360°C) %weight 16.7 Yield Distillate Under Vacuum (360 - 540°C) %weight 22.5 Vacuum Residue Yield (540°C+) %weight 1.9
  • the CAD cut is then converted into an FCC unit.
  • All of the fresh feed from Table 1 is sent to a bubbling bed hydroconversion section A, in the presence of hydrogen.
  • Said section comprises a three-phase reactor containing a NiMo/alumina hydroconversion catalyst having a NiO content of 4% by weight and a MoO 3 content of 9% by weight, the percentages being expressed relative to the total mass of the catalyst.
  • the section operates as an updraft bubbling bed of liquid and gas.
  • the conditions applied in the hydroconversion section (A) are shown in Table 18. These operating conditions make it possible to obtain a liquid effluent with a reduced Conradson carbon, metals and sulfur content.
  • the liquid effluent from section A is then sent to a separation section B composed of a single gas/liquid separator operating at the pressure and temperature of the reactors of the first hydroconversion section A.
  • a so-called light and a so-called heavy fraction are thus separated.
  • the so-called light fraction is mainly composed of molecules with a boiling point below 350°C and the so-called heavy fraction is composed of molecules of hydrocarbons boiling at a temperature of at least 350°C.
  • the heavy fraction) from the separation section B is sent alone and in its entirety to a second hydroconversion section C in an ebullated bed, in the presence of hydrogen.
  • Said section comprises a three-phase reactor containing a NiMo/alumina hydroconversion catalyst having a NiO content of 4% by weight and a MoO 3 content of 9% by weight, the percentages being expressed relative to the total mass of the catalyst.
  • the section operates as an updraft bubbling bed of liquid and gas.
  • the conditions applied in the hydroconversion section C are shown in Table 19.
  • the effluent from the hydroconversion section C is sent to a fractionation section D consisting of atmospheric distillation followed by vacuum distillation from which an unconverted heavy vacuum residue fraction (RSV) boiling at a temperature of at least 540°C, the yields of which in relation to the fresh load and the quality are given in table 20.
  • a fractionation section D consisting of atmospheric distillation followed by vacuum distillation from which an unconverted heavy vacuum residue fraction (RSV) boiling at a temperature of at least 540°C, the yields of which in relation to the fresh load and the quality are given in table 20.
  • RSV unconverted heavy vacuum residue fraction
  • the vacuum residue from section D is sent to the deasphalting section E.
  • a DAO fraction is obtained which can be recovered in a conversion process (hydrocracking, FCC or recycling to the hydroconversion process) and a so-called “asphalt” fraction which is difficult to recover.
  • the yields and qualities of these two products are given in Table 22.
  • the DAO fraction from the deasphalting 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 vacuum residue (RSV) originating from an Ural crude whose characteristics are presented in table 1).
  • the liquid fraction from the FCC unit still contains a small unconverted 540°C+ fraction, the yield of which is 1.2% by weight relative to the FCC charge, as indicated in Table 26. example 4, where all the DAO was converted in a hydrocracking unit, the conversion of the DAO is not total here.
  • Table 26 Yields and qualities of effluents from the FCC F unit Unity FCC Gasoline yield (C5 - 220°C) %weight 42.0 Diesel efficiency (220 - 360°C) %weight 14.2 Yield Distillate Under Vacuum (360 - 540°C) %weight 13.8 Vacuum Residue Yield (540°C+) %weight 1.2
  • the conversion of the heavy cut 540°C+ is 86.1% by weight before the deasphalting step, is greater by 26.9% by weight compared to Example 7 at the same temperature level.
  • the amount of unconverted RSV recovered in Example 4 is thus approximately 3 times lower.
  • the unconverted RSV of Example 8 contains lower contents of Conradson carbon and C 7 asphaltenes compared to Example 7, which makes it possible to recover a greater quantity of DAO from the unconverted RSV (66.8% recoverable weight in this example against 54.1% weight in example 7).
  • this scheme according to the invention is accompanied by a lower generation of asphalt corresponding to only 3.6% by weight relative to the fresh starting load.
  • the CAD cut here is converted to an FCC unit.
  • the overall conversion of the 540°C+ heavy cut in the complete scheme is 94.4% by weight relative to the starting heavy cut 540° C.+, i.e. 14.4 conversion points more than in Example 7.
  • the scheme according to the invention therefore makes it possible to exceed a conversion of 90% weight relative to the fresh load.

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Claims (8)

  1. Verfahren zur Umwandlung von Kohlenwasserstoffeinsätzen, von denen mindestens 50 Gew.-%, bevorzugt mindestens 80 Gew.-%, bei einer Temperatur von mindestens 300 °C sieden, umfassend die folgenden aufeinanderfolgenden Schritte:
    - Kohlenwasserstoffeinsatzes in Gegenwart von Wasserstoff unter einem absoluten Druck zwischen 2 MPa und 35 MPa, bei einer Temperatur zwischen 300 °C und 550 °C, mit einer Wasserstoffmenge zwischen 50 Nm3/m3 und 5000 Nm3/m3 mit einem Katalysator ausgeführt, der mindestens ein Metall der Gruppe VIII, das unter Nickel und Cobalt gewählt ist, und mindestens ein Metall der Gruppe VIB, das unter Molybdän und Wolfram gewählt ist, enthält, - gegebenenfalls einen Schritt b) des Abtrennens einer leichten Fraktion ausgehend von einem Teil oder der Gesamtheit des aus der ersten Hydrokonversion hervorgegangenen Abstroms, und es wird mindestens eine schwere Fraktion erhalten, von der mindestens 80 Gew.-% eine Siedetemperatur von mindestens 250 °C aufweisen,
    - in einem Schritt c) wird eine zweite tiefe Hydrokonversion eines Teils oder der Gesamtheit des aus Schritt a) hervorgegangenen flüssigen Abstroms oder der aus Schritt b) hervorgegangenen schweren Fraktion unter einem absoluten Druck zwischen 2 MPa und 35 MPa, bei einer Temperatur zwischen 300 °C und 550 °C, mit einer Wasserstoffmenge zwischen 50 Nm3/m3 und 5000 Nm3/m3 mit einem Katalysator ausgeführt, der mindestens ein Metall der Gruppe VIII, das unter Nickel und Cobalt gewählt ist, und mindestens ein Metall der Gruppe VIB, das unter Molybdän und Wolfram gewählt ist, enthält,
    - einen Schritt d) des Abtrennens eines Teils oder der Gesamtheit des aus der zweiten Hydrokonversion hervorgegangenen Abstroms in mindestens eine leichte Fraktion und mindestens eine schwere Fraktion, von der mindestens 80 Gew.-% eine Siedetemperatur von mindestens 300 °C aufweisen,
    - einen Schritt e) des Entasphaltierens der aus Schritt d) hervorgegangenen schweren Fraktion bei einer Temperatur zwischen 60 °C und 250 °C mit mindestens einem kohlenwasserstoffhaltigen Lösungsmittel mit 3 bis 7 Kohlenstoffatomen und einem Lösungsmittel/Einsatz-Verhältnis (Volumen/Volumen) zwischen 4:1 und 9:1, und es werden eine entasphaltierte Fraktion DAO und ein Asphalt erhalten, wobei das Lösungsmittel aus der Gruppe, die durch Butan, Pentan oder Hexan gebildet wird, sowie ihren Mischungen gewählt ist,
    - einen Schritt f) der Umwandlung eines Teils oder der Gesamtheit der gegebenenfalls destillierten entasphaltierten Fraktion DAO, wobei der Teil oder die Gesamtheit der Fraktion DAO bevorzugt direkt in den Umwandlungsschritt f) geführt wird, wobei der Umwandlungsschritt f) mit einem Verfahren arbeitet, das aus der Gruppe gewählt ist, die durch das Festbett-Hydrocracken, das katalytische Cracken im Fließbett, die Hydrokonversion im wallenden Bett gebildet wird, wobei diese Verfahren ein vorheriges Hydrotreating beinhalten können, und der Katalysator der Hydrokonversion im wallenden Bett von Schritt f) in Form von Extrudaten oder von Kugeln verwendet wird, und wobei die Gesamtraumgeschwindigkeit bei den Schritten a) bis c) weniger als 0,1 h-1 beträgt, wobei die Gesamtgeschwindigkeit der Volumenstrom des flüssigen Einsatzes des Hydrokonversionsschritts a) unter standardmäßigen Temperatur- und Druckbedingungen bezogen auf das Gesamtvolumen der Reaktoren der Schritte a) und c) ist, und der Hydrokonversionskatalysator von Schritt a) und der Hydrokonversionskatalysator von Schritt c) in Form von Extrudaten oder von Kugeln verwendet werden.
  2. Verfahren nach Anspruch 1, bei dem das DAO vor dem Umwandlungsschritt f) so destilliert wird, dass eine schwere Fraktion abgetrennt wird, von der mindestens 80 Gew.-% eine Siedetemperatur von mindestens 375 °C oder mindestens 400 °C oder mindestens 450 °C oder mindestens 500 °C und bevorzugt mindestens 540 °C aufweisen, und die schwere Fraktion teilweise oder vollständig in den Umwandlungsschritt f) geführt wird.
  3. Verfahren nach einem der vorhergehenden Ansprüche, bei dem ein Teil oder die Gesamtheit der entasphaltierten Fraktion DAO einem Festbett-Hydrocracken unterzogen wird in Gegenwart von Wasserstoff, unter einem absoluten Druck zwischen 5 MPa und 35 MPa, bei einer Temperatur zwischen vorteilhafterweise 300 und 500 °C, einer HSV zwischen 0,1 h-1 und 5 h-1 und einer Wasserstoffmenge zwischen 100 Nm3/m3 und 1000 Nm3/m3 flüssiger Einsatz und in Gegenwart eines Katalysators, der mindestens ein unedles Element der Gruppe VIII und mindestens ein Element der Gruppe VIB enthält und einen Träger umfasst, der mindestens einen Zeolithen enthält.
  4. Verfahren nach einem der Ansprüche 1 oder 2, bei dem ein Teil oder die Gesamtheit der entasphaltierten Fraktion DAO einem katalytischen Cracken im Fließbett FCC in Gegenwart eines bevorzugt metallfreien Katalysators unterzogen wird, der Aluminiumoxid, Siliciumoxid, Siliciumoxid-Aluminiumoxid umfasst und bevorzugt mindestens einen Zeolithen umfasst.
  5. Verfahren nach einem der Ansprüche 1 oder 2, bei dem ein Teil oder die Gesamtheit der entasphaltierten Fraktion DAO einer Hydrokonversion im wallenden Bett unterzogen wird, die in Gegenwart von Wasserstoff, unter einem absoluten Druck zwischen 2 MPa und 35 MPa, bei einer Temperatur zwischen 300 °C und 550 °C, einer Wasserstoffmenge zwischen 50 Nm3/m3 und 5000 Nm3/m3 flüssiger Einsatz, einer HSV zwischen 0,1 h-1 und 10 h-1 und in Gegenwart eines Katalysators ausgeführt wird, der einen Träger und mindestens ein Metall der Gruppe VIII, das unter Nickel und Cobalt gewählt ist, und mindestens ein Metall der Gruppe VIB, das unter Molybdän und Wolfram gewählt ist, enthält.
  6. Verfahren nach einem der vorhergehenden Ansprüche, bei dem mindestens ein Teil der entasphaltierten Fraktion DAO im Schritt a) und/oder im Schritt c) recycelt wird.
  7. Verfahren nach einem der vorhergehenden Ansprüche, bei dem im Abtrennschritt d) der aus der zweiten Hydrokonversion hervorgegangene Abstrom in mindestens eine leichte Fraktion und mindestens eine schwere Fraktion getrennt wird, von der mindestens 80 Gew.-% eine Siedetemperatur von mindestens 375 °C oder mindestens 400 °C oder mindestens 450 °C oder mindestens 500 °C und bevorzugt mindestens 540 °C aufweisen.
  8. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die Schritte a) und c) unter einem absoluten Druck zwischen 5 MPa und 25 MPa und bevorzugt zwischen 6 MPa und 20 MPa, bei einer Temperatur zwischen 350 °C und 500 °C und bevorzugt zwischen 370 °C und 430 °C und noch bevorzugter zwischen 380 °C und 430 °C, mit einer Wasserstoffmenge zwischen 100 Nm3/m3 und 2000 Nm3/m3 und ganz besonders bevorzugt zwischen 200 Nm3/m3 und 1000 Nm3/m3 ausgeführt werden, wobei die Raumgeschwindigkeit (HSV) mindestens 0,05 h-1 beträgt bevorzugt zwischen 0,05 h-1 und 0,09 h-1.
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US11788017B2 (en) 2017-02-12 2023-10-17 Magëmã Technology LLC Multi-stage process and device for reducing environmental contaminants in heavy marine fuel oil
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RU2020123947A (ru) 2022-01-21
FR3075810A1 (fr) 2019-06-28
RU2020123947A3 (de) 2022-01-21
SA520412258B1 (ar) 2023-07-09
US20210102130A1 (en) 2021-04-08
PL3728519T3 (pl) 2022-05-16
FR3075810B1 (fr) 2020-09-11
US11485916B2 (en) 2022-11-01
EP3728519A1 (de) 2020-10-28
CN111788286A (zh) 2020-10-16
WO2019121074A1 (fr) 2019-06-27

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