EP3255123B1 - Umwandlungsverfahren, das mindestens eine hydrotreating-phase im festbett und eine hydrocracking-phase in umgehbaren reaktoren umfasst - Google Patents

Umwandlungsverfahren, das mindestens eine hydrotreating-phase im festbett und eine hydrocracking-phase in umgehbaren reaktoren umfasst Download PDF

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EP3255123B1
EP3255123B1 EP17170033.9A EP17170033A EP3255123B1 EP 3255123 B1 EP3255123 B1 EP 3255123B1 EP 17170033 A EP17170033 A EP 17170033A EP 3255123 B1 EP3255123 B1 EP 3255123B1
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weight
reactors
reactor
hydrocracking
catalyst
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French (fr)
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EP3255123A1 (de
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Wilfried Weiss
Pascal Chatron-Michaud
Elodie Tellier
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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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • 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
    • 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
    • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment 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
    • C10G7/00—Distillation of hydrocarbon oils
    • C10G7/06—Vacuum distillation
    • 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

Definitions

  • the present invention relates to the refining and the conversion of heavy hydrocarbon fractions containing, inter alia, sulfur-containing impurities. It relates more particularly to a process for the conversion of heavy petroleum feedstocks of the atmospheric residue and / or vacuum residue type for the production of heavy fractions that can be used as fuel bases, in particular as bunker oil bases with a low sediment content.
  • the process according to the invention also makes it possible to produce atmospheric distillates (naphtha, kerosene and diesel), vacuum distillates and light gases (C1 to C4).
  • the sediment content according to ISO 10307-1 (also known as IP375) is different from the sediment content after aging according to ISO 10307-2 (also known as IP390).
  • the sediment content after aging according to ISO 10307-2 is a much more stringent specification and corresponds to the specification for bunker fuels.
  • a ship may therefore use a sulfur-containing fuel oil if the ship is equipped with a flue gas treatment system that reduces emissions of sulfur oxides.
  • Fuel oils used in shipping generally include atmospheric distillates, vacuum distillates, atmospheric residues and residues. under vacuum from direct distillation or from refining process, including hydrotreating and conversion processes, these sections can be used alone or in mixture. These processes, although known to be suitable for heavy loads loaded with impurities, however, produce hydrocarbon fractions that may include catalyst fines and / or sediments that must be removed to satisfy a product quality such as bunker fuel oil.
  • the sediments may be precipitated asphaltenes.
  • the conversion conditions, and in particular the temperature, cause them to undergo reactions (dealkylation, polycondensation, etc.) leading to their precipitation.
  • the existing sediments in the heavy cut at the end of the process measured according to ISO 10307-1, also known as IP375
  • These sedimentation phenomena generally occur during the implementation of severe conditions (high temperature and residence time) giving rise to high conversion rates, for example greater than 35, 40 or 50% or more, and this depending on the nature of the charge.
  • the formation of potential and / or existing sediments also tends to increase with the aging of the catalysts.
  • the conversion ratio is defined as the mass fraction of organic compounds having a boiling point above 520 ° C in the feed at the inlet of the reaction section minus the mass fraction of organic compounds having a higher boiling point. at 520 ° C at the outlet of the reaction section in the effluent, all divided by the mass fraction of organic compounds having a boiling point above 520 ° C at the inlet of the reaction section in the feedstock.
  • waste treatment processes there is an economic interest in maximizing conversion because, generally, conversion products, especially distillates, are better valued than the unconverted feed or fraction.
  • the temperature is generally lower than in bubbling bed or slurry bed hydrocracking processes. The conversion rate in fixed bed is therefore generally lower, but the implementation is simpler than bubbling bed or "slurry".
  • the conversion rate of hydrotreatment processes in fixed bed is moderate or low, generally less than 45%, usually less than 35% at the end of the cycle, and less than 25% at the beginning of the cycle.
  • the conversion rate generally varies during the cycle due to the increase in temperature to compensate for the catalytic deactivation.
  • sediment production is generally lower in fixed bed hydrotreatment processes than in bubbling bed or slurry bed hydrocracking processes.
  • temperatures sometimes reached from the middle of the cycle and up to the end of the cycle for fixed bed residue hydrotreating processes can lead to a sufficient sediment formation to degrade the quality of an oil, especially an oil. bunker, consisting largely of a heavy fraction from a process of hydrotreatment of residues in fixed bed.
  • the skilled person is familiar with the difference between fixed bed and bed in "slurry".
  • a "slurry" bed is a bed in which the catalyst is sufficiently dispersed in the form of small particles to be suspended in the liquid phase.
  • FR 2 983 866 discloses a continuous process for treating a hydrocarbon feedstock.
  • bypassable reactor is meant a reactor, which can be stopped by the implementation of a “by pass” while the other reactors of the unit are still in operation. Unlike the so-called reactive reactors that can be put back into service while the other (or other) reactor (s) of the unit is (are) in operation, the bypassable reactors can be shut down at any time and usually restarted only when restarting the entire unit
  • a bypassable reactor can be erased at any time and for a longer or shorter duration of the production scheme, while a switchable reactor necessarily stops in favor of another. which restarts.
  • Another advantage of the new process incorporating a hydrocracking step in passable reactors is that it becomes possible to operate these hydrocrackable reactors at an average temperature over the entire cycle that is higher than that of the reactors.
  • the fixed bed hydrotreatment section thus leading to a higher conversion without the formation of sediment, generally increased by the higher temperature, is problematic for the quality of the product.
  • the temperature of the by-passable reactor requiring the shutdown of the reactor is between 405 ° C and 425 ° C.
  • the passable hydrocracking section is stopped in such a way as to prevent the generation of sediments, in particular potential sediments, while allowing hydrotreatment to be continued on the upstream reactors.
  • the hydrocracking section is implemented from the beginning of the cycle of the unit and for at least 30% of the cycle, or even at least 50% of the cycle.
  • the stopping temperature of the hydrocracking section in passable reactors is to be determined by the operator by monitoring the sediment content of the effluent, in particular the potential sediments, as soon as the sediment content after aging ( IP390) is greater than 0.05 or 0.08% by weight for example, it is time to stop the hydrocracking section in passable reactors.
  • the average temperature of the process is a mass weighting of the average temperatures of the different beds. It is calculated taking into account for each reactor its average temperature and its weight of catalysts.
  • the weighted average temperature will be calculated as (T1 * m1 + T2 * m2) / (m1 + m2).
  • the catalysts of the hydrotreatment section are little deactivated and therefore active at moderate temperatures which leads to the production of very stable effluents with no sediment, there is therefore an interest in exploiting this margin of stability by applying a hydrocracking step in passable reactors operating at a higher temperature and allowing a gain in conversion.
  • the coking and the increase of the pressure drop are not problematic in the hydrocracking section, since the bypassable reactors can be stopped without stopping the unit, which then makes it possible to reduce the pressure drop of the section. reaction by subtraction of the loss of charges from the reactors by passables.
  • the invention relates to a method as defined in claim 1.
  • One of the objectives of the present invention is to propose a process coupling conversion and desulphurization of heavy petroleum feedstocks for the production of fuel oils and low-sulfur fuel oil bases.
  • Another objective of the process according to the invention is the production of bunker fuels or bunker oil bases with a low sediment content, that is to say, after aging less than or equal to 0.1% by weight, this being achieved by the implementation of steps a), b), c) and d) during the first part of the cycle, then by stopping the reactors by passables in the second part of the cycle.
  • Another object of the present invention is to jointly produce, by the same method, atmospheric distillates (naphtha, kerosene, diesel), vacuum distillates and / or light gases (C1 to C4).
  • the bases of the naphtha and diesel type can be upgraded to refineries for the production of automotive and aviation fuels, such as, for example, super-fuels, Jet fuels and gas oils.
  • the figure 1 describes a scheme for implementing the invention without limiting its scope.
  • the hydrocarbon feedstock (1) and hydrogen (2) are brought into contact in a hydrodemetallation step (a) in permutable reactors, in which the hydrogen (2) can be introduced at the inlet of the first catalytic bed and between two beds of step a).
  • the effluent (3) resulting from the hydrodemetallation stage a) in swarfable reactor reactors is sent to a fixed bed hydrotreatment stage b), in which additional hydrogen (4) can be introduced as input of the first catalytic bed and between two beds of step b).
  • the effluent (5) resulting from the fixed bed hydrotreating step b) is sent to a step c) of hydrocracking in passable reactors in which additional hydrogen (6) can be introduced at the inlet of the first catalytic bed and between two beds of step c).
  • this reactor is short-circuited by means of valves, that is to say that the supply of this reactor is directly connected to the reactor. the effluent line of this reactor. If there is only a single passable reactor or when all the bypassable reactors are stopped, the effluent (5) resulting from the fixed bed hydrotreatment step is introduced directly at the inlet of the step d) separation.
  • the effluent (7) from the hydrocracking step c) in passable reactors is sent in a step of separation d) for obtaining at least a light hydrocarbon fraction (8) and a heavy fraction (9) containing compounds boiling at least 350 ° C. and having a sediment content after aging less than or equal to 0.1% by weight.
  • the figure 2 describes a simplified diagram of implementation of the sequence of reactors of the invention without limiting the scope thereof.
  • the reactors are represented but it is understood that all the equipment necessary for operation are present (balloons, pumps, exchangers, ovens, columns, etc.).
  • the main streams containing the hydrocarbons are represented, but it is understood that hydrogen-rich gas streams (make-up or recycle) can be injected at the inlet of each catalytic bed or between two beds.
  • the charge (1) enters a hydrodemetallation step in reactive guard reactors consisting of reactors Ra and Rb.
  • the effluent (2) of the hydrodemetallation step in permutable guard reactors is sent to the fixed bed hydrotreating step consisting of the reactors R1, R2 and R3.
  • the fixed bed hydrotreating reactors can for example be loaded respectively with hydrodemetallation, transition and hydrodesulfurization catalysts.
  • the effluent (3) of the fixed bed hydrotreating step is sent to the per passable hydrocracking step represented by a reactor Rc.
  • Each reactor Ra, Rb, Rc can be taken offline without stopping the rest of the unit.
  • only Ra and Rb which are permutable reactors can be stopped so as to change the catalyst and then be restarted without stopping the rest of the unit.
  • This catalyst change (rinsing, unloading, reloading, sulphurization and restarting) is generally allowed by a not shown packaging section.
  • the reactor Rc stops during the cycle without stop the rest of the unit but will only be restarted after the complete shutdown of the unit, the purpose of this stop being to unload and reload all deactivated catalysts.
  • the reactors After a certain time, the reactors reach on average a critical temperature because of the catalytic deactivation of all the catalysts, it is then time in the sequence 4 to stop the reactor Rc by passable hydrocracking, until the end of the cycle, so as to control the production of sediments, in particular potential sediments. During the next cycle, it is possible to restart with the switchable hydrodemetallization reactor Rb at the head. It is also possible to retain all or part of the catalysts of the previous cycle if it is not completely deactivated, which may for example be the case if a switchable hydrodemetallization reactor is put back online shortly before the total shutdown of the reactor. 'unit.
  • the deactivation time of the hydrodemetallation reactive reactors is a function of the treated feedstock, in particular the metal content.
  • the operating time of the hydrocracking section in permutable reactors is a function of the load and of the applied severity (temperature and residence time in particular).
  • the feedstock treated in the process according to the invention is advantageously a hydrocarbon feed having an initial boiling point of at least 340 ° C. and a final boiling point of at least 440 ° C.
  • its initial boiling point is at least 350 ° C., preferably at least 375 ° C.
  • its final boiling point is at least 450 ° C., preferably at least 460 ° C. C, more preferably at least 500 ° C, and even more preferably at least 600 ° C.
  • the hydrocarbon feedstock according to the invention may be chosen from atmospheric residues, vacuum residues resulting from direct distillation, crude oils, crude head oils, deasphalting resins, asphalts or deasphalting pitches, process residues. conversion products, aromatic extracts from lubricant base production lines, oil sands or derivatives thereof, oil shales or their derivatives, source rock oils or their derivatives, whether alone or in combination.
  • the fillers being treated are preferably atmospheric residues or vacuum residues, or mixtures of these residues.
  • the hydrocarbon feedstock treated in the process may contain, among other things, sulfur-containing impurities.
  • the sulfur content may be at least 0.1% by weight, preferably at least 0.5% by weight, preferably at least 1% by weight, more preferably at least 2% by weight. .
  • the hydrocarbon feedstock treated in the process may contain, inter alia, metallic impurities, in particular nickel and vanadium.
  • metallic impurities in particular nickel and vanadium.
  • the sum of the nickel and vanadium contents is generally at least 10 ppm, preferably at least 50 ppm, preferably at least 100 ppm.
  • This co-charge may be a hydrocarbon fraction or a lighter hydrocarbon fraction mixture, which may preferably be chosen from the products resulting from a fluid catalytic cracking (FCC) process according to the English terminology. Saxon), a light cut (LCO or "light cycle oil” according to the English terminology), a heavy cut (HCO or "heavy cycle oil” according to the English terminology), a decanted oil, a residue of FCC, a gas oil fraction, especially a fraction obtained by atmospheric distillation or under vacuum, such as vacuum gas oil, or may come from another refining process such as coking or visbreaking.
  • FCC fluid catalytic cracking
  • the co-charge may also advantageously be one or more cuts resulting from the process of liquefying coal or biomass, aromatic extracts, or any other hydrocarbon cuts, or non-petroleum fillers such as pyrolysis oil.
  • the heavy hydrocarbon feedstock according to the invention may represent at least 50%, preferably 70%, more preferably at least 80%, and even more preferably at least 90% by weight of the total hydrocarbon feedstock treated by the process according to the invention.
  • the process according to the invention makes it possible to obtain conversion products, in particular distillates and a heavy hydrocarbon fraction with a low sulfur content.
  • This heavy hydrocarbon fraction may be produced in such a way that its sediment content after aging is less than or equal to 0.1% by weight, this being allowed by the stopping (bypass or bypass) of at least one reactor of the hydrocracking section in passable reactors.
  • Step a) During step a) of hydrodemetallization, the feedstock and hydrogen are contacted on a hydrodemetallization catalyst loaded in at least two reactive reactors, under hydrodemetallation conditions.
  • the goal is to reduce the impurity content and thus protect the downstream hydrotreating step from the deactivation and clogging, hence the notion of aging reactors.
  • These reactors hydrodemetallation guards are implemented as permutable reactors (technology "PRS" for "Permutable Reactor System” according to the English terminology) as described in the patent FR2681871 .
  • These permutable reactors are generally fixed beds located upstream of the fixed bed hydrotreatment section and equipped with lines and valves so as to be permuted between them, that is to say for a system with two permutable reactors Ra and Rb, Ra can be in front of Rb and vice versa.
  • Each reactor Ra, Rb can be taken offline so as to change the catalyst without stopping the rest of the unit.
  • This catalyst change (rinsing, unloading, reloading, sulphurization and restart) is generally allowed by a conditioning section (set of equipment outside the main high pressure loop).
  • the permutation for catalyst change occurs when the catalyst is no longer sufficiently active (poisoning by metals and coking) and / or the clogging reaches a loss of pressure too high.
  • step a) of hydrodemetallation hydrodemetallation reactions (commonly called HDM), but also hydrodesulfurization reactions (commonly called HDS), hydrodenitrogenation reactions (commonly called HDN) accompanied by Hydrogenation, hydrodeoxygenation, hydrodearomatization, hydroisomerization, hydrodealkylation, hydrocracking, hydrodephalting and Conradson carbon reduction reactions.
  • Step a) is called hydrodemetallation because it removes the majority of the metals from the charge.
  • the hydrodemetallation stage a) in permutable reactors according to the invention is carried out at a temperature of between 350.degree. C. and 430.degree. C., and at an absolute pressure of between 11 MPa and 26 MPa, preferably between 14.degree. MPa and 20 MPa.
  • the temperature is usually adjusted according to the desired level of hydrodemetallation and the duration of the targeted treatment.
  • the space velocity of the hydrocarbon feedstock commonly referred to as VVH, which is defined as the volumetric flow rate of the feedstock divided by the total volume of the catalyst, can be in a range of 0.1 h -1. at 5 h -1 , preferably from 0.15 h -1 to 3 h -1 , and more preferably from 0.2 h -1 to 2 h -1 .
  • the amount of hydrogen mixed with the feedstock may be between 100 and 5000 normal cubic meters (Nm3) per cubic meter (m3) of liquid feedstock, preferably between 200 Nm3 / m3 and 2000 Nm3 / m3, and more preferably between 300 Nm3 / m3 and 1000 Nm3 / m3.
  • the hydrodemetallation stage a) in permutable reactors can be carried out industrially in at least two reactors in a fixed bed and preferably in a downflow of liquid.
  • the hydrodemetallization catalysts used are preferably known catalysts. They may be granular catalysts comprising, on a support, at least one metal or metal compound having a hydro-dehydrogenating function.
  • These catalysts may advantageously be catalysts comprising at least one Group VIII metal, generally selected from the group consisting of nickel and cobalt, and / or at least one Group VIB metal, preferably molybdenum and / or tungsten.
  • a catalyst comprising from 0.5% to 10% by weight of nickel, preferably from 1% to 5% by weight of nickel (expressed as nickel oxide NiO), and from 1% to 30% by weight of nickel.
  • weight of molybdenum preferably from 3% to 20% by weight of molybdenum (expressed as molybdenum oxide MoO3) on a mineral support.
  • This support may for example be chosen from the group consisting of alumina, silica, silica-aluminas, magnesia, clays and mixtures of at least two of these minerals.
  • this support may contain other doping compounds, in particular oxides selected from the group consisting of boron oxide, zirconia, ceria, titanium oxide, phosphoric anhydride and a mixture of these oxides.
  • oxides selected from the group consisting of boron oxide, zirconia, ceria, titanium oxide, phosphoric anhydride and a mixture of these oxides.
  • alumina support is used and very often a support of alumina doped with phosphorus and possibly boron.
  • phosphorus pentoxide P2O5 When phosphorus pentoxide P2O5 is present, its concentration is less than 10% by weight.
  • B2O5 boron trioxide When B2O5 boron trioxide is present, its concentration is less than 10% by weight.
  • the alumina used can be a y (gamma) or ⁇ (eta) alumina. This catalyst is most often in the form of extrudates.
  • the total content of metal oxides of groups VIB and VIII may be from 5% to 40% by weight, preferably from 5% to 30% by weight, and the weight ratio expressed as metal oxide between metal (or metals) of group VIB on metal (or metals) of group VIII is generally between 20 and 1, and most often between 10 and 2.
  • Catalysts that can be used in the hydrodemetallation step a) in permutable reactors are, for example, indicated in the patent documents.
  • step a) of hydrodemetallation is introduced, optionally with hydrogen, in a step b) of hydrotreating in fixed bed to be contacted on at least one hydrotreatment catalyst.
  • Hydrotreatment commonly known as HDT
  • HDT Hydrotreatment
  • hydrodesulfurization reactions commonly referred to as HDS
  • hydrodenitrogenation reactions commonly referred to as HDN
  • hydrodemetallation reactions commonly referred to as HDM
  • the hydrotreatment step b) comprises a first hydrodemetallation stage (HDM) b1) carried out in one or more hydrodemetallation zones in fixed beds and a second hydrodesulphurization second stage (b2) (HDS). performed in one or more hydrodesulfurization zones in fixed beds.
  • first hydrodemetallation step b1) the effluent from step a) is contacted on a hydrodemetallization catalyst under hydrodemetallation conditions and then during said second step b2) d.
  • hydrodesulfurization the effluent of the first hydrodemetallation step b1) is brought into contact with a hydrodesulfurization catalyst, under hydrodesulfurization conditions.
  • This process known as HYVAHL-F TM, is for example described in the patent US 5417846 .
  • step b1) of hydrodemetallization hydrodemetallation reactions are carried out but at the same time also a part other hydrotreating reactions, and in particular hydrodesulfurization and hydrocracking reactions.
  • hydrodesulfurization step b2) hydrodesulphurization reactions are carried out, but also part of the other hydrotreatment reactions, in particular hydrodemetallation and hydrocracking reactions.
  • Those skilled in the art sometimes define a transition zone in which all types of hydrotreatment reactions occur.
  • the hydrotreatment stage b) comprises a first hydrodemetallation stage (HDM) b1) carried out in one or more hydrodemetallation zones in fixed beds, a second transition stage b2) carried out in one or more a plurality of transition zones in fixed beds, and a third hydrodesulphurization (HDS) step b3) carried out in one or more hydrodesulfurization zones in fixed beds.
  • first hydrodemetallation step b1) the effluent from step a) is contacted on a hydrodemetallization catalyst under hydrodemetallation conditions and then during said second step b2).
  • the effluent of the first hydrodemetallation step b1) is brought into contact with a transition catalyst, under transition conditions, and then during said third hydrodesulfurization step b3), the effluent from the second stage b2) is contacted with a hydrodesulfurization catalyst under hydrodesulfurization conditions.
  • the hydrotreating step b) according to the invention is carried out under hydrotreatment conditions. It is implemented at a temperature between 350 ° C and 430 ° C and under an absolute pressure between 14 MPa and 20 MPa. The temperature is usually adjusted according to the desired level of hydrotreatment and the duration of the targeted treatment. Most often, the space velocity of the hydrocarbon feedstock, commonly referred to as VVH, which is defined as the volumetric flow rate of the feedstock divided by the total volume of the catalyst, can be in a range of 0.1 h -1. at 5 h -1 , preferably from 0.1 h -1 to 2 h -1 , and more preferably from 0.1 h -1 to 1 h -1 .
  • VVH space velocity of the hydrocarbon feedstock
  • the amount of hydrogen mixed with the feedstock may be between 100 and 5000 normal cubic meters (Nm3) per cubic meter (m3) of liquid feedstock, preferably between 200 Nm3 / m3 and 2000 Nm3 / m3, and more preferably between 300 Nm3 / m3 and 1500 Nm3 / m3.
  • the hydrotreating step b) can be carried out industrially in one or more liquid downflow reactors.
  • the hydrotreatment catalysts used are preferably known catalysts. They may be granular catalysts comprising, on a support, at least one metal or metal compound having a hydro-dehydrogenating function. These catalysts may advantageously be catalysts comprising at least one Group VIII metal, generally selected from the group consisting of nickel and cobalt, and / or at least one Group VIB metal, preferably molybdenum and / or tungsten. For example, it is possible to use a catalyst comprising from 0.5% to 10% by weight of nickel, preferably from 1% to 5% by weight of nickel (expressed as nickel oxide NiO), and from 1% to 30% by weight of nickel.
  • nickel oxide NiO nickel oxide
  • molybdenum preferably from 3% to 20% by weight of molybdenum (expressed as molybdenum oxide MoO3) on a mineral support.
  • This support may for example be chosen from the group consisting of alumina, silica, silica-aluminas, magnesia, clays and mixtures of at least two of these minerals.
  • this support may contain other doping compounds, in particular oxides selected from the group consisting of boron oxide, zirconia, ceria, titanium oxide, phosphoric anhydride and a mixture of these. oxides.
  • oxides selected from the group consisting of boron oxide, zirconia, ceria, titanium oxide, phosphoric anhydride and a mixture of these. oxides.
  • an alumina support is used and very often a support of alumina doped with phosphorus and possibly boron.
  • P2O5 phosphorus pentoxide P2O5
  • B2O5 boron trioxide When B2O5 boron trioxide is present, its concentration is less than 10% by weight.
  • the alumina used may be a gamma ( ⁇ ) or ⁇ (eta) alumina. This catalyst is most often in the form of extrudates.
  • the total content of metal oxides of groups VIB and VIII may be from 3% to 40% by weight and generally from 5% to 30% by weight and the weight ratio expressed as metal oxide between metal (or metals) of group VIB on metal (or metals) of group VIII is generally between 20 and 1, and most often between 10 and 2.
  • Catalysts that can be used in the hydrodemetallation step b1) are, for example, indicated in the patent documents.
  • Catalysts that can be used in the hydrodesulfurization step b2) are, for example, indicated in the patent documents EP 0113297 , EP 0113284 , US 6589908 , US 4818743 or US 6332976 .
  • hydrodemetallation step b1) hydrodemetallation (HDM) then a step b2) of transition, then a step b3) hydrodesulfurization (HDS), it is preferred to use specific catalysts adapted to each step.
  • Catalysts that can be used in the hydrodemetallation step b1) are, for example, indicated in the patent documents. EP 0113297 , EP 0113284 , US 5221656 , US 5827421 , US 7119045 , US 5622616 and US 5089463 .
  • Catalysts that can be used in the transition stage b2), which are active in hydrodemetallation and hydrodesulphurization, are described, for example, in the US Pat.
  • patent document FR 2940143 Catalysts that can be used in the hydrodesulfurization step b3) are, for example, indicated in the patent documents EP 0113297 , EP 0113284 , US 6589908 , US 4818743 or US 6332976 . It is also possible to use a transition catalyst as described in the patent document FR 2940143 for sections b1), b2) and b3).
  • step b) of hydrotreatment is introduced into a stage c) of hydrocracking in passable reactors.
  • Hydrogen can also be injected upstream of the different catalytic beds composing the hydrocrackable bypassable reactors.
  • any type of hydrotreating reaction (HDM, HDS, HDN, etc.) is also produced. Specific conditions, including temperature, and / or the use of one or more specific catalysts, promote the desired cracking or hydrocracking reactions.
  • the reactors of the hydrocracking step c) are used as bypassable reactors.
  • passable reactors we mean a set of at least one reactor, which can be stopped by the implementation of a bypass (short circuit using lines and valves) while the other (or the other) reactor (s) of the unit (ie the hydrodemetallation section and / or the hydrotreatment section) is (are) in operation.
  • the bypassable reactors do not have this possibility (or the restarting is not desired), they will be put back into service when the whole unit is restarted.
  • the hydrocracking step c) is carried out under hydrocracking conditions. It is carried out at a temperature of between 350.degree. C. and 430.degree. absolute pressure between 14 MPa and 20 MPa.
  • the temperature is usually adjusted according to the desired level of hydrocracking and the duration of the intended treatment.
  • the average temperature at the beginning of the cycle of the per passable reactor hydrocracking step c) is always greater by at least 5 ° C., preferably by at least 10 ° C., more preferably by at least 15 ° C at the average temperature at the beginning of the cycle of the hydrotreatment step b). This difference may decrease during the cycle due to the increase of the temperature of the hydrotreating step b) to compensate for the catalytic deactivation.
  • the average temperature over the entire cycle of step c) of hydrocracking in passable reactors is always at least 5 ° C higher than the average temperature over the entire cycle of step b) hydrotreating.
  • the space velocity of the hydrocarbon feedstock can be in a range of 0.1 h -1. at 5 h -1 , preferably from 0.2 h -1 to 2 h -1 , and more preferably from 0.25 h -1 to 1 h -1 .
  • the amount of hydrogen mixed with the feedstock may be between 100 and 5000 normal cubic meters (Nm3) per cubic meter (m3) of liquid feedstock, preferably between 200 Nm3 / m3 and 2000 Nm3 / m3, and more preferably between 300 Nm3 / m3 and 1500 Nm3 / m3.
  • the hydrocracking step c) can be carried out industrially in at least one fixed-bed reactor, and preferably with a downflow of liquid.
  • the hydrocracking catalysts used may be hydrocracking or hydrotreatment catalysts. They may be granular catalysts, in the form of extrudates or beads, comprising, on a support, at least one metal or metal compound having a hydro-dehydrogenating function. These catalysts may advantageously be catalysts comprising at least one Group VIII metal, generally selected from the group consisting of nickel and cobalt, and / or at least one Group VIB metal, preferably molybdenum and / or tungsten. For example, it is possible to use a catalyst comprising from 0.5% to 10% by weight of nickel, preferably from 1% to 5% by weight of nickel (expressed as nickel oxide NiO), and from 1% to 30% by weight of nickel.
  • nickel oxide NiO nickel oxide
  • molybdenum preferably from 5% to 20% by weight of molybdenum (expressed as molybdenum oxide MoO3) on a mineral support.
  • This support may for example be chosen from the group consisting of alumina, silica, silica-aluminas, magnesia, clays and mixtures of at least two of these minerals.
  • this support may contain other doping compounds, in particular oxides selected from the group consisting of boron oxide, zirconia, ceria, titanium oxide, phosphoric anhydride and a mixture of these oxides. Most often an alumina support is used and very often a support of alumina doped with phosphorus and possibly boron.
  • the alumina used may be a gamma ( ⁇ ) or ⁇ (eta) alumina. This catalyst is most often in the form of extrudates.
  • the total content of metal oxides of groups VIB and VIII may be from 5% to 40% by weight and in general from 7% to 30% by weight and the weight ratio expressed as metal oxide between metal (or metals) of group VIB on metal (or metals) of group VIII is generally between 20 and 1, and most often between 10 and 2.
  • the hydrocracking step can in part or in all advantageously use a bifunctional catalyst, having a hydrogenating phase in order to be able to hydrogenate the aromatics and achieve the equilibrium between the saturated compounds and the corresponding olefins and a phase acid that promotes the hydroisomerization and hydrocracking reactions.
  • the acid function is advantageously provided by supports with large surface areas (generally 100 to 800 m2.g-1) having a surface acidity, such as halogenated aluminas (chlorinated or fluorinated in particular), combinations of boron oxides and aluminum, amorphous silica-aluminas and zeolites.
  • the hydrogenating function is advantageously provided either by one or more metals of group VIII of the periodic table of the elements, such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, or by an association of at least a group VIB metal of the periodic table such as molybdenum and tungsten and at least one non-noble group VIII metal (such as nickel and cobalt).
  • the catalyst must also advantageously have a high resistance to impurities and asphaltenes due to the use of a heavy load.
  • the bifunctional catalyst used comprises at least one metal selected from the group consisting of Group VIII and VIB metals, taken alone or as a mixture, and a support comprising 10 to 90% by weight of a zeolite containing iron and 90% by weight. at 10% by weight of inorganic oxides.
  • the Group VIB metal used is preferably selected from tungsten and molybdenum and the Group VIII metal is preferably selected from nickel and cobalt.
  • the bifunctional catalyst is preferably prepared according to the method of preparation described in Japanese Patent Application No. 2289,419 (IKC) or EP 0 384 186 .
  • monofunctional catalysts and bifunctional catalysts of the alumina, amorphous silica-alumina or zeolitic type may be used in a mixture or in successive layers.
  • the catalysts used in the process according to the present invention are preferably subjected to an in-situ or ex-situ sulphurization treatment.
  • the method according to the invention further comprises a step d) of separation make it possible to obtain at least one gaseous fraction and at least one heavy liquid fraction.
  • the effluent obtained at the end of step c) of hydrocracking (or of step b) of hydrotreatment when the reactor (s) are passable comprises a liquid fraction and a gaseous fraction containing the gases. , especially H2, H2S, NH3, and C1-C4 hydrocarbons.
  • This gaseous fraction can be separated from the effluent by means of separating devices that are well known to those skilled in the art, in particular by means of one or more separator flasks that can operate at different pressures and temperatures, possibly associated with stripping means with steam or hydrogen and one or more distillation columns.
  • the effluent obtained at the end of step c) of hydrocracking or hydrotreatment step b) when the at least one reactor is passed through is advantageously separated in at least one separator tank into at least one a gaseous fraction and at least one heavy liquid fraction.
  • separators may for example be high temperature high pressure separators (HPHT) and / or high temperature low pressure separators (HPBT).
  • this gaseous fraction is preferably treated in a hydrogen purification means so as to recover the hydrogen that is not consumed during the hydrotreatment and hydrocracking reactions.
  • the hydrogen purification means may be an amine wash, a membrane, a PSA type system, or more of these means arranged in series.
  • the purified hydrogen can then advantageously be recycled in the process according to the invention, after possible recompression.
  • the hydrogen may be introduced at the inlet of the hydrodemetallization step a) and / or at different locations during the hydrotreatment step b) and / or at the inlet of the hydrocracking step c) and / or at different locations during step c) hydrocracking.
  • the separation step d) first comprises an atmospheric distillation, in which the liquid hydrocarbon fraction (s) obtained (s) after separation is (are) fractionated by atmospheric distillation. in at least one atmospheric distillate fraction and at least one atmospheric residue fraction, followed by vacuum distillation in which the atmospheric residue fraction obtained after atmospheric distillation is fractionated by vacuum distillation into at least one vacuum distillate fraction and at least one residual fraction. under vacuum.
  • the vacuum distillate fraction typically contains vacuum gas oil fractions.
  • the vacuum distillate fraction can be recovered as a distillate type marine fuel (according to ISO8217) with a very low sulfur content or can be incorporated into a residual type oil pool (according to ISO8217).
  • the vacuum distillate fraction can be sent in a fluidized catalytic cracking process or a fixed bed hydrocracking process.
  • At least a portion of the atmospheric residue fraction or a portion of the vacuum residue fraction may optionally be recycled to the hydrocracking step c).
  • the atmospheric residue fraction and / or the vacuum residue fraction can be sent to a catalytic cracking process.
  • the atmospheric residue fraction and / or the vacuum residue fraction can be used as fuel oil or as fuel oil base, possibly as a base of low sulfur bunker oil.
  • Part of the vacuum residue fraction and / or part of the vacuum distillate fraction may be fed into a catalytic cracking or bubbling bed hydrocracking step.
  • this bubbling bed hydrocracking stage is fed at least in part by a heavy liquid fraction coming from a high-temperature high-pressure separator.
  • part of the atmospheric distillate fraction and / or vacuum distillate fraction according to the invention can be left in the heavy liquid hydrocarbon fraction so that the viscosity of the mixture is directly that of a desired oil grade, for example 180 or 380 cSt at 50 ° C.
  • the liquid hydrocarbon fractions in particular the heavy fractions containing the atmospheric residue and / or the vacuum residue, according to the invention may, at least in part, advantageously be used as fuel oil bases or as fuel oil, in particular as a base for bunker oil or as bunker oil with a sediment content (after aging) less than or equal to 0.1% by weight.
  • fuel oil is meant in the invention a hydrocarbon fraction that can be used as a fuel.
  • oil base is meant in the invention a hydrocarbon fraction which, mixed with other bases, is a fuel oil.
  • the liquid hydrocarbon fractions from step d) can be mixed with one or more fluxing bases selected from the group consisting of light-cutting oils of a catalytic cracking, heavy cutting oils of a catalytic cracking, the residue of a catalytic cracking, a kerosene, a gas oil, a vacuum distillate and / or a decanted oil.
  • one or more fluxing bases selected from the group consisting of light-cutting oils of a catalytic cracking, heavy cutting oils of a catalytic cracking, the residue of a catalytic cracking, a kerosene, a gas oil, a vacuum distillate and / or a decanted oil.
  • kerosene, gas oil and / or vacuum distillate produced in the process of the invention will be used.
  • the filler is a mixture of atmospheric residues (RA) of Middle Eastern origin. This mixture is characterized by a high amount of metals (100 ppm by weight) and sulfur (4.0% by weight), as well as 7% of [370-].
  • the hydrotreatment process involves the use of three reactors in fixed beds (R1, R2 and R3) with a downward flow of liquid in which the so-called hydrodemetallation (HDM) and hydrotreatment (HDT) stages take place.
  • HDM hydrodemetallation
  • HDT hydrotreatment
  • the effluent obtained at the end of these two steps is flash separated to obtain a liquid fraction and a gaseous fraction containing the gases, in particular H 2, H 2 S, NH 3, and C 1 -C 4 hydrocarbons.
  • the liquid fraction is then stripped in a column, then fractionated in an atmospheric column and then a vacuum column in several sections (Bp-350 ° C, 350-520 ° C and 520 ° C +).
  • the reactor R1 is charged with hydrodemetallization catalyst and the reactors R2, R3 with hydrotreatment catalyst.
  • the process is carried out under a hydrogen partial pressure of 15 MPa, a reactor temperature at the beginning of the cycle of 360 ° C. and at the end of the cycle of 420 ° C.
  • Table 1 shows the hourly space velocities (WH) for each catalytic reactor, and the corresponding average temperatures (WABT) obtained over the entire cycle according to the mode of operation described.
  • the WABT is an average temperature over the height of the bed and also averaged over time over the duration of a cycle.
  • the process according to the invention is carried out in this example with the same filler, the same catalysts, and under the same operating conditions for the reactor R1.
  • the reactor R2 is operated under the same operating conditions but its VVH is larger.
  • the method according to the invention comprises the use of a new bypassable hydrocracking reactor noted Rc, replacing the reactor R3 which appears in the hydrotreating section (HDT) of the prior art.
  • This hydrocracking step is carried out at high temperature downstream of the hydrodemetallation and hydrotreatment steps in a fixed bed which take place in the reactors R1 and R2.
  • Table 2 below gives an example of operation of the bypassable reactor Rc.
  • Table 2 Operations around the bypassable reactor according to the invention Fixed bed reactors Bypassable Hydrocracking Reactor sequences HDM / Transition HDT offline HCK 1 R1 R2 - rc 2 R1 R2 rc -
  • the reactor Rc of the hydrocracking step is charged with a hydrocracking catalyst.
  • the process is carried out under a hydrogen partial pressure of 15 MPa, a reactor temperature at the beginning of the cycle of 390 ° C., and at the end of the cycle of 420 ° C.
  • the reactor Rc is taken offline until the end of the cycle via the use of a bypass to limit the formation of sediment.
  • Table 3 shows the hourly space velocity (WH) for each catalytic reactor and the corresponding average temperatures (WABT) obtained over the entire cycle according to the operating mode described. Table 3: Operational conditions of the different sections VVH (h-1) WABT (° C) HDM and HDT in fixed bed R1 0.50 390 R2 0.40 390 HCK bypass rc 0.67 405 Total 0.17 394
  • Table 4 shows the comparison of the yields and hydrogen consumption obtained according to the non-compliant example and according to the example according to the invention.
  • Table 4 Comparison of average yields obtained during the cycle
  • VVH is the ratio of the volume flow rate of charge to the volume of catalyst contained in the reactor.

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Claims (6)

  1. Kontinuierliches Verfahren zur Behandlung einer Kohlenwasserstoffcharge, die mindestens eine Kohlenwasserstofffraktion mit einem Schwefelgehalt von mindestens 0,1 Gew.-%, einer anfänglichen Siedetemperatur von mindestens 340°C und einer endgültigen Siedetemperatur von mindestens 440°C enthält, wobei das Verfahren die folgenden Schritte umfasst:
    a) einen Schritt der Hydroentmetallisierung in Gegenwart der Kohlenwasserstoffcharge und des Wasserstoffs und eines Hydroentmetallisierungs-Katalysators, bei dem mindestens zwei vertauschbare Reaktoren zu den folgenden Betriebsbedingungen eingesetzt werden:
    - Temperatur zwischen 350°C und 430°C,
    - absoluter Druck zwischen 11 MPa und 26 MPa, bevorzugt zwischen 14 MPa und 20 MPa,
    - VVH (definiert als der Volumenstrom der Charge, geteilt durch das Gesamtvolumen des Katalysators) zwischen 0,1 h-1 und 5 h-1, vorzugsweise zwischen 0,15 h-1 und 3 h-1 und noch bevorzugter zwischen 0,2 h-1 und 2 h-1,
    b) einen Schritt der Hydrobehandlung im Festbett, umfassend mindestens einen Reaktor, in dem der aus Schritt a) kommende Abfluss mit mindestens einem Katalysator zur Hydrobehandlung bei einer Temperatur zwischen 350°C und 430°C und unter einem absoluten Druck zwischen 14 MPa und 20 MPa in Kontakt gebracht wird,
    c) einen Schritt des Hydrokrackens im Festbett des aus dem Schritt b) kommenden Abflusses in Gegenwart eines Katalysators zum Hydrokracken, in dem mindestens ein umgehbarer Reaktor, d.h. ein Reaktor, der durch den Einsatz eines "Bypass" angehalten werden kann, während die anderen Reaktoren der Einheit weiter funktionieren, zu den folgenden Betriebsbedingungen eingesetzt wird:
    - Temperatur zwischen 350°C und 430°C, wobei der Reaktor angehalten wird, sobald die Temperatur des umgehbaren Reaktors zwischen 405°C und 425°C beträgt,
    - absoluter Druck zwischen 14 MPa und 20 MPa,
    d) einen Schritt der Trennung des aus dem Schritt des Hydrokrackens c) kommenden Abflusses, um mindestens eine gasförmige Fraktion und mindestens eine schwere flüssige Fraktion zu erhalten, wobei die schwere flüssige Fraktion in eine atmosphärische Destillation geschickt wird, die mindestens ein atmosphärisches Destillat und einen atmosphärischen Rückstand erzeugt, wobei der atmosphärische Rückstand zur Gänze oder zum Teil in eine Vakuumdestillation geschickt wird, die einen Vakuumrückstand erzeugt, wobei die atmosphärischen Rückstände und die Vakuumrückstände zu einem Verfahren eines katalytischen Krackens geschickt oder auch als Heizöl oder als Heizölbasis verwendet werden können.
  2. Verfahren zur Behandlung einer Kohlenwasserstoffcharge nach Anspruch 1, bei dem der Schritt der Hydroentmetallisierung a) einen Katalysator zur Hydrometallisierung verwendet, umfassend 0,5 bis 10 Gew.-% Nickel, vorzugsweise 1 bis 5 Gew.-% Nickel (ausgedrückt in Nickeloxid (NiO) und 1 bis 30 Gew.-% Molybdän, vorzugsweise 3 bis 20 Gew.-% Molybdän (ausgedrückt in Molybdänoxid MoO3), auf einem mineralischen Träger.
  3. Verfahren zur Behandlung einer Kohlenwasserstoffcharge nach Anspruch 1, bei dem der Schritt der Hydrobehandlung b) einen Katalysator verwendet, umfassend 0,5 bis 10 Gew.-% Nickel, vorzugsweise 1 bis 5 Gew.-% Nickel (ausgedrückt in Nickeloxid (NiO) und 1 bis 30 Gew.-% Molybdän, vorzugsweise 5 bis 20 Gew.-% Molybdän (ausgedrückt in Molybdänoxid MoO3), auf einem mineralischen Träger, der in der Gruppe ausgewählt ist, umfassend Aluminiumoxid, Siliziumoxid, die Silizium-Aluminium-Oxide, Magnesiumoxid, die Tonerden und die Mischungen mindestens zweier dieser Mineralien.
  4. Verfahren zur Behandlung einer Kohlenwasserstoffcharge nach Anspruch 1, bei dem der Schritt c) des Hydrokrackens einen Katalysator verwendet, umfassend 0,5 bis 10 Gew.-% Nickel, vorzugsweise 1 bis 5 Gew.-% Nickel (ausgedrückt in Nickeloxid (NiO) und 1 bis 30 Gew.-% Molybdän, vorzugsweise 5 bis 20 Gew.-% Molybdän (ausgedrückt in Molybdänoxid MoO3), auf einem mineralischen Träger, der in der Gruppe ausgewählt ist, umfassend Aluminiumoxid, Siliziumoxid, die Silizium-Aluminium-Oxide, Magnesiumoxid, die Tonerden und die Mischungen mindestens zweier dieser Mineralien.
  5. Verfahren zur Behandlung einer Kohlenwasserstoffcharge nach Anspruch 1, bei dem der Trennungsschritt d) mindestens eine atmosphärische Destillation umfasst, die es ermöglicht, mindestens eine Fraktion eines atmosphärischen Destillats und mindestens eine Fraktion eines atmosphärischen Rückstands zu erhalten.
  6. Verfahren zur Behandlung einer Kohlenwasserstoffcharge nach Anspruch 1, bei dem der Trennungsschritt d) mindestens eine Vakuumdestillation umfasst, die es ermöglicht, mindestens eine Fraktion eines Vakuumdestillats und mindestens eine Fraktion eines Vakuumrückstands zu erhalten.
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FR3052458B1 (fr) 2019-12-27
US10266779B2 (en) 2019-04-23
FR3052458A1 (fr) 2017-12-15
ES2721257T3 (es) 2019-07-30
EP3255123A1 (de) 2017-12-13
US20170355914A1 (en) 2017-12-14

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