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    • 专利摘要:
    The invention relates to a process for converting a hydrocarbon feedstock containing at least one hydrocarbon fraction having a sulfur content of at least 0.1% by weight, an initial boiling point of at least 340.degree. a final boiling temperature of at least 440 ° C to obtain a heavy fraction having a sediment content after aging less than or equal to 0.1% by weight, said process comprising the following steps: a) a step of hydrocracking of the feedstock in the presence of hydrogen in at least one reactor containing a catalyst supported in a bubbling bed, b) a step of separating the effluent obtained at the end of step a), c) a step of maturation of the heavy fraction resulting from the separation step b), d) a step of separating the sediments from the heavy fraction resulting from the curing step c) to obtain said heavy fraction.
    公开号:FR3027911A1
    申请号:FR1460628
    申请日:2014-11-04
    公开日:2016-05-06
    发明作者:Wilfried Weiss；Jeremie Barbier
    申请人:IFP Energies Nouvelles IFPEN；
    IPC主号:
    专利说明:

    [0001] The present invention relates to the refining and conversion of heavy hydrocarbon fractions containing, inter alia, sulfur-containing impurities. It relates more particularly to a process for converting heavy petroleum feeds of the atmospheric residue type and / or vacuum residue for the production of heavy fractions that can be used as fuel bases, in particular 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 (Cl to C4).
    [0002] The quality requirements for marine fuels are described in ISO 8217. The sulfur specification now focuses on SOx emissions (Annex VI of the MARPOL Convention of the International Maritime Organization) and results in a recommendation in terms of quality. Sulfur less than or equal to 0.5% by weight outside the Sulfur Emission Control Areas (ZCES or Emissions Control Areas / ECA) by 2020-2025 and less than or equal to 0.1% by weight in the ZCESCs. According to Annex VI of the MARPOL Convention, the sulfur contents mentioned above are equivalent contents leading to SOx emissions. A ship will therefore be able to use a sulfur fuel oil if the vessel is equipped with a flue gas treatment system that reduces sulfur oxide emissions. Another very restrictive recommendation is the sediment content after aging according to ISO 10307-2 (also known as IP390) which must be less than or equal to 0.1%.
    [0003] 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. On the other hand, terrestrial fuel oils, in particular fuel oils that can be used for the production of heat and / or electricity, may also be subject to stability specifications, in particular maximum sediment contents, the thresholds of which vary according to the places of production. because there is no international harmonization as in the case of maritime transport. There is, however, an interest in reducing the sediment content of terrestrial fuel oils.
    [0004] Residue hydrocracking processes convert low value residues to higher value added distillates. The resulting heavy fraction corresponding to the unconverted residual cut is generally unstable. It contains sediments that are mainly precipitated asphaltenes.
    [0005] This unstable residual cut can not therefore be valorized as fuel oil, especially as bunker oil without a specific treatment since the hydrocracking is operated under severe conditions leading to a high conversion rate.
    [0006] US Pat. No. 6,447,671 describes a process for converting heavy petroleum fractions comprising a first bubbling bed hydrocracking step, a step of removing the catalyst particles contained in the hydrocracking effluent, and then a step of hydrotreating in a bed. fixed.
    [0007] The US2014 / 0034549 application describes a residue conversion process using a bubbling bed hydrocracking step and a step with an upflow reactor associated with a so-called "stripper" reactor. The sediment content of the final effluent is reduced relative to the effluent of the boiling bed stage. However, the sediment content after aging is not less than 0.1% by weight, as required for marketing as a residual type marine fuel. Patent FR2981659 describes a process for converting heavy petroleum fractions comprising a first bubbling bed hydrocracking step and a fixed bed hydrotreating step comprising reactive reactors. The hydrocracking process partially converts heavy feeds to produce atmospheric distillates and / or vacuum distillates. Although ebullated bed technology is known to be suitable for heavy loads loaded with impurities, the bubbling bed inherently produces catalyst fines and sediments which must be removed to satisfy a high water quality. product such as bunker fuel oil. The fines come mainly from the attrition of the catalyst in the bubbling bed. The sediments may be precipitated asphaltenes. Initially in the feedstock, the hydrocracking conditions and in particular the temperature cause them to undergo reactions (dealkylation, polymerization, etc.) leading to their precipitation. Irrespective of the nature of the charge, these phenomena generally occur during the implementation of severe conditions giving rise to conversion rates (for compounds boiling above 540 ° C: 540 ° C.), this is - ie greater than 30, 40 or 50% depending on the nature of the load. The applicant in his research has developed a new process incorporating a step of maturation and separation of sediments downstream of a hydrocracking step. Surprisingly, it has been found that such a process makes it possible to obtain heavy fractions having a low sediment content after aging, said heavy fractions being advantageously able to be used wholly or partly as fuel oil or as fuel oil base, in particular as bunker oil or bunker oil base meeting the specifications, namely and a sediment content after aging less than or equal to 0.1% by weight. An advantage of the process according to the invention is to avoid in particular the risk of clogging of the boat engines and in the case of possible processing steps implemented downstream of the hydrocracking step of avoiding clogging of the engine. or catalytic bed (s) used. More particularly, the invention relates to a process for converting a hydrocarbon feed containing at least one hydrocarbon fraction having a sulfur content of at least 0.1% by weight, an initial boiling temperature of at least 340 ° C and a final boiling temperature of at least 440 ° C to obtain a heavy fraction having a sediment content after aging less than or equal to 0.1% by weight, said process comprising the following steps: ) a step of hydrocracking the feedstock in the presence of hydrogen in at least one reactor containing a catalyst supported in a bubbling bed, b) a step of separating the effluent obtained at the end of step a) into minus a light fraction of hydrocarbons containing fuels bases and a heavy fraction containing compounds boiling at least 350 ° C, c) a stage of maturation of the heavy fraction resulting from stage b) of separation allowing the conversion part of the existing sediment potential sediments, carried out for a period of between 1 and 1500 minutes, at a temperature between 50 and 350 ° C, and a pressure below 20 MPa, d) a sediment separation step of the heavy fraction resulting from the curing step c) to obtain said heavy fraction.
    [0008] In order to form the fuel oil in accordance with the viscosity recommendations, the heavy fractions obtained by the present process can be mixed with fluxing bases so as to achieve the target viscosity of the desired fuel grade.
    [0009] Another point of interest of the process is the partial conversion of the feedstock making it possible to produce, particularly by hydrocracking, atmospheric distillates or vacuum distillates (naphtha, kerosene, diesel, vacuum distillate), which can be used as bases in plants. fuel pools directly or after passing through another refining process such as hydrotreating, reforming, isomerization, hydrocracking or catalytic cracking. Brief Description of Figure 1 Figure 1 illustrates a schematic view of the process according to the invention showing a hydrocracking zone, a separation zone, a zone of maturation and separation of sediments. The feedstock treated in the process according to the invention are advantageously chosen from atmospheric residues, vacuum residues resulting from direct distillation, crude oils, crude head oils, deasphalted oils, deasphalting resins, asphalts or deasphalting pitches, residues resulting from conversion processes, aromatic extracts from lubricant base production lines, tar sands or their derivatives, oil shales or their derivatives, whether taken alone or in combination with mixed. These fillers may advantageously be used as they are or further diluted by a hydrocarbon fraction or a mixture of hydrocarbon fractions which may be chosen from products derived from a process for catalytic cracking in a fluid bed (FCC according to the initials of the name "Anglo-Saxon"). of "Fluid Catalytic Cracking"), a light cutting oil (LCO), a heavy cutting oil (HCO), a decanted oil (OD according to the initials of the English name "Decanted Oil"), a residual FCC, or may come from distillation, gas oil fractions including those obtained by atmospheric or vacuum distillation, such as vacuum gas oil. The heavy feeds may also advantageously comprise cuts from the process of liquefying coal or biomass, aromatic extracts, or any other hydrocarbon cuts or non-petroleum feedstocks such as pyrolysis oil. The fillers according to the invention generally have a sulfur content of at least 0.1% by weight, an initial boiling point of at least 340 ° C. and a final boiling point of at least 440 ° C. preferably a final boiling temperature of at least 540 ° C. Advantageously, the feedstock may contain at least 1% C7 asphaltenes and at least 5 ppm metals, preferably at least 2% C7 asphaltenes and at least 25 ppm metals. The fillers according to the invention are preferably atmospheric residues or residues under vacuum, or mixtures of these residues. Step a): Hydrocracking The feedstock according to the invention is subjected to a hydrocracking step which is carried out in at least one reactor containing a catalyst supported on a bubbling bed and preferably operating with an upward flow of liquid and gas. The objective of the hydrocracking step is to convert the heavy fraction into lighter cuts while partially refining the charge. As bubbling bed technology is widely known, only the main operating conditions will be repeated here. Bubbling bed technologies use extruded bead catalysts supported in the form of extrudates, the diameter of which is generally of the order of 1 mm or less than 1 mm. The catalysts remain inside the reactors and are not evacuated with the products. The temperature levels are high in order to obtain high conversions while minimizing the amounts of catalysts used. The catalytic activity can be kept constant by replacing the catalyst in line. It is therefore not necessary to stop the unit to change the spent catalyst, nor to increase the reaction temperatures along the cycle to compensate for deactivation. In addition, operating at constant operating conditions provides consistent yields and product qualities along the cycle. Also, because the catalyst is kept agitated by a large recycling of liquid, the pressure drop on the reactor remains low and constant. The conditions of hydrocracking step a) in the presence of hydrogen are usually conventional bubbling bed hydrocracking conditions of a liquid hydrocarbon fraction. It is advantageously carried out under a hydrogen partial pressure of 5 to 35 MPa, often 8 to 25 MPa and usually 12 to 20 MPa at a temperature of 330 to 500 ° C and often 350 to 450 ° C. The hourly space velocity (VVH) and the hydrogen partial pressure are important factors that are chosen according to the characteristics of the product to be treated and the desired conversion. The VVH, defined as the volumetric flow rate of the feed divided by the total volume of the reactor, is generally in a range of from 0.05 hr -1 to 5 hr -1, preferably from 0.1 hr -1 to 2 h -1 and more preferably 0.2 h -1 to 1 h -1. The amount of hydrogen mixed with the feedstock is usually 50 to 5000 Nm3 / m3 (normal cubic meters (Nm3) per cubic meter (m3) of feedstock) and most often 100 to 1000 Nm3 / m3 and preferably 200 to 500 Nm3 / m3. It is possible to use a conventional granular hydrocracking catalyst comprising, on an amorphous support, at least one metal or metal compound having a hydro-dehydrogenating function. This catalyst may be a catalyst comprising Group VIII metals, for example nickel and / or cobalt, most often in combination with at least one Group VIB metal, for example molybdenum and / or tungsten. For example, a catalyst comprising from 0.5 to 10% by weight of nickel and preferably from 1 to 5% by weight of nickel (expressed as nickel oxide NiO) and from 1 to 30% by weight of molybdenum of preferably from 5 to 20% by weight of molybdenum (expressed as molybdenum oxide MoO 3) on an amorphous mineral support. This support will for example be chosen from the group formed by alumina, silica, silica-aluminas, magnesia, clays and mixtures of at least two of these minerals. This support may also contain other compounds and for example oxides chosen from the group formed by boron oxide, zirconia, titanium oxide and phosphoric anhydride. Most often an alumina support is used and very often a support of alumina doped with phosphorus and possibly boron. When phosphorus pentoxide P205 is present, its concentration is usually less than 20% by weight and most often less than 10% by weight. The concentration of boron trioxide B 2 O 3 is usually from 0 to 10% by weight. The alumina used is usually a gamma or eta alumina. This catalyst is most often in the form of extrudates. The total content of metal oxides of groups VI and VIII is often 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 VI on metal (or metals) of group VIII is in general from 20 to 1 and most often from 10 to 2. The used catalyst is partly replaced by fresh catalyst, generally by withdrawal at the bottom of the reactor and introduction at the top of the catalyst reactor fresh or new at regular time interval, that is to say for example by puff or almost continuously. The catalyst can also be introduced from below and withdrawn from the top of the reactor. For example, fresh catalyst can be introduced every day. The replacement rate of spent catalyst with fresh catalyst may be, for example, from about 0.05 kilograms to about 10 kilograms per cubic meter of charge. This withdrawal and this replacement are performed using devices allowing the continuous operation of this hydrocracking step. The unit usually comprises a recirculation pump for maintaining the bubbling bed catalyst by continuously recycling at least a portion of the liquid withdrawn at the top of the reactor and reinjected at the bottom of the reactor. It is also possible to send the spent catalyst withdrawn from the reactor into a regeneration zone in which the carbon and the sulfur contained therein are eliminated before it is reinjected in the hydrocracking step a). Most often, the hydrocracking step a) is carried out under the conditions of the H-OILO process as described, for example, in US Pat. No. 6,270,654. The hydrocracking can be carried out in a single reactor or in several (generally two) reactors arranged in series. The use of at least two ebullated bed reactors in series results in higher quality and better yielding products, thus limiting the energy and hydrogen requirements in possible post-treatments. In addition, the hydrocracking into two reactors makes it possible to have improved operability in terms of the flexibility of the operating conditions and of the catalytic system. Generally, the temperature of the second reactor is preferably at least 5 ° C higher than that of the first bubbling bed reactor. The pressure of the second reactor is 0.1 to 1 MPa lower than for the first reactor to allow the flow of at least a portion of the effluent from the first step without pumping is necessary. The different temperature operating conditions in the two hydrocracking reactors are selected to be able to control the hydrogenation and conversion of the feedstock to desired products in each reactor. Optionally, the effluent obtained at the end of the first hydrocracking reactor is separated from the light fraction and at least a portion, preferably all, of the residual effluent is treated in the second reactor. hydrocracking. This separation can be carried out in an inter-stage separator as described in US Pat. No. 6,270,654 and makes it possible in particular to avoid excessive hydrocracking of the light fraction in the second hydrocracking reactor. It is also possible to transfer in whole or in part the spent catalyst withdrawn from the first lower temperature hydrocracking reactor, directly into the second hydrocracking reactor, operating at a higher temperature or transferring in full or in part. part used catalyst withdrawn from the second hydrocracking reactor directly to the first hydrocracking reactor. This cascade system is described in US4816841.
    [0010] The hydrocracking step may also be carried out in at least one reactor operating in a hybrid bed mode, that is to say operating in a bubbling bed with a supported catalyst associated with a dispersed catalyst consisting of very fine catalyst particles. forming a suspension with the charge to be treated.
    [0011] A hybrid bed has two populations of catalyst, a population of bubbling bed catalyst to which is added a population of "dispersed" type catalyst. The term "dispersed" refers to an implementation of the reactor in which the catalyst is in the form of very fine particles, that is to say generally a size of between 1 nanometer (ie 10-9 m) and 150 microns, preferably between 0.1 and 100 microns, and even more preferably between 10 and 80 microns.
    [0012] In a first variant, the hydrocracking stage may comprise a first bubbling bed reactor followed by a second hybrid bed type reactor (that is to say bubbling bed type with "dispersed" type catalyst injection). .
    [0013] In a second variant, the hydrocracking step may comprise a first hybrid bed type reactor followed by a second hybrid type reactor. In a third variant, the hydrocracking step may comprise a single hybrid bed type reactor.
    [0014] The "disperse" catalyst used in the hybrid bed reactor may be a sulfide catalyst preferably containing at least one member selected from the group consisting of Mo, Fe, Ni, W, Co, V, Ru. These catalysts are generally monometallic or bimetallic (by combining, for example, a non-noble group VIIIB element (Co, Ni, Fe) and a group VIB element (Mo, W) .The catalysts used may be heterogeneous solid powders ( such as natural ores, iron sulphate, etc.), dispersed catalysts derived from water-soluble precursors such as phosphomolybdic acid, ammonium molybdate, or a mixture of Mo or Ni oxide. The catalysts used are derived from soluble precursors in an organic phase (oil-soluble catalysts) .The precursors are generally organometallic compounds such as the naphthenates of Mo, Co and Fe. , or Ni, or the Mo octoates, or multi-carbonyl compounds of these metals, for example 2-ethyl hexanoates of Mo or Ni, acetylacetonates of Mo or Ni, C7-C12 fatty acid salts of Mo or W , etc. They can be used in the presence of a surfactant to improve the dispersion of the metals, when the catalyst is bimetallic. The catalysts are in the form of dispersed particles, colloidal or otherwise depending on the nature of the catalyst. Such precursors and catalysts that can be used in the process according to the invention are widely described in the literature. In general, the catalysts are prepared before being injected into the feed. The preparation process is adapted according to the state in which the precursor is and of its nature. In all cases, the precursor is sulfided (ex-situ or in-situ) to form the catalyst dispersed in the feedstock. In the case of so-called oil-soluble catalysts, the precursor is advantageously mixed with a carbonaceous feedstock (which may be a part of the feedstock to be treated, an external feedstock, a recycled fraction, etc.), the mixture is then sulphurized by addition of a sulfur compound (preferred hydrogen sulphide or optionally an organic sulphide such as DMDS in the presence of hydrogen) and heated. The preparations of these catalysts are described in the literature. The "disperse" catalyst particles as defined above (powders of metallic mineral compounds or of precursors soluble in water or in oil) generally have a size of between 1 nanometer and 150 micrometers, more preferably between 0.1 and 100 microns, and even more preferably between 10 and 80 microns. The content of catalytic compounds (expressed as weight percentage of metal elements of group VIII and / or of group VIB) is between 0 and 10% by weight, preferably between 0 and 1% by weight. Additives may be added during the preparation of the catalyst or to the "dispersed" catalyst before it is injected into the reactor. These additives are described in the literature. The preferred solid additives are inorganic oxides such as alumina, silica, mixed Al / Si oxides, supported spent catalysts (eg, on alumina and / or silica) containing at least one group VIII element (such as that Ni, Co) and / or at least one group VIB element (such as Mo, W). For example, the catalysts described in the application US2008 / 177124. Carbonaceous solids of low hydrogen content (eg, 4% hydrogen) such as coke or milled activated carbon, optionally pretreated, may also be used. Mixtures of such additives can also be used. The particle size of the additive is generally between 10 and 750 microns, preferably between 100 and 600 microns. The content of any solid additive present at the inlet of the reaction zone of the "dispersed" hydrocracking process is between 0 and 10% by weight, preferably between 1 and 3% by weight, and the content of catalytic compounds (expressed as weight percentage of metal elements of group VIII and / or group VIB) is between 0 and 10% by weight, preferably between 0 and 1% by weight. The hybrid bed reactor (s) used in the hydrocracking zone therefore consist of two populations of catalysts, a first population using supported catalysts in the form of extrudates whose diameter is advantageously between 0.8 and 1.2 mm. , generally equal to 0.9 mm or 1.1 mm and a second population of "dispersed" type catalyst discussed above. The fluidization of the catalyst particles in the bubbling bed is enabled by the use of a boiling pump which allows a recycle of liquid, generally inside the reactor. The flow rate of liquid recycled by the boiling pump is adjusted so that the supported catalyst particles are fluidized but not transported, so that these particles remain in the bubbling bed reactor (with the exception of catalyst fines that can be formed by attrition and entrained with the liquid since these fines are small). In the case of a hybrid bed, the "dispersed" type catalyst is also entrained with the liquid since the "dispersed" type catalyst consists of particles of very small size. Step b): Separation of the Hydrocracking Effluent The effluent obtained at the end of the hydrocracking step a) undergoes at least one separation step, optionally supplemented by further additional separation steps, allowing the separation of the hydrocracking effluent. separating at least a light fraction of hydrocarbons containing fuels bases and a heavy fraction containing boiling compounds at least 350 ° C.
    [0015] The separation step may advantageously be carried out by any method known to those skilled in the art such as, for example, the combination of one or more high and / or low pressure separators, and / or distillation stages and / or or high and / or low pressure stripping. Preferably, the separation step b) makes it possible to obtain a gaseous phase, at least a light fraction of hydrocarbons of the naphtha, kerosene and / or diesel type, a vacuum distillate fraction and a vacuum residue fraction and / or a fraction of atmospheric residue. The separation may be carried out in a fractionation section which may first comprise a high temperature high pressure separator (HPHT), and optionally a low temperature high pressure separator (HPBT), and / or atmospheric distillation and / or distillation under empty. The effluent obtained at the end of step a) is separated (generally in an HPHT separator) into a light fraction and a heavy fraction containing predominantly boiling compounds at least 350 ° C. The cutting point of the separation is advantageously between 200 and 400 ° C.
    [0016] In a variant of the process of the invention, during step b), the effluent from the hydrocracking may also undergo a succession of flashes comprising at least one high temperature high pressure balloon (HPHT) and a low pressure balloon high temperature (BPHT) for separating a heavy fraction which is sent in a steam stripping step for removing from said heavy fraction at least a light fraction rich in hydrogen sulfide. The heavy fraction recovered at the bottom of the stripping column contains compounds boiling at least 350 ° C. but also atmospheric distillates. According to the process of the invention, said heavy fraction separated from the light fraction rich in hydrogen sulphide is then sent to the maturation step c) and then to the sediment separation step d). In a variant, at least a portion of the so-called heavy fraction from step b) is fractionated by atmospheric distillation into at least one atmospheric distillate fraction containing at least one light fraction of naphtha, kerosene and / or diesel type hydrocarbons. and an atmospheric residue fraction. At least a part of the atmospheric residue fraction can be sent in the maturation step c) and then in the sediment separation step d).
    [0017] The atmospheric residue may also be at least partially fractionated by vacuum distillation into a vacuum distillate fraction containing vacuum gas oil and a vacuum residue fraction. Said fraction vacuum residue is advantageously sent at least partly in the maturation step c) and then in the sediment separation step d). At least a portion of the vacuum distillate and / or the vacuum residue may also be recycled to the hydrocracking step a). Irrespective of the separation method used, the light fraction (s) obtained may (may) undergo further separation steps, possibly in the presence of the light fraction obtained from the internal separator. stage between the two hydrocracking reactors. Advantageously, it (s) is (are) subject (s) to atmospheric distillation to obtain a gaseous fraction, at least a light fraction of naphtha, kerosene and / or diesel type hydrocarbons and a vacuum distillate fraction. Part of the atmospheric distillate and / or the vacuum distillate from the separation step b) may constitute a part of a fuel oil as a fluxing agent. These cuts can also be marine fuels with low viscosity (MGO or MGO, Marine Diesel Oil or Marine Gas Oil according to English terminology). Another part of the vacuum distillate can still be upgraded by hydrocracking and / or catalytic cracking in a fluidized bed. The gaseous fractions resulting from the separation step preferably undergo a purification treatment to recover the hydrogen and recycle it to the hydrocracking reactors (step a)). The recovery of different fuel base cuts (LPG, naphtha, kerosene, diesel and / or vacuum gas oil) obtained from the present invention is well known to those skilled in the art. The products obtained can be integrated in fuel tanks (also called "pools" fuels according to the English terminology) or undergo additional refining steps. The fraction (s) naphtha, kerosene, gas oil and vacuum gas oil may be subjected to one or more treatments (hydrotreatment, hydrocracking, alkylation, isomerization, catalytic reforming, catalytic cracking or thermal or other) to bring them to the specifications. required (sulfur content, smoke point, octane, cetane, etc ...) separately or in mixture. Advantageously, the vacuum distillate leaving the bubbling bed after separation can be hydrotreated. This hydrotreated vacuum distillate may be used as a fluxing agent for the fuel oil pool having a sulfur content of less than or equal to 0.5% by weight or may be used directly as oil with a sulfur content of less than or equal to 0.1% by weight. Part of the atmospheric residue, vacuum distillate and / or vacuum residue may undergo further refining steps, such as hydrotreatment, hydrocracking, or fluidized catalytic cracking. Step c): Maturation of the sediments The heavy fraction obtained at the end of the separation step b) contains organic sediments which result from the hydrocracking conditions and the catalyst residues. Part of the sediments consist of asphaltenes precipitated under hydrocracking conditions and are analyzed as existing sediments (IP375). Depending on the hydrocracking conditions, the sediment content in the heavy fraction varies. From an analytical point of view, existing sediments (IP375) and sediments after aging (IP390) are distinguished from potential sediments. However, high hydrocracking conditions, that is to say when the conversion rate is for example greater than 30, 40 or 50% depending on the load, cause the formation of existing sediments and potential sediments. In order to obtain a fuel oil or base of reduced sediment fuel oil, in particular bunker oil or bunker oil base meeting the recommendations for a sediment content after aging (IP390) less than or equal to 0.1 %, the method according to the invention comprises a maturation step making it possible to improve the sediment separation efficiency and thus to obtain stable fuel oils or oil bases, ie a sediment content after lower aging. or equal to 0.1% by weight. The maturation step according to the invention makes it possible to form all the existing and potential sediments (by converting the potential sediments into existing sediments) so as to separate them more efficiently and thus respect the sediment content after aging (IP390) of 0.1% maximum weight. The curing stage according to the invention is advantageously carried out for a residence time of between 1 and 1500 minutes, preferably between 25 and 300 minutes, more preferably between 60 and 240 minutes, at a temperature between 50 and 350 ° C, preferably between 75 and 300 ° C and more preferably between 100 and 250 ° C, a pressure advantageously less than 20 MPa, preferably less than 10 MPa, more preferably less than 3 MPa and even more preferentially lower at 1.5 MPa. The ripening step may be carried out using an exchanger or a heating furnace followed by one or more capacity (s) in series or in parallel such (s) as a horizontal or vertical balloon, optionally with a settling function to remove some of the heavier solids, and / or a piston reactor. A stirred and heated tank may also be used, and may be provided with a bottom draw to remove some of the heavier solids. Advantageously, step c) of maturation of the heavy fraction resulting from step b) is carried out in the presence of an inert gas and / or an oxidizing gas. Stage c) of maturation is carried out in the presence of an inert gas such as nitrogen, or in the presence of an oxidizing gas such as oxygen, or in the presence of a mixture containing an inert gas and an oxidizing gas such as air or depleted air by nitrogen. The use of an oxidizing gas accelerates the maturation process.
    [0018] In the case where the maturation stage is carried out in the presence of an inert and / or oxidizing gas, said gas is mixed with the heavy fraction resulting from stage b) before the stage of maturation and separation of this gas after maturation so as to obtain a liquid fraction at the end of the c) stage of maturation. Such a gas / liquid implementation can for example be carried out in a bubble column. According to another embodiment, the inert and / or oxidizing gas may also be introduced during the d) stage of maturation, for example by means of a bubbling (injection of gas from below) in a stirred tank which allows to promote gas / liquid contact.
    [0019] At the end of the curing step c), at least one hydrocarbon fraction with an enriched content of existing sediments is obtained which is sent to step d) of separation of the sediments.
    [0020] Step d): Separation of sediments The method according to the invention further comprises a step d) of separating sediments and catalyst residues. The heavy fraction obtained at the end of the curing step c) contains precipitated asphaltene-type organic sediments which result from the hydrocracking and maturation conditions. This heavy fraction may also contain catalyst fines resulting from the attrition of extruded type catalysts in the implementation of hydrocracking reactor. This heavy fraction may optionally contain "dispersed" catalyst residues in the case of the implementation of a hybrid reactor.
    [0021] Thus, at least a portion of the heavy fraction resulting from the curing step c) is subjected to a separation of the sediments and the catalyst residues, by means of at least one physical separation means chosen from a filter, a membrane separation, a bed of organic or inorganic type filtering solids, electrostatic precipitation, a centrifugation system, decantation, auger withdrawal. A combination, in series and / or in parallel, of several separation means of the same type or different type can be used during this step d) separation of sediments and catalyst residues. One of these solid-liquid separation techniques may require the periodic use of a light rinsing fraction, resulting from the process or not, allowing for example the cleaning of a filter and the evacuation of sediments. The heavy fraction resulting from step d) with a reduced sediment content can advantageously be used as a base for fuel oil or as fuel oil, in particular as a bunker oil or bunker oil base, having a sediment content after aging of less than 0, 1% weight Advantageously, said heavy fraction is mixed with one or more fluxing bases selected from the group consisting of catalytically cracked light cutting oils, catalytically cracked heavy cutting oils, catalytic cracking residue, kerosene, a gas oil, a vacuum distillate and / or a decanted oil. Step e) optional: optional separation step The effluent obtained at the end of step d) of sediment separation can undergo an optional separation step allowing the separation of at least one light fraction of hydrocarbons containing fuels bases. and a heavy fraction containing predominantly boiling compounds at least 350 ° C. This separation step can advantageously be carried out by any method known to those skilled in the art such as, for example, the combination of one or more high and / or low pressure separators, and / or distillation stages and / or or high and / or low pressure stripping. This optional step e) of separation is similar to the separation step b) and will not be further described. Preferably, this separation step makes it possible to obtain at least a light fraction of hydrocarbons of the naphtha, kerosene and / or diesel type, a vacuum distillate fraction and a vacuum residue fraction and / or an atmospheric residue fraction. Part of the atmospheric residue and / or the vacuum residue can also be recycled to the hydrocracking step a).
    [0022] Step f): Optional hydrotreatment step The sulfur content of the heavy fraction resulting from step d) or e) when the latter is used, and containing predominantly compounds boiling at least 350 ° C., is a function of operating conditions of the hydrocracking step but also the sulfur content of the original charge. Thus, for low sulfur feeds, generally less than 1.5% by weight, it is possible to directly obtain a heavy fraction with less than 0.5% by weight sulfur as required for vessels without treatment. fumes 20 and operating outside the ZCSEs by 2020-2025. For more sulfurous feedstocks, whose sulfur content is generally greater than 1.5% by weight, the sulfur content of the heavy fraction may exceed 0.5% by weight. In such a case, a step f) of hydrotreatment in a fixed bed is made necessary in the case where the refiner wishes to reduce the sulfur content, in particular for a bunker oil base or a bunker oil intended to be burned on a ship without smoke treatment. The fixed bed hydrotreating step f) is carried out on at least a portion of the heavy fraction resulting from step d) or e) when step e) is carried out. The heavy fraction from step f) can advantageously be used as a base of fuel oil or as fuel oil, especially as a base of bunker oil or as bunker oil, having a sediment content after aging less than 0.1% by weight. Advantageously, said heavy fraction is mixed with one or more fluxing bases selected from the group consisting of catalytically cracked light cutting oils, catalytically cracked heavy cutting oils, catalytic cracking residue, kerosene, a gas oil, a vacuum distillate and / or a decanted oil. The heavy fraction resulting from the sediment separation step d) or e) when step e) is carried out is sent to the hydrotreatment step f) comprising one or more hydrotreatment zones in fixed beds. The sending in a fixed bed of a heavy fraction devoid of sediment is an advantage of the present invention since the fixed bed will be less subject to clogging and increased pressure drop.
    [0023] Hydroprocessing (HDT) is understood to mean, in particular, hydrodesulphurization (HDS) reactions, hydrodenitrogenation (HDN) reactions and hydrodemetallation (HDM) reactions, but also hydrogenation, hydrodeoxygenation, hydrodearomatization, hydrodenetration, hydroisomerization, hydrodealkylation, hydrocracking, hydro-deasphalting and Conradson carbon reduction. Such a method of hydrotreating heavy cuts is widely known and can be related to the process known as HYVAHLFTM described in US5417846.
    [0024] The person skilled in the art easily understands that in the hydrodemetallization stage, hydrodemetallation reactions are mainly carried out but also part of the hydrodesulfurization reactions. Similarly, in the hydrodesulfurization step, hydrodesulphurization reactions are mainly carried out but also part of the hydrodemetallation reactions.
    [0025] According to one variant, a co-charge may be introduced with the heavy fraction in the hydrotreatment step f). This co-charge may be chosen from atmospheric residues, vacuum residues from direct distillation, deasphalted oils, aromatic extracts from lubricant base production lines, hydrocarbon fractions or a mixture of hydrocarbon fractions which can be used. chosen from the products resulting from a fluid-bed catalytic cracking process: a light cutting oil (LCO), a heavy cutting oil (HCO), a decanted oil, or possibly derived from distillation, the gas oil fractions including those obtained by atmospheric distillation or under vacuum, such as vacuum gas oil. The hydrotreatment step can advantageously be carried out at a temperature of between 300 and 500 ° C., preferably 350 ° C. to 420 ° C. and under a hydrogen partial pressure advantageously between 2 MPa and 25 MPa. preferably between 10 and 20 MPa, an overall hourly space velocity (VVH) ranging from 0.1 hr -1 to 5 hr -1 and preferably from 0.1 hr -1 to 2 hr, an amount of hydrogen mixed with the charge usually from 100 to 5000 Nm3 / m3 (normal cubic meters (Nm3) per cubic meter (m3) of liquid charge), most often from 200 to 2000 Nm3 / m3 and preferably from 300 to 1500 Nm3 / m3. Usually, the hydrotreatment step is carried out industrially in one or more liquid downflow reactors. The hydrotreatment temperature is generally adjusted according to the desired level of hydrotreatment. The hydrotreatment catalysts used are preferably known catalysts and are generally granular catalysts comprising, on a support, at least one metal or metal compound having a hydrodehydrogenating function. These catalysts are advantageously catalysts comprising at least one Group VIII metal, generally selected from the group consisting of nickel and / or cobalt, and / or at least one Group VIB metal, preferably molybdenum and / or tungsten. For example, a catalyst comprising from 0.5 to 10% by weight of nickel and preferably from 1 to 5% by weight of nickel (expressed as nickel oxide NiO) and from 1 to 30% by weight of molybdenum, preferably from 5 to 20% by weight of molybdenum (expressed as molybdenum oxide MoO 3) on a mineral support. This support will, for example, be selected from the group formed by alumina, silica, silica-aluminas, magnesia, clays and mixtures of at least two of these minerals. Advantageously, this support contains other doping compounds, in particular oxides chosen from the group formed by 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 concentration of phosphoric anhydride P2O5 is usually between 0 or 0.1% and 10% by weight. The concentration of boron trioxide B205 is usually between 0 or 0.1% and 10% by weight. The alumina used is usually alumina or TI. This catalyst is most often in the form of extrudates. The total content of metal oxides of groups VIB and VIII is often 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 usually 20 to 1 and most often 10 to 2.
    [0026] In the case of a hydrotreatment step including a hydrodemetallation step (HDM), then a hydrodesulfurization step (HDS), it is most often used specific catalysts adapted to each step. Catalysts that can be used in the hydrodemetallation (HDM) stage are for example indicated in patents EP113297, EP113284, US5221656, US5827421, US7119045, US5622616 and US5089463. Hydrodemetallation (HDM) catalysts are preferably used in the reactive reactors. Catalysts that can be used in the hydrodesulfurization (HDS) stage are for example indicated in patents EP113297, EP113284, US6589908, US4818743 or US6332976. It is also possible to use a mixed catalyst that is active in hydrodemetallization and hydrodesulfurization for both the hydrodemetallation (HDM) section and the hydrodesulfurization (HDS) section as described in patent FR2940143.
    [0027] Prior to the injection of the feed, the catalysts used in the process according to the present invention are preferably subjected to an in-situ or ex-situ sulphurization treatment.
    [0028] Step c1) Optional step of separation of the hydrotreatment effluent The optional separation step g) may advantageously be carried out by any method known to those skilled in the art such as, for example, the combination of one or more high and / or low pressure separators, and / or distillation and / or high and / or low pressure stripping stages. This optional separation step g) is similar to the separation step b) and will not be further described. In an alternative embodiment of the invention, the effluent obtained in step f) may be at least partly, and often entirely, sent to a separation step g), comprising atmospheric distillation and / or vacuum distillation. The effluent of the hydrotreatment stage is fractionated by atmospheric distillation into a gaseous fraction, at least one atmospheric distillate fraction containing the fuels bases (naphtha, kerosene and / or diesel) and an atmospheric residue fraction. At least a portion of the atmospheric residue can then be fractionated by vacuum distillation into a vacuum distillate fraction containing vacuum gas oil and a vacuum residue fraction. The vacuum residue fraction and / or the vacuum distillate fraction and / or the atmospheric residue fraction may be at least partly the bases of low-sulfur fuel oils having a sulfur content of less than or equal to 0.5% by weight and a sediment content after aging less than or equal to 0.1%. The vacuum distillate fraction can constitute a fuel oil base having a sulfur content of less than or equal to 0.1% by weight.
    [0029] Part of the vacuum residue and / or the atmospheric residue can also be recycled to the hydrocracking step a).
    [0030] Fluxaqe To obtain a fuel oil, the heavy fractions from steps d) and / or e) and / or f) and / or g) can be mixed with one or more fluxing bases selected from the group consisting of light cutting oils. catalytic cracking, catalytically cracked heavy cutting oils, catalytic cracking residue, kerosene, gas oil, vacuum distillate and / or decanted oil. Preferably, kerosene, gas oil and / or vacuum distillate produced in the process of the invention will be used. Advantageously, kerosene, gas oil and / or vacuum distillate obtained in process separation steps b) or g) will be used.
    [0031] DETAILED DESCRIPTION OF FIG. 1 FIG. 1 represents an exemplary implementation according to the invention without limiting its scope.
    [0032] In FIG. 1, the charge (10), preheated in the chamber (92), mixed with recycled hydrogen (14) and additional hydrogen (90) preheated in the enclosure (91), is introduced via line (96) into the hydrocracking step at the bottom of the first bubbling bed reactor (98) operating at an upward flow of liquid and gas and containing at least one hydrocracking catalyst of the supported type.
    [0033] Advantageously, a co-charge (94) can be introduced. Advantageously, the first bubbling bed reactor operates in hybrid mode, the "dispersed" type catalyst is then introduced via line (100) upstream of the first hydrocracking reactor (98).
    [0034] Advantageously, the converted effluent (104) from the reactor (98) may be separated from the light fraction (106) in an inter-stage separator (108). All or part of the effluent from (110) inter-stage separator (108) is advantageously mixed with additional hydrogen (157), if necessary preheated (not shown).
    [0035] This mixture is then injected by the pipe (112) into a second hydrocracking reactor (102) also in a bubbling bed operating at an upward flow of liquid and gas containing at least one hydrocracking catalyst of the supported type. Advantageously, the second bubbling bed reactor operates in hybrid mode, the "dispersed" type catalyst is then injected upstream of the first reactor (98) in the case of two hybrid reactors in series, or the "dispersed" type catalyst. is injected upstream of the second reactor (102) via a pipe not shown in the case of a first bubbling bed reactor followed in the second hybrid reactor. The operating conditions, in particular the temperature, in this reactor are chosen to reach the desired conversion level, as previously described. The effluent from the hydrocracking reactors is sent via line (134) into a high temperature high pressure (HPHT) separator (136) from which a gaseous fraction (138) and a heavy fraction (140) are recovered. The gaseous fraction (138) is sent generally via an exchanger (not shown) or a dry cooler (142) for cooling to a low temperature high pressure separator (HPBT) (144) from which a gaseous fraction (146) containing the gaseous fraction (146) is recovered. gas (H2, H2S, NH3, C1-C4 hydrocarbons ...) and a liquid fraction (148). The gaseous fraction (146) of the low temperature high pressure separator (HPBT) (144) can be processed in a hydrogen purification unit (150) from which hydrogen (152) is recovered for recycling via the compressor. (154) and line (156) and / or line (157) to the hydrocracking section. Gases containing undesirable nitrogen and sulfur compounds are removed from the plant (flow (158) which may represent a plurality of streams, in particular a flow rich in H 2 S and one or more purges containing light hydrocarbons) The liquid fraction (148) of the separator High temperature low pressure (HPBT) (144) is advantageously relaxed in the device (160) to be sent to the fractionation system (172).
    [0036] The heavy fraction (140) resulting from the high temperature high pressure separation (HPHT) (136) is advantageously relaxed in the device (174) and then sent to the fractionation system (172). Optionally, a medium pressure separator (not shown) after the expander (174) can be installed to recover a vapor phase that is sent to the purification unit (150) and / or a dedicated medium pressure purification unit (not shown ), and a liquid phase which is fed to the fractionation section (172). Fractions (148) and (140) may be sent together, after expansion, to the system (172). The fractionation system (172) comprises an atmospheric distillation system for producing a gaseous effluent (176), at least a so-called light fraction (178), containing in particular naphtha, kerosene and diesel, and an atmospheric residue fraction (180). ). All or part of the atmospheric residue fraction (180) can be sent to a vacuum distillation column (184) to recover a fraction containing the vacuum residue (186) and a vacuum distillate fraction (188) containing vacuum gas oil . The atmospheric residue fraction (182) and / or the vacuum residue fraction (186) are subjected to a stage of maturation and separation of sediments and catalyst residues in order to constitute desired oil bases. An atmospheric residue (182) fraction is optionally preheated in an oven or exchanger (205) to achieve the temperature necessary for maturation (conversion of potential sediments into existing sediments) that occurs in the capacity (207). The purpose of the capacity (207) is to provide a residence time necessary for maturation, it can therefore be a horizontal or vertical flask, a buffer tank, a stirred tank or a reactor piston. The heating function can be integrated with the capacity in the case of a stirred stirred tank according to an embodiment not shown. The capacity (207) may also allow settling so as to evacuate a portion of the solids (208).
    [0037] The maturing stream (209) is then subjected to solid-liquid separation (191) to obtain a sediment-reduced fraction (212) and a sediment-rich fraction (211). Similarly, a vacuum residue type fraction (186) is optionally preheated in an oven or exchanger (213) so as to reach the temperature necessary for the maturation that takes place in the capacity (215). The purpose of the capacity (215) is to provide a residence time necessary for maturation, it can therefore be a horizontal or vertical flask, a buffer tank, a stirred tank or a reactor piston. The heating function can be integrated with the capacity in the case of a stirred stirred tank according to an embodiment not shown. The capacity (215) may also allow settling so as to evacuate a portion of the solids (216). The maturation stream (217) is then subjected to a solid-liquid separation (192) to obtain a sediment-reduced fraction (219) and a sediment-rich fraction (218). According to a mode not shown, the curing devices (207) and (215) can operate in the presence of a gas, in particular an inert or oxidizing gas, or a mixture of inert gas and oxidizing gas. In case of use of gas during maturation, a device not shown will separate the gas from the liquid. According to a mode not shown, it is also possible to carry out a step of maturation and separation of the sediments and catalyst residues on a heavy fraction resulting from the hydrocracking effluent separation step, for example on a heavy cut from a separator, for example on the flow (140) before or after the expansion (174). An advantageous mode not shown may consist in operating the stage of maturation and separation of the sediments on the stream recovered at the bottom of a stripping column. When the stage of maturation and separation of sediments and catalyst residues is operated upstream of a distillation column, this column is less prone to fouling.
    [0038] At least a portion of the streams (188) and / or (212) and / or (219) constitutes one or more desired oil bases, in particular bases for low-sediment fuels. Some of the streams (188) and / or (212) and / or (219), before or after the optional sediment ripening and separation step, may be recycled via line (190) to step hydrocracking. EXAMPLES: The following example illustrates the invention without, however, limiting its scope. The treated feed is a vacuum residue (RSV Ural) whose characteristics are shown in Table 1.
    [0039] Table 1: Characteristics of the load Section RSV Ural Density 15/4 1,018 Sulfur% mass 2,60 Carbon Conradson 14 Asphaltenes C7 (° / 0 mass) 4.1 NI + V ppm 172 350 ° C + (° / 0 mass of 97 , Compounds boiling above 350 ° C.) 540 ° C. + (° / 0 mass of 70.3 compounds boiling above 540 ° C.) The feedstock is subjected to a hydrocracking step in two successive reactors in a bed whirlpool.
    [0040] According to a variant made in a second experiment, the two boiling bed reactors are operated in hybrid mode, that is to say using a dispersed catalyst injected at the inlet of the first reactor in addition to the supported catalysts. The operating conditions of the hydrocracking section are given in Table 2. The NiMo catalyst on Alumina used is sold by the company Axens under the reference H0C458. Table 2: Operating conditions hydrocracking section 2 beds 2 hybrid bubbling bubbling beds NiMo catalyst on NiMo on Alumina alumina + Naphthenate Mo Bubble bed temperature R1 (° C) 420 420 Boiling bed temperature R2 (° C) 425 425 Partial hydrogen pressure , MPa 15 VVHc (Sm3 / h load / m3 supported catalysts), h-1 0.55 0.55 VVHR (Sm3 / h load / m3 reactors), h-1 0.3 0.3 Concentration of dispersed catalyst ( ppm of precursor in the input charge hybrid beds) 0 100 H2 input (Nm3 / m3 load) 600 600 VVI-Ic: ratio between the hourly volumetric flow rate of charge and the volume of catalysts supported without boiling VVHR: ratio between the hourly volume flow rate charge and the volume of the reactors The hydrocracking effluents are then subjected to a separation comprising an atmospheric distillation and making it possible to recover a gaseous fraction and a heavy fraction. The heavy fraction (350 ° C + fraction) is then treated according to two variants: A) No additional treatment (not in accordance with the invention) B) A sediment maturation step (4h at 150 ° C. carried out in a stirred tank heated in the presence of a 50/50 air / nitrogen mixture at a pressure of 0.5 MPa) and then a step of physically separating the sediments using a filter (according to the invention) According to the two previous variants A) and B), the 350 ° C + fractions are distilled in the laboratory for the qualities and yields of vacuum distillate and vacuum residue. The yields as well as the sulfur content and the viscosity (for heavy cuts) according to the two embodiments of the hydrocracking step (bubbling beds or hybrid beds) are indicated in Table 3. Table 3: Yields, content Sulfur and viscosity bubbling bed section (% wt / load) 2 bubbling beds 2 Hybrid bubbling beds Products Yield S Viscosity Yield S Viscosity (% wt) (% wt) at 100 ° C (wt%) (wt%) at 100 ° C (Cst) (Cst) NH3 0.08 0.08 H2S 2.29 2.30 cl-c4 (gas) 3.94 4.62 Naphtha (PI-180 ° C) 9.53 0.07 11.70 0.12 Diesel (180-350 ° C) 24.81 0.17 28.87 0.20 Vacuum Distillates (350-540 ° C) 39.73 0.45 7.4 36.12 0.51 7.2 Residue vacuum (540 + ° C) 21.13 0.76 277 17.93 0.88 579 Sum 101.51 101.61 H2 consumed (° / 0 wt / load) 1.51 1.61 Charge stage of ripening: sum of yields Distillates under vacuum (350-540 ° C) and Vacuum residue (540 + ° C) 60.86 0.56 54.05 0.63 Yield = Yield, wt = weight The operating conditions of the A hydrocracking step coupled with a step of maturation and separation of the sediments according to the invention carried out on the heavy fraction resulting from the atmospheric distillation have an impact on the stability of the effluents obtained. This is illustrated by the post-aging sediment contents measured in the atmospheric residues (350 ° C + cut). The performance is summarized in Table 4 below.
    [0041] Table 4: Summary of performances with or without ripening and sediment separation Hydrocracking 2 Hydrocracking 2 bubbling beds bubbling beds (420/425 ° C) hybrids (420/425 ° C) Hydrodesulphurization rate (%) 78.5 75.8 Conversion rate (%) 70 74.5 Maturation No Yes No Yes Sediment separation No Yes No Yes Sediment content after aging (IP390) in section 350 ° C + 0.8 <0.1 0.7 <0.1 Conversion rate = ((cutting quantity 540 ° C + load - cutting quantity 540 ° C + effluent) / (cutting quantity 540 ° C + load)) Hydrodesulfurization rate = ((amount of sulfur in the feedstock - amount of sulfur in the effluent) / amount of sulfur in the feedstock According to the invention, whether the hydrocracking step is carried out with two bubbling beds or two hybrid beds, it is possible to obtain stable and stable effluents. low sediment content as soon as a stage of maturation then a stage of separation of the sediments are put are implemented. It is also possible to subject the effluents from the ripening and sediment separation stages to a fixed bed hydrotreatment stage. The operating conditions of the hydrotreating step are given in Table 5. The CoMoNi on Alumina catalysts used are sold by Axens under the references HF858, HM848 and HT438.
    [0042] Table 5: Operating conditions of the hydrotreatment stage carried out on the 350+ sections resulting from the hydrocracking step after their passage to the stage of maturation and separation of the sediments. HDM and HDS catalysts 302 7 9 1 1 CoMoNi on alumina Temperature at the start of the cycle (° C) 370 Partial pressure H2 (MPa) 15 VVH (h-1, Sm3 / h fresh load / m3 of fixed bed catalyst) 0.21 H2 / HC fixed bed section out of H2 consumption (Nm3 / m3 fresh feed) 1000 5 The effluents from the hydrotreating step are then separated and analyzed. The vacuum distillate fractions contain less than 0.2% by weight of sulfur. The fractions under vacuum contain less than 0.5% by weight of sulfur. Thus, vacuum distillate fractions and vacuum residues (or atmospheric residue fractions) with low sulfur content and low sediment content after aging are obtained. These fractions thus constitute excellent fuel oil bases and in particular excellent fuel oil bases.
    权利要求:
    Claims (15)
    [0001]
    1) Process for converting a hydrocarbon feed containing at least one hydrocarbon fraction having a sulfur content of at least 0.1% by weight, an initial boiling point of at least 340 ° C. and an end temperature boiling point of at least 440 ° C to obtain a heavy fraction having a sediment content after aging less than or equal to 0.1% by weight, said process comprising the following steps: a) a step of hydrocracking of the charge in the presence of hydrogen in at least one reactor containing a catalyst supported in bubbling bed, b) a step of separating the effluent obtained at the end of step a) into at least a light fraction of hydrocarbons containing fuel bases and a heavy fraction containing compounds boiling at least 350 ° C., c) a step of maturation of the heavy fraction resulting from the separation step b) allowing the transformation of part of the sediment potential sediments, carried out for a period of between 1 and 1500 minutes, at a temperature of between 50 and 350 ° C, and a pressure of less than 20 MPa, d) a step of separating sediments from the heavy fraction obtained from step c) of maturing to obtain said heavy fraction. 20
    [0002]
    2) A process according to claim 1 wherein the hydrocracking step a) is carried out under a hydrogen partial pressure of 5 to 35 MPa, at a temperature of 330 to 500 ° C, a space velocity of 0, 05 h-1 to 5 h-1 and the amount of hydrogen mixed with the feed is 50 to 5000 Nm 3 / m 3,
    [0003]
    3) Process according to claim 1 or 2 wherein the hydrocracking step is carried out in at least one reactor operating in hybrid bed mode, that is to say operating in a bubbling bed with a supported catalyst associated with a dispersed catalyst consisting of very fine catalyst particles forming a suspension with the charge to be treated.
    [0004]
    4) Method according to one of the preceding claims wherein the step of maturation of the heavy fraction from step b) is carried out in the presence of an inert gas and / or an oxidizing gas.
    [0005]
    5) Method according to one of the preceding claims wherein the step d) of separation is carried out by means of at least one separation means selected from a filter, a separation membrane, a bed of organic-type filtering solids or inorganic, electrostatic precipitation, centrifugation system, decantation, auger withdrawal.
    [0006]
    6) Method according to one of the preceding claims wherein at least a portion of the so-called heavy fraction from step b) is fractionated by atmospheric distillation into at least one atmospheric distillate fraction containing at least a light fraction of hydrocarbons from naphtha, kerosene and / or diesel type and an atmospheric residue fraction.
    [0007]
    7) Method according to one of the preceding claims wherein the effluent obtained at the end of step d) sediment separation undergoes a separation step e), to separate at least a light fraction of hydrocarbons containing fuel bases and a heavy fraction containing predominantly boiling compounds at least 350 ° C.
    [0008]
    8) Method according to one of the preceding claims further comprising a f) fixed bed hydrotreating step implemented on at least part of the heavy fraction from step d) or e) in which is passed under hydrotreatment conditions, the heavy fraction and hydrogen on a hydrotreatment catalyst.
    [0009]
    9) The method of claim 8 wherein the hydrotreatment step is carried out at a temperature between 300 and 500 ° C, a hydrogen partial pressure of between 2 MPa and 25 MPa, a global time space velocity (VVH) is ranging from 0.1 hr-1 to 11-1, a quantity of hydrogen mixed with the feed of 100 to 5000 Nm3 / m3.
    [0010]
    10) A method according to claim 8 or 9 wherein a cc-filler is introduced with the heavy fraction in the hydrotreatment step f).
    [0011]
    11) The method of claim 10 wherein the co-charge is selected from atmospheric residues, vacuum residues from direct distillation, deasphalted oils, aromatic extracts from lubricant bases production lines, hydrocarbon fractions or a mixture of hydrocarbon fractions that may be chosen from products derived from a fluid-bed catalytic cracking process: a light cutting oil (LCO), a heavy cutting oil (H-CO), a decanted oil, or which may come distillation, gas oil fractions including those obtained by atmospheric or vacuum distillation, such as vacuum gas oil.
    [0012]
    12) Method according to one of the preceding claims wherein the treated feedstock is selected from atmospheric residues, vacuum residues from direct distillation, crude oils, crude oils topped, deasphalted oils, deasphalting resins, asphalts or deasphalting pitches, residues resulting from conversion processes, aromatic extracts from lubricant base production lines, oil sands or their derivatives, oil shales or their derivatives, whether taken alone or as a mixture.
    [0013]
    13). Process according to one of the preceding claims wherein the final boiling point of the feedstock is at least 540 ° C.
    [0014]
    14) Method according to one of the preceding claims wherein the feed contains at least 1% of C7 asphaltenes and at least 5 ppm of metals.
    [0015]
    15) Method according to one of the preceding claims wherein the heavy fractions from steps d) and / or e) and / or f) and / or g) are mixed with one or more fluxing bases selected from the group consisting of catalytic cracked light cutting oils, catalytic cracked heavy cutting oils, catalytic cracking residue, kerosene, gas oil, vacuum distillate and / or decanted oil.
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    FR3084372A1|2020-01-31|PROCESS FOR THE TREATMENT OF A HEAVY HYDROCARBON LOAD COMPRISING HYDROTREATMENT IN A FIXED BED, TWO DEASPHALTAGES AND A HYDROCRACKING IN A BOTTLE OF ASPHALT
    WO2016192893A1|2016-12-08|Method for converting feedstocks comprising a visbreaking step, a precipitation step and a sediment separation step, in order to produce fuel oils
    同族专利:
    公开号 | 公开日
    RU2015146921A|2017-05-18|
    US20160160136A1|2016-06-09|
    FR3027911B1|2018-04-27|
    RU2678764C2|2019-02-01|
    CN105586085B|2019-08-06|
    CA2911122A1|2016-05-04|
    RU2015146921A3|2018-12-12|
    EP3018187B1|2017-10-25|
    EP3018187A1|2016-05-11|
    US9840674B2|2017-12-12|
    KR20160052435A|2016-05-12|
    ES2656416T3|2018-02-27|
    CN105586085A|2016-05-18|
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    法律状态:
    2015-11-05| PLFP| Fee payment|Year of fee payment: 2 |
    2016-05-06| PLSC| Search report ready|Effective date: 20160506 |
    2016-11-21| PLFP| Fee payment|Year of fee payment: 3 |
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    2019-11-28| PLFP| Fee payment|Year of fee payment: 6 |
    2020-11-26| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1460628|2014-11-04|
    FR1460628A|FR3027911B1|2014-11-04|2014-11-04|METHOD FOR CONVERTING PETROLEUM LOADS COMPRISING A BOILING BED HYDROCRACKING STEP, MATURATION STEP AND SEDIMENT SEPARATION STEP FOR THE PRODUCTION OF LOW SEDIMENT FOLDS|FR1460628A| FR3027911B1|2014-11-04|2014-11-04|METHOD FOR CONVERTING PETROLEUM LOADS COMPRISING A BOILING BED HYDROCRACKING STEP, MATURATION STEP AND SEDIMENT SEPARATION STEP FOR THE PRODUCTION OF LOW SEDIMENT FOLDS|
    EP15306716.0A| EP3018187B1|2014-11-04|2015-10-27|Process for converting petroleum feedstocks comprising an ebullating-bed hydrocracking stage, a maturation stage and a stage of separating the sediments for the production of fuel oils with a low sediment content|
    ES15306716.0T| ES2656416T3|2014-11-04|2015-10-27|Method of conversion of oil charges comprising a bubbling bed hydrocracking stage, a maturation stage and a sediment separation stage for the production of fuel oil with a low sediment content|
    RU2015146921A| RU2678764C2|2014-11-04|2015-10-30|Process for converting petroleum feedstocks comprising fluidised-bed hydrocracking stage, ageing stage and stage of separating sediments for production of fuel oils with low sediment content|
    CA2911122A| CA2911122A1|2014-11-04|2015-11-02|Conversion process for oil feedstocks including a hydrocracking stage in an ebullating bed, a maturation stage and a separation stage for the production of fuels with low sediment content|
    KR1020150153798A| KR20160052435A|2014-11-04|2015-11-03|Process for converting petroleum feedstocks comprising an ebullating-bed hydrocracking stage, a maturation stage and a stage of separating the sediments for the production of fuel oils with a low sediment content|
    US14/931,395| US9840674B2|2014-11-04|2015-11-03|Process for converting petroleum feedstocks comprising an ebullating-bed hydrocracking stage, a maturation stage and a stage of separating the sediments for the production of fuel oils with a low sediment content|
    CN201510738992.2A| CN105586085B|2014-11-04|2015-11-04|For producing the petroleum method for transformation of the fuel oil with low sediment content|
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