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    • 专利摘要:
    The invention relates to a method for treating a hydrocarbon feedstock, said process comprising the following steps: a) a hydrotreatment step, in which the hydrocarbon feedstock and hydrogen are brought into contact on a hydrotreatment catalyst, b ) an optional step of separation of the effluent from step a) hydrotreatment, c) a step of hydrocracking at least a portion of the effluent from step a) or at least a portion of the heavy fraction resulting from step b), d) a step of separating the effluent resulting from step c), e) a sediment precipitation step, f) a step of physically separating the sediments of the heavy liquid fraction resulting from step e), g) a step of recovering a liquid hydrocarbon fraction having a sediment content, measured according to the method ISO 10307-2, of less than or equal to 0.1% by weight.
    公开号:FR3036705A1
    申请号:FR1554964
    申请日:2015-06-01
    公开日:2016-12-02
    发明作者:Wilfried Weiss；Isabelle Merdrignac；Jeremie Barbier；Ann Forret
    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 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). The quality requirements for marine fuels are described in ISO 8217. The Sulfur specification now attaches to SO emissions (Annex VI of the MARPOL Convention of the International Maritime Organization) and results in a recommendation. in sulfur content 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 % weight in ZCES. Another very stringent 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%. The sediment content after aging is a measurement carried out according to the method described in the ISO 10307-2 standard (also known to those skilled in the art under the name of IP390). In the rest of the text will therefore read "sediment content after aging", the sediment content measured according to the ISO 10307-2 method. The reference to IP390 will also indicate that the measurement of the sediment content after aging is performed according to the ISO 10307-2 method. 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. According to Annex VI of the MARPOL Convention, a vessel may therefore use sulfur-containing fuel if the ship is equipped with a flue gas treatment system to reduce emissions of sulfur oxides.
    [0002] Process for the refining and conversion of heavy petroleum feedstocks comprising a first fixed bed hydrotreatment stage and then a bubbling bed hydrocracking stage have been described in patent documents FR 2764300 and EP 0665282. EP 0665282 describes a hydrotreatment process for heavy oils with the aim of extending the life of the reactors. The method described in FR 2764300 describes a process for obtaining fuels (gasoline and diesel) having in particular a low sulfur content. The fillers treated in this process do not contain asphaltenes. The fuel oils used in marine transport generally comprise atmospheric distillates, vacuum distillates, atmospheric residues and vacuum residues from direct distillation or from refining processes, in particular hydrotreatment and conversion processes, these slices can be used alone or mixed. These processes, although known to be suitable for heavy loads loaded with impurities, however, produce hydrocarbon fractions comprising catalyst fines and sediments which must be removed to satisfy a product quality such as bunker fuel oil. The sediments may be precipitated asphaltenes. Initially in the charge, the conversion conditions and in particular the temperature make them undergo reactions (dealkylation, polycondensation ...) leading to their precipitation. In addition to the existing sediments in the heavy cut at the exit of the process (measured according to ISO 10307-1 also known as IP375), there are also, according to the conversion conditions, sediments qualified as potential sediments which do not appear. only after physical, chemical and / or thermal treatment. The set of sediments including potential sediments is measured according to ISO 10307-1, also known as IP390. These phenomena generally occur during the implementation of severe conditions giving rise to high conversion rates, for example higher. 40 or 50% or more, depending on the nature of the load. The applicant in his research has developed a new process incorporating a sediment precipitation and separation step downstream of a fixed bed hydrotreatment step and a hydrocracking step. Surprisingly, it has been found that such a method makes it possible to obtain liquid hydrocarbon fractions having a low sediment content after aging (measured according to the ISO 10307-2 method), said fractions being advantageously able to be used totally or in part. as fuel oil or 3036705 as fuel oil base meeting future specifications, namely and a sediment content after aging less than or equal to 0.1% by weight. More specifically, the invention relates to a process for treating 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 a final boiling temperature of at least 440 ° C, said process comprising the following steps a) a fixed bed hydrotreating step, wherein the hydrocarbon feedstock and hydrogen are contacted on a hydrotreatment catalyst, b) an optional step of separating the effluent from step a) of hydrotreatment into at least a light hydrocarbon fraction containing fuel bases and a heavy fraction containing compounds boiling at least 350 ° C, c) a step of hydrocracking at least a portion of the effluent from step a) or at least a portion of the heavy fraction from step b), in at least a reactor containing a catalyst supported in a boiled bed lonnant, d) a step of separating the effluent from step c) to obtain at least a gaseous fraction and at least one heavy liquid fraction, e) a precipitation step in which the heavy liquid fraction resulting from the step d) of separation is brought into contact with a distillate cut of which at least 20% by weight has a boiling temperature greater than or equal to 100 ° C, for a period of less than 500 minutes, at a temperature between 25 and 350 C., and a pressure of less than 20 MPa, f) a step of physically separating the sediments of the heavy liquid fraction resulting from the precipitation step e) to obtain a liquid hydrocarbon fraction, g) a step of recovering a liquid hydrocarbon fraction having a sediment content, measured according to the method ISO 10307-2, less than or equal to 0.1% by weight, of separating the liquid hydrocarbon fraction from step f) of the disti It is introduced in step e). One of the objectives of the present invention is to propose a process for the conversion of heavy petroleum feedstocks for the production of fuel oils and oil bases, in particular 3036705 4 bunker oils and bunker oil bases, with a low sediment content after aging. (measured according to the method ISO 10307-2) less than or equal to 0.1% by weight. Another object of the present invention is to jointly produce, by the same process, atmospheric distillates (naphtha, kenylene, diesel), vacuum distillates and / or light (Cl-C4) gases. 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. Brief Description of Figure 1 Figure 1 shows a schematic view of the process according to the invention showing a hydrotreating zone, a separation zone, a hydrocracking zone, another separation zone, a precipitation zone, a physical separation zone of the sediments and a recovery zone of the fraction of interest.
    [0003] The feedstock treated in the process according to the invention is advantageously a hydrocarbon feedstock having an initial boiling point of at least 340 ° C and a final boiling point of at least 440 ° C. Preferably, its initial boiling point is at least 350 ° C., preferably at least 375 ° C., and 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 agents, aromatic extracts from lubricant base production lines, oil sands or derivatives thereof, oil shales or their derivatives, parent rock oils or their derivatives, alone or in admixture. In the present invention, the fillers being treated are preferably atmospheric residues or vacuum residues, or mixtures of these residues.
    [0004] Advantageously, the filler may contain at least 1% of C7 asphaltenes and at least 5 ppm of metals, preferably at least 2% of C7 asphaltenes and at least 25 ppm of metals. 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, at least 0.5% by weight, preferably at least 1% by weight, more preferably at least 4% by weight, still more preferably at least 5% by weight. These charges can advantageously be used as they are. Alternatively, they can be diluted by co-charging. This co-charge may be a hydrocarbon fraction or a mixture of lighter hydrocarbon fractions, which may preferably be chosen from products resulting from a process of fluid catalytic cracking (FCC or "Fluid Catalytic Cracking" according to the English terminology). -Saxonne), a light cutting oil (LCO or "light cycle oil" according to the English terminology), a heavy cutting oil (HCO or "heavy cycle oil" according to the English terminology), a decanted oil 15 , an FCC residue, a gas oil fraction, especially a fraction obtained by atmospheric distillation or under vacuum, such as, for example, vacuum gas oil, or possibly from another refining process. 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 feedstocks 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 relates to the production of a liquid hydrocarbon fraction having a sediment content after aging less than or equal to 0.1% by weight. The process according to the invention comprises a first step a) of fixed bed hydrotreating, optionally a step b) of separating the effluent from step a) of hydrotreatment into a light fraction and a heavy fraction, followed by a step c) bubbling bed hydrocracking of at least a portion of the effluent from step a) or at least a portion of the heavy fraction from step b), a step d) of separating the effluent from step c) to obtain at least a gaseous fraction and at least one heavy liquid fraction, a step e) of sediment precipitation of the heavy liquid fraction resulting from step d ) A step f) of physical separation of the sediments of the heavy liquid fraction resulting from step e) and finally a step g) of recovery of a liquid hydrocarbon fraction having a sediment content after aging less than or equal to 0.1% by weight. The objective of the hydrotreatment is both to refine, that is, to substantially reduce the content of metals, sulfur and other impurities, while improving the hydrogen to carbon ratio (H / C) and all by transforming the hydrocarbon feed more or less partially into lighter cuts. The effluent obtained in step a) of hydrotreatment in a fixed bed can then be sent to step c) of hydrocracker Ige in a bubbling bed either directly or after being subjected to a sepr step: -M light fractions. Step c) allows partial conversion of the feedstock to produce an effluent including catalyst fines and sediments which must be removed to meet a product quality such as bunker oil. The process according to the invention is characterized in that it comprises a precipitation step e) and a step f) of physical separation of the sediments carried out under conditions which make it possible to improve the sediment separation efficiency and thus of obtain fuel oils or fuel bases having a sediment content after aging less than or equal to 0.1% by weight. One of the interests of the sequence of a hydrotreatment in a fixed bed and then a bubbling bed hydrocracking resides in the fact that the charge of the bubbling bed hydrocracking reactor is already at least partially hydrotreated. In this way, it is possible to obtain equivalent conversion of hydrocarbon effluents of better quality, especially with lower sulfur contents. In addition, the catalyst consumption in the bubbling bed hydrocracking reactor is greatly reduced compared to a process without prior fixed bed hydrotreatment. Step a) Hydroprocessing The filler according to the invention is subjected according to the process of the present invention to a fixed bed hydrotreating step a) in which the feedstock and hydrogen are contacted on a catalyst of the present invention. hydrotreating. Hydroprocessing, commonly known as HDT, is understood to mean catalytic treatments with a hydrogen supply that makes it possible to refine, that is to say, to substantially reduce the content of metals, sulfur and other impurities, hydrocarbon feedstocks, while improving the hydrogen-to-carbon ratio of the feed and transforming the feed more or less partially into lighter cuts. Hydroprocessing includes, in particular, hydrodesulfurization reactions (commonly referred to as HDS), hydrodenitrogenation reactions (commonly referred to as HDN) and hydrodemetallation reactions (commonly referred to as HDM), accompanied by hydrogenation, hydrodeoxygenation reactions. hydrodearomatization, hydroisomerization, hydrodealkylation, hydrocracking, hydro-deasphalting and Conradson carbon reduction. According to a preferred variant, the hydrotreatment step a) comprises a hydrodemetallation first step (a) (HDM) carried out in one or more hydrodemetallation zones in fixed beds and a second hydrodesulphurization second stage (a2) (HDS). carried out in one or more hydrodesulfurization zones in fixed beds. During said first hydrodemetallation step a1), the feedstock and hydrogen are contacted on a hydrodemetallization catalyst, under hydrodemetallation conditions, and then during said second hydrodesulfurization step a2), the effluent of the first hydrodemetallation step (a1) is contacted with a hydrodesulfurization catalyst under hydrodesulfurization conditions. This process, known as HYVAHL-FTM, is for example described in US Pat. No. 5,417,846. According to a variant of the invention, when the feedstock contains more than 100 ppm or more than 200 ppm of metals and / or when Since the feedstock comprises impurities such as iron derivatives, it may be advantageous to use permutable reactors ("PRS" technology for "Permutable Reactor System" according to the English terminology) as described in US Pat. FR2681871. These permutable reactors are generally fixed beds located upstream of the fixed bed hydrodemetallation section. Those skilled in the art readily understand that, in the hydrodemetallization step, hydrodemetallization reactions are carried out, but also part of the other hydrotreatment reactions and in particular hydrodesulfurization reactions. Similarly, in the hydrodesulphurization step, hydrodesulphurization reactions are carried out, but also part of the other hydrotreatment reactions and in particular hydrodemetallation reactions. One skilled in the art understands that the hydrodemetallization step begins where the hydrotreatment step begins, where the metal concentration is maximum. Those skilled in the art understand that the hydrodesulfurization step ends where the hydrotreatment step ends, where sulfur removal is most difficult. Between the hydrodemetallation step and the hydrodesulfurization step, the skilled person sometimes defines a transition zone in which all types of hydrotreatment reaction occur.
    [0005] The step a) of hydrotreatment according to the invention is carried out under hydrotreatment conditions. It can advantageously be carried out at a temperature of between 300 ° C. and 500 ° C., preferably between 350 ° C. and 420 ° C. and under an absolute pressure of between 5 MPa and 35 MPa, preferably between 11 MPa and 20 ° C. 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 0.11-1-1 to 2 h -1, and more preferably from 0.1 h -1 to 0.45 h -1, the amount of hydrogen mixed with the feed may be be between 100 and 5000 normal cubic meters (Nm3) per cubic meter (m3) of liquid charge, preferably between 200 Nm3 / m3 and 2000 Nm3 / m3, and more preferably between 300 Nm3 / m3 and 1500 Nm3 / m3. Step a) of hydrotreatment 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. molybdenum weight, preferably from 5% to 20% by weight of molybdenum (expressed as molybdenum oxide MoO 3) 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. Advantageously, 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. When phosphorus pentoxide P205 is present, its concentration is less than 10% by weight. When boron trioxide B205 is present, its concentration is less than 10% by weight. The alumina used may be y (gamma) or hal (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.
    [0006] In the case of a hydrotreatment step including a hydrodemetallation step (HDM) and then a hydrodesulfurization step (HDS), specific catalysts adapted to each step are preferably used. Catalysts that can be used in the hydrodemetallization step are for example indicated in patent documents EP 0113297, EP 0113284, US Pat. No. 5,222,056, US Pat. No. 5,827,421, US Pat. No. 711,905,5, US Pat. No. 5,622,616 and US Pat. No. 5,089,463. HDM catalysts are preferably used. in permutable reactors. Catalysts that can be used in the hydrodesulphurization step are, for example, indicated in patent documents EP 0113297, EP 0113284, US Pat. No. 6,589,088, US Pat. No. 4,818,743 or US Pat. No. 6,332,976.
    [0007] It is also possible to use a mixed catalyst, active in hydrodemetallation and in hydrodesulfurization, for both the hydrodemetallation section and the hydrodesulfurization section as described in patent document FR 2940143. Prior to injection of the The catalysts used in the process according to the present invention are preferably subjected to an in situ or ex situ sulfurization treatment. Step b) Optional separation The separation step of the effluent from step a) of hydrotreatment is optional. In the case where the step of separating the effluent from step a) of hydrotreatment is not implemented, at least part of the effluent from step a) of hydrotreatment is 25 introduced in the section allowing the implementation of the bubbling bed hydrocracking step c) without changing the chemical composition and without significant loss of pressure. By "significant pressure loss" is meant a pressure loss caused by a valve or expansion turbine, which could be estimated at a pressure loss of more than 10% of the total pressure. Those skilled in the art generally use these pressure losses or relaxations during the separation steps. When the separation step is carried out on the effluent from step a) of hydrotreatment, this is optionally supplemented by further additional separation steps, making it possible to separate at least one light fraction and at least one heavy fraction. By "light fraction" is meant a fraction in which at least 90% of the compounds have a boiling point below 350 ° C. By "heavy fraction" is meant a fraction in which at least 90% of the compounds have a boiling point greater than or equal to 350 ° C. Preferably, the light fraction obtained during the separation step b). comprises a gaseous phase and at least a light fraction of hydrocarbons of the naphtha, kerosene and / or diesel type, the heavy fraction preferably comprises a vacuum distillate fraction and a vacuum residue fraction and / or an atmospheric residue fraction.
    [0008] The separation step b) may be carried out by any method known to those skilled in the art. This method can be selected from high or low pressure separation, high or low pressure distillation, high or low pressure stripping, and combinations of these different methods that can operate at different pressures and temperatures.
    [0009] According to a first embodiment of the present invention, the effluent from step a) of hydrotreating undergoes a step b) of separation with decompression. According to this embodiment, the separation is preferably carried out in a fractionation section which may firstly comprise a high temperature high pressure separator (HPHT), and possibly a low temperature high pressure separator (HPBT), followed optionally later by an atmospheric distillation section and / or a vacuum distillation section. The effluent of step a) can be sent to a fractionation section, generally in an HPHT separator making it possible to obtain a light fraction and a heavy fraction containing predominantly boiling compounds at at least 350 ° C. In general, the separation is preferably not made according to a precise cutting point, rather it is similar to an instantaneous type separation (or flash according to the English terminology). The cutting point of the separation is advantageously between 200 and 400 ° C. Preferably, said heavy fraction can then be fractionated by atmospheric distillation into at least one atmospheric distillate fraction, preferably containing at least a light fraction of naphtha, kerosene and / or diesel type hydrocarbons, and an atmospheric residue fraction. At least a portion of the atmospheric residue fraction can also be fractionated by vacuum distillation into a vacuum distillate fraction, preferably containing vacuum gas oil, and a vacuum residue fraction. At least a portion of the vacuum residue fraction and / or the atmospheric residue fraction are advantageously fed to the hydrocracking step c). Part of the vacuum residue fraction and / or the atmospheric residue fraction can (also) be used directly as a fuel oil base, especially as a base of low sulfur fuel oil. Part of the vacuum residue fraction and / or the atmospheric residue fraction may also be sent to another conversion process, including a fluidized catalytic cracking process. According to a second embodiment, the effluent from step a) hydrotreatment undergoes a step b) separation without decompression. According to this embodiment, the effluent of the hydrotreatment step a) is sent to a fractionation section, generally in an HPHT separator, having a cutting point between 200 and 450 ° C. allowing to obtain at least 20 a light fraction and at least one heavy fraction. In general, the separation is preferably not made according to a precise cutting point, it is rather like a separation of the instantaneous type (or flash according to the English terminology). The heavy fraction can then be directly sent to the hydrocracking step c). The light fraction may undergo other separation steps. Advantageously, it may be subjected to an atmospheric distillation which makes it possible to obtain a gaseous fraction, at least a light fraction of liquid hydrocarbons of the naphtha, kerosene and / or diesel type and a vacuum distillate fraction, the last of which may be at least partly sent in step c) of hydrocracking. Another part of the vacuum distillate can be used as a fluxing agent for a fuel oil. Another part of the vacuum distillate can be upgraded by being subjected to a hydrocracking and / or catalytic cracking step in a fluidized bed. No-decompression separation provides better thermal integration and saves energy and equipment. In addition, this embodiment has technical and economic advantages since it is not necessary to increase the flow pressure after separation before the subsequent hydrocracking step. Intermediate fractionation without decompression being simpler than fractionation with decompression, the investment cost is therefore advantageously reduced.
    [0010] The gaseous fractions resulting from the separation step preferably undergo a purification treatment to recover the hydrogen and recycle it to the hydrotreating and / or hydrocracking reactors, or even to the precipitation stage. The presence of the separation step between the hydrotreatment step a) and the hydrocracking step c) advantageously makes it possible to have two independent hydrogen circuits, one connected to the hydrotreating, other to hydrocracking, and which, if necessary, can be connected to each other. The addition of hydrogen can be done at the hydrotreatment section or at the level of the hydrocracking section or at both. The recycle hydrogen can supply the hydrotreatment section or the hydrocracking section or both. A compressor may possibly be common to both hydrogen circuits. The fact of being able to connect the two hydrogen circuits makes it possible to optimize the management of hydrogen and to limit the investments in terms of compressors and / or purification units of the gaseous effluents. The various embodiments of the hydrogen management that can be used in the present invention are described in the patent application FR 2957607.
    [0011] The light fraction obtained at the end of the separation step b), which comprises hydrocarbons of the naphtha, kerosene and / or diesel or other type, in particular LPG and vacuum gas oil, can be recovered according to the methods which are well known. of the skilled person. The products obtained can be incorporated into fuel formulations (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, for example hydrotreatment, hydrocracking, alkylation, isomerization, catalytic reforming, catalytic or thermal cracking, to bring them in a controlled manner. separated or in mixture with the required specifications which may relate to the sulfur content, the point of smoke, the octane number, cetane, and others.
    [0012] The light fraction obtained at the end of step b) may be used at least in part to form the distillate cut according to the invention used in step e) of sediment precipitation, or to be mixed with said distillate cut according to the invention.
    [0013] A portion of the heavy fraction from the separation step b) can be used to form the distillate cut according to the invention used in the sediment precipitation step e). Step c) bubbling bed hydrocracking 5 At least a portion of the effluent from step a) of hydrotreatment or at least a portion of the heavy fraction from step b) is sent according to the method of the present invention in a step c) of hydrocracking which is carried out in at least one reactor, advantageously two reactors, containing at least one catalyst supported bubbling bed. Said reactor can operate at an upward flow of liquid and gas.
    [0014] The main purpose of hydrocracking is to convert the heavy hydrocarbon feedstock into lighter cuts while partially refining it. According to one embodiment of the present invention, part of the initial hydrocarbon feedstock can be injected directly into the hydrocracking section c) in bubbling bed, mixed with the effluent from the hydrotreating section a) in fixed bed or the heavy fraction from step b), without this portion of the hydrocarbon feedstock being treated in the hydrotreatment section a) in a fixed bed. This embodiment can be likened to a partial short circuit of the hydrotreatment section a) in a fixed bed. According to one variant, a co-charge may be introduced at the inlet of the hydrocracking section c) in a bubbling bed with the effluent of the hydrotreatment section a) in fixed bed or the heavy fraction resulting from step b ). 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 may be chosen from products derived from a fluid-bed catalytic cracking process, in particular a light cutting oil (LCO), a heavy cutting oil (HCO), a decanted oil, or possibly derived from distillation, the gasoil fractions in particular those obtained by atmospheric or vacuum distillation, such as, for example, vacuum gas oil. According to another variant and in the case where the hydrocracking section has several bubbling bed reactors, this co-charge may be partially or totally injected into one of the reactors downstream of the first reactor.
    [0015] The hydrogen necessary for the hydrocracking reaction may already be present in sufficient quantity in the effluent resulting from the hydrotreatment stage a) injected at the inlet of the hydrocracking section c) in an ebullated bed. However, it is preferable to provide an additional supply of hydrogen at the inlet of the hydrocracking section c). In the case where the hydrocracking section has several bubbling bed reactors, hydrogen can be injected at the inlet of each reactor. The injected hydrogen may be a make-up stream and / or a recycle stream. Bubbling bed technology is well known to those skilled in the art. Only the main operating conditions will be described here. Bubbling bed technologies conventionally employ supported catalysts in the form of extrudates, the diameter of which is generally of the order of 1 millimeter or less. The catalysts remain inside the reactors and are not evacuated with the products, except during the makeup and catalyst withdrawal phases necessary to maintain the catalytic activity. The temperature levels can be elevated to achieve high conversions while minimizing the amounts of catalysts employed. 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 the deactivation. In addition, working at constant operating conditions advantageously makes it possible to obtain efficiencies and qualities of products const along the cycle. Also, because the catalyst is maintained in agitation by a recyck important ge de liquid, the pressure drop on the reactor remains low and constant. Because of the attrition of the catalysts in the reactors, the products leaving the reactors may contain fine particles of catalyst. The conditions of the bubbling bed hydrocracking step c) may be conventional bubbling bed hydrocracking conditions of a hydrocarbon feedstock. It can be operated under an absolute pressure of between 2.5 MPa and 35 MPa, preferably between 5 MPa and 25 MPa, more preferably between 6 MPa and 20 MPa, and even more preferably between 11 MPa and 20 MPa at a temperature between 330 ° C and 550 ° C, preferably between 350 ° C and 500 ° C. Spatial velocity (VVH) and hydrogen partial pressure are parameters that are set according to the characteristics of the product to be treated and the desired conversion. The VVH which is defined as the volumetric flow rate of the feedstock divided by the total volume of the reactor is generally in a range from 0.111-1 to 1011-1, preferably from 0.1 hr-1 to 5 hr-1 and more preferably from 0.1 hr-1 to hr-1. The amount of hydrogen mixed with the feedstock is usually from 50 to 5000 normal cubic meters (Nm3) per cubic meter (m3) of liquid feed, most often from 100 Nm3 / m3 to 1500 Nm3 / m3 and preferably 200 Nm3 A conventional granular hydrocracking catalyst comprising, on an amorphous support, at least one metal or metal compound having a hydrodehydrogenating function, can be used / m3 at 1200 Nm3 / m3. 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, it is possible to use 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 nickel. molybdenum weight, preferably from 5% to 20% by weight of molybdenum (expressed as molybdenum oxide MoO 3) on an amorphous 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 also contain other compounds and for example oxides selected from the group consisting of boron oxide, zirconia, titanium oxide, phosphoric anhydride. Most often an alumina support is used and very often a support of alumina doped with phosphorus and possibly boron. When P205 phosphoric anhydride is present, its concentration is usually less than 20% by weight and most often less than 10% by weight. When B2O3 boron trioxide is present, its concentration is usually less than 10% by weight. The alumina used is usually y (gamma) or n (eta) alumina. This catalyst may be in the form of extrudates. The total content of Group VI and VIII metal oxides may range from 5% to 40% by weight, preferably from 7% to 30% by weight, and the weight ratio of metal oxide (or metals) to metal oxide. Group VI on metal (or metals) Group VIII is between 20 and 1, preferably between 10 and 2. The used catalyst can be partly replaced by fresh catalyst, usually by withdrawal at the bottom of the reactor and introduction at the top fresh or new catalyst reactor at regular time interval, i.e., for example by puff or continuously 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 the 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 hydrocracking reactor usually comprises a recirculation pump for maintaining the bubbling bed catalyst by continuous recycling of 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 (b). The hydrocracking step c) according to the process of the invention can be carried out under the conditions of the H-01LO process as described, for example, in US Pat. No. 6,270,654. Bubble bed hydrocracking can be carried out in a single reactor or in several reactors, preferably two, arranged in series. The fact of using at least two bubbling bed reactors in series makes it possible to obtain products of better quality and with better performance. In addition, the hydrocracking into two reactors makes it possible to have improved operability in terms of the flexibility of the operating conditions and the catalytic system. Preferably, the temperature of the second bubbling bed reactor is at least 5 ° C higher than that of the first bubbling bed reactor. The pressure of the second reactor can be 0.1 MPa 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 20 without the need for pumping. . The different operating conditions in terms of temperature in the two hydrocracking reactors are selected to be able to control the hydrogenation and the conversion of the feedstock into the desired products in each reactor. In the case where the hydrocracking step c) is carried out in two sub-steps c1) and c2) in two reactors arranged in series, the effluent obtained at the end of the first substep c) may optionally be subjected to a separation step of the light fraction and the heavy fraction, and at least a portion, preferably all, of said heavy fraction can be treated in the second hydrocracking sub-step c2). This separation is advantageously done in an inter-stage separator, as described for example in US Pat. No. 6,270,654, and in particular makes it possible to avoid over cracking of the light fraction in the second hydrocracking reactor. It is also possible to transfer all or part of the used catalyst withdrawn from the reactor of the first sub-step (bl) of hydrocracking, operating at a lower temperature, directly to the reactor of the second substep (b2). operating at higher temperature, or to transfer all or part of the used catalyst withdrawn from the reactor of the second substep (b2) directly to the reactor of the first substep (b1). This cascade system is for example described in US Patent 4816841.
    [0016] The hydrocracking step can also be done with several reactors in parallel (usually two) in the case of large capacity. The hydrocracking step may thus comprise several stages in series, possibly separated from an inter-stage separator, each stage being constituted by one or more reactors in parallel. Step d) The process according to the invention may furthermore comprise a step d) of separation which makes it possible to obtain at least one gaseous fraction and at least one heavy liquid fraction. The effluent obtained at the end of the hydrocracking step c) comprises 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. 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 steam or hydrogen stripping means and one or more distillation columns. The effluent obtained at the end of the hydrocracking step c) is advantageously separated in at least one separator flask into at least one gaseous fraction and at least one heavy liquid fraction. These separators may for example be high temperature high pressure separators (HPHT) and / or high temperature low pressure separators (HPBT). After possible cooling, 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 a plurality of such means arranged in series. The purified hydrogen can then advantageously be recycled in the process according to the invention, after possible recompression. Hydrogen can be introduced at the inlet of hydrotreatment step a) and / or at different locations during step a) of hydrotreatment and / or entry of step c). hydrocracking and / or at different locations during step c) hydrocracking, or even in the precipitation step. The separation step d) may also comprise atmospheric distillation and / or vacuum distillation. Advantageously, the separation step d) further comprises at least one atmospheric distillation, in which the liquid hydrocarbon fraction (s) obtained (s) after separation is (are) fractionated (s) by atmospheric distillation into at least one atmospheric distillate fraction and at least one atmospheric residue fraction. The atmospheric distillate fraction may contain commercially recoverable fuels bases (naphtha, kerosene and / or diesel), for example in the refinery 10 for the production of motor and aviation fuels. In addition, the separation step d) of the process according to the invention may advantageously also comprise at least one vacuum distillation in which the liquid hydrocarbon fraction (s) obtained (s) after separation. and / or the atmospheric residue fraction obtained after atmospheric distillation is (are) fractionated by vacuum distillation into at least one vacuum distillate fraction and at least one vacuum residue fraction. Preferably, the separation step d) comprises, first of all, an atmospheric distillation, in which the liquid hydrocarbon fraction (s) obtained after separation is (are) fractionated (s). ) by atmospheric distillation into 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 residue fraction under vacuum. The vacuum distillate fraction typically contains vacuum gas oil fractions. At least a portion of the vacuum residue fraction can be recycled to the hydrocracking step c). A portion of heavy liquid fraction from step d) of separation can be used to form the distillate cut according to the invention used in step e) sediment precipitation. Step e): Sediment Precipitation The heavy liquid fraction obtained at the separation step d) contains organic sediments which result from the hydrotreating and hydrocracking conditions and the catalyst residues. Part of the sediments consist of asphaltenes precipitated under hydrotreatment and hydrocracking conditions and are analyzed as existing sediments (IP375). Depending on the hydrocracking conditions, the sediment content in the heavy liquid 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 40 or 50%, cause the formation of existing sediments and potential sediments.
    [0017] In order to obtain a fuel oil or a fuel base that meets the recommendations for a sediment content after aging (measured according to the ISO 10307-2 method) of less than or equal to 0.1%, the process according to the invention comprises a precipitation step to improve the sediment separation efficiency and thus to obtain stable fuel oils or oil bases, ie a sediment content after aging less than or equal to 0.1% by weight . The precipitation step according to the process of the invention comprises bringing the heavy liquid fraction coming from the separation step d) into contact with a distillate cut of which at least 20% by weight has a higher boiling point or equal to 100 ° C, preferably greater than or equal to 120 ° C, more preferably greater than or equal to 150 ° C. In a variant according to the invention, the distillate cut is characterized in that it comprises at least 25% by weight having a boiling point greater than or equal to 100 ° C., preferably greater than or equal to 120 ° C. more preferably greater than or equal to 150 ° C. Advantageously, at least 5 wt.% Or even 10 wt.% Of the distillate cut according to the invention has a boiling point of at least 252 ° C. More advantageously, at least 5 wt.% Or even 10 wt.% Of the distillate cut according to the invention has a boiling point of at least 255 ° C. Said distillate cut may partly or even wholly derive from steps b) and / or d) of separation of the invention or another refining process or another chemical process.
    [0018] The use of the distillate cut according to the invention also has the advantage of avoiding the majority use of high value added cuts such as petrochemical cuts, naphtha ..... The distillate cut according to the invention advantageously comprises hydrocarbons having more than 12 carbon atoms, preferably hydrocarbons having more than 13 carbon atoms, more preferably hydrocarbons having between 13 and 40 carbon atoms. The distillate cut may be used in a mixture with a naphtha-type cut and / or a vacuum-type gas oil cut and / or vacuum residue. Said distillate cut may be used in admixture with the light fraction obtained after step b), the heavy fraction resulting from step b), the heavy liquid fraction resulting from step d), these fractions that can be taken alone or as a mixture. In the case where the distillate cut according to the invention is mixed with another cut, a light fraction and / or a heavy fraction as indicated above, the proportions are chosen so that the resulting mixture meets the specifications. of the distillate cut according to the invention. The precipitation step e) according to the invention makes it possible to obtain all the existing and potential sediments (by converting the potential sediments into existing sediments) so as to separate them effectively and thus reach the sediment content after aging (measured according to the method ISO 10307-2) 0.1% maximum weight.
    [0019] The precipitation step e) according to the invention is advantageously carried out for a residence time of less than 500 minutes, preferably less than 300 minutes, more preferably less than 60 minutes, at a temperature between 25 and 350 minutes. ° C, preferably between 50 and 350 ° C, preferably between 65 and 300 ° C and more preferably between 80 and 250 ° C. The pressure of the precipitation step is advantageously less than 20 MPa, preferably less than 10 MPa, more preferably less than 3 MPa and even more preferably less than 1.5 MPa. The mass ratio between the distillate fraction according to the invention and the heavy fraction obtained at the end of the separation step d) is between 0.01 and 100, preferably between 0.05 and 10, more preferably between 0.1. and 5, and even more preferably between 0.1 and 2. When the distillate cut according to the invention is taken from the process, it is possible to accumulate this cut during a start-up period so as to reach the ratio. longed for.
    [0020] The distillate cut according to the invention may also partly come from step g) of recovery of the liquid hydrocarbon fraction. The precipitation step e) can be carried out using several equipment. A static mixer or a stirred tank may optionally be used to promote effective contact between the heavy liquid fraction obtained at the end of the separation step d) and the distillate cut according to the invention. One or more exchangers may be used before or after mixing the heavy liquid fraction obtained at the end of step d) and the distillate cut according to the invention so as to reach the desired temperature. One or more capacity (s) may be used in series or in parallel such as a horizontal or vertical balloon, possibly with a settling function to remove some of the heavier solids. A stirred tank possibly equipped with a jacket for temperature regulation can also be used. This tank can be provided with a bottom withdrawal to remove some of the heavier solids.
    [0021] Advantageously, the precipitation step e) is carried out in the presence of an inert gas and / or an oxidizing gas and / or an oxidizing liquid and / or hydrogen, preferably derived from the process of the invention. invention, especially separation steps b) and / or c). Step e) sediment precipitation can be carried out in the presence of an inert gas such as dinitrogen, or in the presence of an oxidizing gas such as oxygen, ozone or nitrogen oxides, or presence of a mixture containing an inert gas and an oxidizing gas such as air or air depleted by nitrogen. The use of an oxidizing gas has the advantage of accelerating the precipitation process. Step e) sediment precipitation can be carried out in the presence of an oxidizing liquid to accelerate the precipitation process. The term "oxidizing liquid" means an oxygenated compound, for example a peroxide such as hydrogen peroxide, or an inorganic oxidizing solution such as a solution of potassium permanganate or a mineral acid such as sulfuric acid. According to this variant, the oxidizing liquid is then mixed with the heavy liquid fraction from step d) of separation and the distillate cut according to the invention during the implementation of step e) sediment precipitation.
    [0022] At the end of step e), a hydrocarbon fraction with an enriched content of existing sediments mixed at least partly with the distillate cut according to the invention is obtained. This mixture is sent to step f) of physical separation of the sediments. Step f): Separation of sediments The method according to the invention further comprises a step f) of physical separation of sediments and catalyst fines to obtain a liquid hydrocarbon fraction liquid the heavy liquid fraction obtained at the end of step e ) precipitation contains precipitated asphaltene-type organic sediments which result from hydrocracking conditions and precipitation conditions according to the invention. This heavy liquid fraction may also contain catalyst fines resulting from the attrition of extruded type catalysts in the use of hydrocracking reactor. Thus, at least a portion of the heavy liquid fraction from step e) of precipitation is subjected to a separation of sediments and catalyst residues, by means of a physical separation means selected from a filter, a membrane of separation, a bed of organic or inorganic type filter solids, electrostatic precipitation, electrostatic filter, centrifuge system, decantation, centrifugal decanter, auger withdrawal, or physical extraction. A combination, in series and / or in parallel and can operate sequentially, of several separation means of the same type or different type can be used during this step f) 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. At the end of step f) of separation of the sediments, a liquid hydrocarbon fraction (with a sediment content after aging of less than or equal to 0.1% by weight) is obtained, comprising a portion of the distillate fraction according to the invention. invention introduced in step e). Step q) Recovery of the liquid hydrocarbon fraction According to the invention, the mixture resulting from stage f) is advantageously introduced into a stage g) of recovery of the liquid hydrocarbon fraction having a sediment content after aging less than or equal to 0 1% by weight of separating the liquid hydrocarbon fraction from step f) of the distillate cut introduced in step e).
    [0023] Step g) is a separation step similar to steps b) and d) of separation. Step g) can be implemented by means of separator balloon type equipment and / or distillation columns so as to separate on the one hand at least part of the distillate cut introduced during step e) and on the other hand the liquid hydrocarbon fraction having a sediment content after aging less than or equal to 0.1% by weight. Advantageously, a portion of the distillate cut separated from step g) is recycled to the precipitation step e). Said liquid hydrocarbon fraction may advantageously be used as a base for fuel oil or as fuel oil, in particular as a base for bunker oil or as bunker oil, having a sediment content after aging of less than 0.1% by weight. Advantageously, said liquid hydrocarbon fraction is mixed with one or more fluxing bases selected from the group consisting of catalytic cracking light cutting oils, catalytic cracking heavy cutting oils, catalytic cracking residue, a kerosene, a gas oil, a vacuum distillate and / or a decanted oil, the distillate cut according to the invention. According to a particular embodiment, part of the distillate cut according to the invention can be left in the sediment-reduced liquid hydrocarbon fraction so that the viscosity of the mixture is directly that of a desired grade of fuel oil. for example 180 or 380 cSt at 50 ° C.
    [0024] The liquid hydrocarbon fractions according to the invention may, at least in part, advantageously be used as oil bases or as fuel oil, in particular as a base for bunker oil or as bunker oil with a sediment content after aging (measured according to the method ISO 10307-2) less than or equal to 0.1% by weight.
    [0025] By "oil" is meant in the invention a hydrocarbon fraction that can be used as a fuel.Fuel oil base is understood to mean a hydrocarbon fraction which, when mixed with other bases, constitutes a fuel oil. to obtain a fuel oil, the liquid hydrocarbon fractions from step f) or g) can be mixed with one or more fluxing bases selected from the group consisting of light catalytic cracking oils, heavy cutting oils catalytic cracking residue, a catalytic cracking residue, a kerosene, a gas oil, a vacuum distillate and / or a decanted oil, the distillate cut according to the invention. Preferably, kerosene, gas oil and / or vacuum distillate produced in the process of the invention will be used.
    [0026] Optionally, a portion of the fluxes may be introduced as part or all of the distillate cut according to the invention. Figure 1 schematically depicts an exemplary implementation of the invention without limiting the scope thereof.
    [0027] The hydrocarbon feedstock (1) and hydrogen (2) are contacted in a fixed bed hydrotreating zone (step a). The effluent (3) from the hydrotreatment zone is sent to a separation zone (optional separation step b)) making it possible to obtain at least one light hydrocarbon fraction (4) and a heavy fraction (5). containing compounds boiling at not less than 350 ° C. The effluent (3) from the hydrotreatment zone 15, in particular in the absence of the optional step b), or a heavy fraction (5) from the separation zone b) (when the step b) is implementation) is sent to the bubbling bed hydrocracking zone c). The effluent (6) from the hydrocracking zone c) is sent to a separation zone d) to obtain at least one gaseous fraction (7) and at least one heavy liquid fraction (8). This liquid fraction (8) is brought into contact with the distillate cut (9) according to the invention during a step e) of precipitation in the zone e) of precipitation. The effluent (10) consisting of a heavy fraction and sediment is treated in a physical separation zone f) for removing a fraction comprising sediments (12) and recovering a reduced-content liquid hydrocarbon fraction (11). in sediments. The liquid hydrocarbon fraction (11) is then treated in a zone g) of recovery firstly of the liquid hydrocarbon fraction (14) having a sediment content after aging less than or equal to 0.1% by weight, and on the other hand, a fraction (13) containing at least a portion of the distillate cut introduced in step e) in zone e). Several variants as indicated in the description may be made according to the invention. Some variants are described below. Alternatively, the separation zone b) between the fixed bed hydrotreatment zone a) and the bubbling bed hydrocracking zone c) is carried out with decompression. In another variant, the separation zone b) between the fixed bed hydrotreating zone a) and the bubbling bed hydrocracking zone c) is carried out without decompression. It is also possible for at least part of the effluent from the hydrotreating zone a) to be introduced directly into the bubbling bed hydrocracking zone c) without changing the chemical composition and without significant loss of pressure. that is to say without decompression. The following example illustrates the invention without, however, limiting its scope. A vacuum residue (RSV Ural) containing 87.0% by weight of compounds boiling at a temperature above 520 ° C, having a density of 9.5 ° API and a sulfur content of 2.72% was treated. weight. The feedstock was subjected to a hydrotreatment step including two permutable reactors. The three NiCoMo catalysts on Alumina used in series are sold by the company Axens under the references HF858 (hydrodemetallation catalyst: HDM), HM848 (transition catalyst) and HT438 (hydrodesulphurization catalyst: HDS). The operating conditions are given in Table 1. Table: Operating conditions fixed bed - hydrotreatment NiCoMo on alumina The effluent of the hydrotreatment is then subjected to a separation step making it possible to recover a light fraction (gas) and a heavy fraction containing a majority of compounds boiling above 350 ° C (350 ° C + fraction). The heavy fraction (350 ° C + fraction) is then treated in a hydrocracking step comprising two successive bubbling bed reactors. The operating conditions of the hydrocracking step are given in Table 2. Temperature (° C) Partial pressure H2 (MPa) VVH (h-1, Sm3 / h fresh feed / m3 fixed bed catalyst) 0.18 1000 fresh charge) H2 / HO inlet fixed bed section excluding H2 consumption (Nm3 / m3 HDM catalysts, transition and HDS 3036705 26 TFilleau 2: Ongoing condi- tions of I .Fràr of hydrocrn (lime 2 NiMo bubbling beds on alumina 423 Catalysts Temperature R1 (° C) Temperature R2 (° C) Partial pressure H2 (MPa) VVH "reactors" (h-1, Snri3 / h cool load / m3 of reactors) NI- "bubbling bed catalysts" (h-1, Sm3 / h fresh load / m3 of bubbling bed catalysts) H2 / HC hydrocracking section input H2 consumption (Nm3 / m3 fresh feed) The NiMo catalyst on Alumina used is sold by the company Axens under the reference HOC-548. effluent from the hydrocracking step is then subjected to a separation step 5 to separate a gaseous fraction and a heavy liquid fraction by means of parators. The heavy liquid fraction is then distilled in an atmospheric distillation column so as to recover distillates and an atmospheric residue. Samples, weighed and analyzed make it possible to establish an overall material balance of the hydrotreatment sequence in fixed bed + hydrocracking in a bubbling bed.
    [0028] The yields and the sulfur contents of each fraction obtained in the effluents leaving the overall flows are given in Table 3 below: ______________________________________ Table 3 Yield (Yield) and sulfur content (S) of the Ir effluent The atmospheric residue RA (350 ° C fraction + the sum of the vacuum distillate and the vacuum residue) is subjected to a treatment according to several variants: A) a variant A (no) according to the invention) in which the atmospheric residue RA is filtered by means of a metallic porous filter of Pan® brand. The sediment content after aging is measured on the atmospheric residue recovered after separation of the sediments. B) a variant B in which a precipitation step (in accordance with the invention) is carried out by mixing, with stirring at 80 ° C. for 1 minute, the atmospheric residue RA and a distillate cut according to the invention in different proportions described in FIG. Table 5: 0 C1-04 (gas) 4.0 0 94.12 Yield (% w) S (% wt) 0.7 2.7 Products Naphtha (PI - 100 ° C) Heavy Nadhta (100-150 °) C) Kerosene (150 ° C-225 ° C) Diesel (225 ° C - 350 ° C) Vacuum distillate (350 ° C - 520 ° C) Vacuum residue (520 ° C +) Hydrotreatment fixed bed + separation + Hydrocracking 2 bubbling beds (423/431 ° C) 3036705 28 - mixture 1: mixture of 50% by weight of atmospheric residue (RA) and 50% by weight of the distillate fraction X, - mixture 2: mixture of 50% by weight of atmospheric residue ( RA) and 50% by weight of the distillate cut Y, 5 - mixture 3: mixture of 50% by weight of atmospheric residue (RA) and 50% by weight of the distillate cut Z. The corresponding atmospheric residue at the 350 ° C + fraction of the effluent from the hydrocracking stage is characterized by a sediment content (IP375) of 0.3% m / m and a sediment content after aging (IP390) of 0.7% m / m.
    [0029] The simulated distillation curves of X, Y and Z distillate slices in blends 1, 2 and 3 are shown in Table 4. TABLE 4 Simulated distillate curves of neck, distillate X. Y and The different mixtures lead to the appearance of existing sediments (IP375) and are then subjected to a step of physically separating the sediments and catalyst residues by means of a Palle brand metal porous filter. This step of physical separation of the sediments is followed by a distillation step of the mixture making it possible to recover, on the one hand, the atmospheric residue with a reduced sediment content, and on the other hand the distillate cut. Distillate cup X ° Wt. Distilled temperature (° C) 5 105 10 156 20 198 30 230 40 252 50 271 60 70 80 90 Cutting distillate Y% weight Temperature diilled (° C) 5 153 10 198 20 225 30 year Cutting distillate 7 ° distilled weight (° C) 5 223 235 252 268 282 295 308 321 331 342 348 244 10 20 30 262 40 277 50 294 60 308 70 322 80 40 50 291 60 308 70 324 80 339 347 336 90 347 95 3036705 29 Table 5: Sediment Precipitation and Separation No Precipitation (Non-Compliant) 100 Mixture 1 (RA + Distillate Cup X) 50 50.V1 Mixture 2 (RA + Distillate Cup Y) Mixture 3 ( RA + Distillate cup Z) 50 50 50 0.57a 0.4 <0.1 b <01b Proportion of the atmospheric residue (RA in the mixture (/ 0 m / m) proportion of the distillate fraction in the mixture (° / 0 m / m) sediment sediment of the mixture (measurement according to IP375a m / m) Sediment content of the atmospheric residue RA recovered (measurement according to P390b (Yorn / m) The operating conditions of the hydrocracking step coupled with the different treatment variants (sediment separation with precipitation stage and recovery of the distillate cut (variant B) or without precipitation step (variant A) of the atmospheric residue (RA) 5 have an impact on the stability of the effluents obtained. This is illustrated by the post-aging sediment concentrations measured in the atmospheric residue RA (350 ° C + cut) before (0.7% w / w) and after (<0.1% w / w) the precipitation and separation stage. sediments, then recovery of the distillate cut. Thus, the atmospheric residues obtained according to the invention constitute excellent oil bases, especially bunker oil bases having a sediment content after aging (IP 390) of less than 0.1% by weight. The atmospheric residue RA treated according to the case "mixture 3" of Table 5 having a sediment content after aging of less than 0.1%, a sulfur content of 0.37% w / w and a viscosity of 590 cSt at 50 ° C. C is mixed with process diesel (Table 3) having a sulfur content of 0.05% w / w and a viscosity of 2.5 cSt at 50 ° C, in RA / diesel 90/10 ratios. (m / m). The resulting blend has a viscosity of 336 cSt at 50 ° C, a sulfur content of 0.34% w / w and a sediment content after aging (IP390) of less than 0.1 wt%. This mixture thus constitutes a quality bunker oil, which can be sold according to grade RMG or IFO 380, with low sediment content and low sulfur content. For example, it may be burned outside ECA zones 5 by 2020-25 without the vessel being equipped with flue-gas scrubbing to remove the sulfur oxides.
    权利要求:
    Claims (5)
    [0001]
    REVENDICATIONS1. A process for treating a hydrocarbon feedstock 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 temperature of boiling at least 440 ° C, said process comprising the following steps: a) a fixed bed hydrotreating step, wherein the hydrocarbon feedstock and hydrogen are contacted on a hydrotreatment catalyst, b) an optional step of separating the effluent from step a) of hydrotreatment into at least a light hydrocarbon fraction containing fuels bases and a heavy fraction containing compounds boiling at least 350 ° C, c) a step of hydrocracking at least a portion of the effluent from step a) or at least a portion of the heavy fraction from step b) in at least one reactor containing a supported catalyst; bubbling bed, d) a separation step of the effluent from step c) to obtain at least one gaseous fraction and at least one heavy liquid fraction, e) a sediment precipitation step in which the heavy liquid fraction from step d) of separation is put in contact with a distillate cut of which at least 20% by weight has a boiling temperature greater than or equal to 100 ° C, for a period of less than 500 minutes, at a temperature between 25 and 350 ° C, and a lower pressure at 20 MPa, f) a step of physically separating the sediments of the heavy liquid fraction resulting from the precipitation step e) to obtain a liquid hydrocarbon fraction, g) a step of recovering a liquid hydrocarbon fraction having a content of sediments, measured according to method ISO 10307-2, less than or equal to 0.1% by weight, consisting in separating the liquid hydrocarbon fraction resulting from step f) from the distillate cut introduced during the step e).
    [0002]
    2. The method of claim 1 wherein the distillate cut comprises at least 25 wt.% Having a boiling temperature greater than or equal to 100 ° C. 3036705 32
    [0003]
    3. Process according to either of claims 1 and 2 wherein at least 5% by weight of the distillate fraction has a boiling point of at least 252 ° C.
    [0004]
    4. Method according to one of the preceding claims wherein the distillate cut comprises hydrocarbons having more than 12 carbon atoms.
    [0005]
    5. Method according to one of the preceding claims wherein the distillate cut comes in part, if not all stages b) and / or d) separation or other refining process or another chemical process . A process as claimed in any one of the preceding claims wherein a portion of the distillate cut separated from step g) is recycled to the precipitation step e). 7. Method according to one of the preceding claims wherein the hydrotreatment step a) comprises a first hydrodétététation step al) carried out in one or more hydrodemetallation zones in fixed beds and a second step a2) subsequent to hydrodesulfurization carried out in one or more fixed bed hydrodesulfurization zones. Process according to one of the preceding claims, in which the hydrotreatment step a) is carried out at a temperature of between 300 ° C. and 500 ° C. under a hydrogen partial pressure of between 5 MPa and 35 MPa, with a the space velocity of the hydrocarbon feedstock in a range from 0.1 hr-1 to 5 hr-1, and the amount of hydrogen blended with the feed is between 100 Nm3 / m3 and 5000 Nm3 / m3. 9. Method according to one of the preceding claims wherein the hydrocracking step c) is carried out under an absolute pressure of between 2.5 MPa and 35 MPa, at a temperature between 330 ° C and 550 ° C, with a space velocity in a range of 0.1 W1 to 10 h-1, and the amount of hydrogen mixed with the feed is 50 Nm3 / m3 to 5000 Nm3 / m3. 10. Method according to one of the preceding claims wherein the precipitation step is carried out in the presence of an inert gas and / or an oxidizing gas and / or an oxidizing liquid and / or hydrogen, preferably from separation steps b) and / or c). The method according to one of the preceding claims wherein the separation step f) is carried out by means of a separation means chosen from a filter, a separation membrane, a bed of organic-type filtering solids or inorganic, electrostatic precipitation, centrifugation, decantation, auger withdrawal, or physical extraction. 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. The process of claim 12 wherein the feedstock contains at least 1% C7 asphaltenes and at least 5 ppm metals. Process according to one of the preceding claims, in which the liquid hydrocarbon fractions resulting from step 0 or g) are mixed with one or more fluxing bases selected from the group consisting of light cutting oils of a catalytic cracking, the catalytic cracked heavy-cutting oils, the catalytic cracking residue, a kerosene, a gas oil, a vacuum distillate and / or a decanted oil, the distillate cut according to claims 1 to 4, to obtain an oil .
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    同族专利:
    公开号 | 公开日
    CN107912046A|2018-04-13|
    US20180163144A1|2018-06-14|
    ES2728582T3|2019-10-25|
    TW201715031A|2017-05-01|
    JP2018521162A|2018-08-02|
    PT3303523T|2019-06-12|
    JP6670856B2|2020-03-25|
    WO2016192891A1|2016-12-08|
    FR3036705B1|2017-06-02|
    KR20180014775A|2018-02-09|
    EP3303523B1|2019-03-06|
    TWI691591B|2020-04-21|
    EP3303523A1|2018-04-11|
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    法律状态:
    2016-06-07| PLFP| Fee payment|Year of fee payment: 2 |
    2016-12-02| PLSC| Publication of the preliminary search report|Effective date: 20161202 |
    2017-06-22| PLFP| Fee payment|Year of fee payment: 3 |
    2018-06-27| PLFP| Fee payment|Year of fee payment: 4 |
    2020-06-26| PLFP| Fee payment|Year of fee payment: 6 |
    优先权:
    申请号 | 申请日 | 专利标题
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    US15/578,580| US20180163144A1|2015-06-01|2016-04-20|Method for converting feedstocks comprising a hydrotreatment step, a hydrocracking step, a precipitation step and a sediment separation step, in order to produce fuel oils|
    PCT/EP2016/058745| WO2016192891A1|2015-06-01|2016-04-20|Method for converting feedstocks comprising a hydrotreatment step, a hydrocracking step, a precipitation step and a sediment separation step, in order to produce fuel oils|
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    CN201680032049.2A| CN107912046A|2015-06-01|2016-04-20|Including hydrotreating step, hydrocracking step, settling step and deposit separating step to produce the raw material method for transformation of fuel oil|
    JP2017562076A| JP6670856B2|2015-06-01|2016-04-20|Feedstock conversion method for producing fuel oil, comprising a hydrotreating step, a hydrocracking step, a precipitation step, and a precipitate separation step|
    PT16717176T| PT3303523T|2015-06-01|2016-04-20|Method for converting feedstocks comprising a hydrotreatment step, a hydrocracking step, a precipitation step and a sediment separation step, in order to produce fuel oils|
    TW105116914A| TWI691591B|2015-06-01|2016-05-30|Process for the conversion of feeds, comprising a hydrotreatment step, a hydrocracking step, a precipitation step and a step of separating sediments, for the production of fuel oils|
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