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    • 专利摘要:
    A process for treating a hydrocarbon feed having a sulfur content of at least 0.5 wt.%, An asphaltene content of at least 1 wt.%, An initial boiling temperature of at least 1 wt. 340 ° C and a final boiling point of at least 480 ° C, to obtain at least one deasphalted oil fraction having a sulfur content of less than or equal to 0.5% by weight and a lower sediment content or equal to 0.1% by weight, comprising the following successive stages: a) a hydrotreating step, b) optionally a separation step of the effluent obtained at the end of step a), c) a step hydroconversion of at least a portion of the effluent from step a) or at least a portion of the heavy fraction from step b) and optionally at least a portion of the light fraction from step b), d) a step of separating the effluent from step c), e) at least one step of disasphon selective alteration of at least a portion of the liquid hydrocarbon fraction resulting from step d), f) a step of recycling at least a portion of said unsaturated oil fraction from step e) upstream of the step a) of hydrotreatment and / or at the entry of the hydroconversion stage c).
    公开号:FR3014897A1
    申请号:FR1362748
    申请日:2013-12-17
    公开日:2015-06-19
    发明作者:Isabelle Merdrignac；Wilfried Weiss；Jerome Majcher
    申请人:IFP Energies Nouvelles IFPEN；
    IPC主号:
    专利说明:

    [0001] FIELD OF THE INVENTION 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 the treatment of heavy petroleum feedstocks for the production of fuel oils and oil bases, in particular bunker oil and bunker oil bases with low sulfur content. TECHNOLOGICAL BACKGROUND While regulations on sulfur content in land-based fuels, typically gasoline and diesel, had become very stringent in recent decades, regulations on sulfur content in marine fuels so far as not binding. Indeed, marine fuels currently on the market can contain up to 3.5% or 4.5% by weight of sulfur. As a result, ships have become the main source of sulfur dioxide (SO2) emissions. In order to reduce these emissions, the International Maritime Organization (IMO) has submitted recommendations in terms of specifications for marine fuels (Annex VI of the MARPOL Convention). These recommendations are presented in the 2012 version of ISO 8217. The recommendations now focus on SOx emissions from marine fuels. The equivalent sulfur content recommended by 2020 or 2025 is less than or equal to 0.5% by weight for vessels operating outside the "Sulfur Emission Control Areas" (ZCES or SECA, "Sulfur Emission Control Areas "according to the English terminology). Within IMAS, the IMO predicts an equivalent sulfur content of 0.1% or less by 2015, and another very stringent recommendation is the post-aging sediment the ISO 10307-2 standard must be less than or equal to 0.1% by weight. The fuel oils used in marine transport generally include atmospheric distillates, vacuum distillates, atmospheric residues and vacuum residues from direct distillation or from refining processes, including hydrotreating processes and These cuts can be used alone or as a mixture. An object of the present invention is to provide a method of converting heavy oil feedstock for the production of fuel oil bases, especially in the form of a stable deasphalted oil with a low sulfur content and sediment after aging even with a high conversion. Indeed, during the conversion step, the high conversion of a heavy charge (comprising for example at least 75% of compounds having a boiling point greater than 540 ° C.) under severe conversion conditions, 'accompanied by sediment formation mainly related to the precipitation of asphaltenes and render the unconverted heavy fraction unstable and unfit for use as bunker oil or bunker oil bases. The implementation of the process according to the invention with a selective deasphalting step allows the production of a high conversion stable bunker oil during the hydroconversion stage. Another object of the present invention is to jointly produce, by the same method, atmospheric distillates (naphtha, kerosene, diesel), vacuum distillates and / or light (C 1 to C 4) gases. The implementation of the process according to the invention, in particular a high conversion hydroconversion stage, makes it possible to greatly improve the yields of distillates with respect to a bunker fuel production process using only a step 25 of fixed bed hydrotreatment and a boiling bed hydroconversion stage. 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.
    [0002] Methods for refining and converting heavy petroleum feedstocks comprising a first fixed bed hydrotreatment stage and then a bubbling bed hydroconversion stage have been described in patent documents CA 1238005, EP 1343857 and EP 0665282.
    [0003] EP 0665282, which describes a process for the hydrotreatment of heavy oils, aims to extend the life of the reactors. CA 1238005 describes a process for converting a heavy liquid hydrocarbon feedstock using a plurality of reactors in series, wherein the conversion rate is improved by special recycling of the heavy fraction obtained. The process disclosed in EP 1343857 is described as a hydrotreatment process that can implement a hydrodemetallation section, which can be preceded by a guard zone of the reactive reactor type, and a hydrodesulfurization section.
    [0004] The applicant in his research has developed a process for the production of fuel oils and oil bases from deasphalted oil obtained with good performance and good stability, despite the implementation of a high conversion, by the implementation implementing successively a fixed bed hydrotreating step, a hydroconversion step and a step of deasphalting the heavy fraction resulting from the hydroconversion step. It has been observed that the implementation of the deasphalting step according to the invention, in addition to the elimination of organic sediments formed by the precipitation of asphaltenes, allows the elimination of the fine catalysts which results in an improved stability of deasphalted oil and a sediment content after reduced aging.
    [0005] SUMMARY DESCRIPTION OF THE INVENTION The invention relates to a process for treating a hydrocarbon feedstock having a sulfur content of at least 0.5% by weight, an asphaltene content of at least 1% by weight, a temperature initial boiling point of at least 340 ° C and a final boiling temperature of at least 480 ° C, thereby obtaining at least one deasphalted oil fraction having a sulfur content of less than or equal to 0.5% by weight and a sediment content less than or equal to 0.1% by weight, comprising the following successive steps: a) a fixed bed hydrotreatment step, in which the hydrocarbon feedstock and hydrogen are contacted on at least one hydrotreatment catalyst, b) optionally a step of separating the effluent obtained at the end of step a) of hydrotreatment into at least a light fraction and at least one heavy fraction, c) a step hydroconversion of at least a portion of the effluent of step a) or at least a portion of the heavy fraction resulting from step b) and optionally at least a portion of the light fraction resulting from step b) in at least one reactor containing at least minus a catalyst supported in bubbling bed, d) a step of separating the effluent from step c) to obtain at least one gaseous fraction and a liquid hydrocarbon fraction, e) at least one selective deasphalting step for separating at least one asphalt fraction and at least one deasphalted oil fraction, the deasphalting step being at least carried out by contacting at least a portion of the liquid hydrocarbon fraction resulting from step d) with a mixture of at least one minus a polar solvent and at least one apolar solvent under subcritical conditions for the solvent mixture used. f) a step of recycling at least a portion of said deasphalted oil fraction from step e) upstream of the hydrotreatment step a) and / or at the entry of step c) of hydroconversion. Advantageously, the deasphalting step e) comprises at least two deasphalting stages in series making it possible to separate at least one asphalt fraction, at least one deasphalted oil fraction called heavy DAO and at least one light deasphalted oil fraction called light DAO, at least one of said deasphalting steps being carried out by contacting at least a portion of the liquid hydrocarbon fraction resulting from step d) with a mixture of at least one polar solvent and at least one apolar solvent under the conditions subcritical for the solvent mixture used.
    [0006] Advantageously, at least a portion of the so-called heavy DAO desalted oil fraction from step e) is recycled upstream of the hydrotreatment step a) and / or at the inlet of the hydroconversion stage c). .
    [0007] Advantageously, step e) is carried out at extraction temperature of between 50 and 350 ° C., and a pressure of between 0.1 and 6 MPa. Advantageously, the fixed bed hydrotreatment stage is carried out at a temperature of between 300 ° C. and 500 ° C., under an absolute pressure of between 2 MPa and 35 MPa, with a space velocity of the hydrocarbon feedstock included in a range ranging from 0.1 h-1 to 5 h-1, and the amount of hydrogen is between 100 Nm3 / m3 and 5000 Nm3 / m3.
    [0008] Advantageously, the polar solvent used in step e) is chosen from pure aromatic or naphtho-aromatic solvents, polar solvents comprising heteroelements, or their mixture or sections rich in aromatics such as sections from the FCC (Fluid Catalytic Cracking), cuts derived from coal, biomass or biomass / coal mixture.
    [0009] Advantageously, the apolar solvent used in step e) comprises a saturated hydrocarbon solvent comprising a carbon number greater than or equal to 2, preferably between 2 and 9.
    [0010] Advantageously, the hydroconversion step c) is carried out under an absolute pressure of between 2.5 MPa and 35 MPa, at a temperature of between 330 ° C. and 550 ° C., with a space velocity ranging from 0 to , 1 h-1 to 5 h-1, and the amount of hydrogen is 50 Nm3 / m3 to 5000 Nm3 / m3.
    [0011] The invention also relates to a deasphalted oil that can be obtained according to the process according to the invention and that can be used as a fuel oil base. DETAILED DESCRIPTION OF THE INVENTION The hydrocarbon feedstock treated in the process according to the invention can be described as a heavy load. It has an initial boiling point of at least 340 ° C and a final boiling temperature of at least 480 ° C. Preferably, its initial boiling point is at least 350 ° C., preferably at least 375 ° C., and its final boiling point is at least 500 ° C., preferably at least 520 ° C. C, more preferably at least 550 ° C, and even more preferably at least 600 ° C. The hydrocarbon feedstock may be chosen from atmospheric residues, vacuum residues from direct distillation, crude oils, crude head oils, deasphalting resins, asphalts or deasphalting pitches, residues resulting from conversion processes. , aromatic extracts from lubricant base production lines, oil sands or derivatives thereof, bituminous 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. The hydrocarbon feedstock treated in the process according to the invention is sulfurized. Its sulfur content is at least 0.5% by weight, preferably at least 1% by weight, more preferably at least 2% by weight, more preferably at least 3% by weight. The metal content of the filler is advantageously greater than 110 ppm of metals (Ni + V), and preferably greater than 150 ppm.
    [0012] In addition, the hydrocarbon feedstock treated in the process according to the invention contains asphaltenes. Its asphaltenes content is at least 1% by weight. By "asphaltene" is meant in the present description heavy hydrocarbon compounds insoluble in n-heptane (also called C7 asphaltenes) but soluble in toluene. The quantification of asphaltenes generally uses standard analyzes as defined, for example, in standards AFNOR T 60-115 (France) or ASTM 893-69 (United States). These charges can advantageously be used as they are. Alternatively, the hydrocarbon feed can be diluted by co-charging. This co-charge may be a hydrocarbon fraction or a lighter hydrocarbon fraction mixture, which may preferably be chosen from the products resulting from a fluid catalytic cracking (FCC) process according to the English terminology. Saxon), a light 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, a FCC residue, a gas oil fraction, especially a fraction obtained by atmospheric distillation or under vacuum, such as vacuum gas oil, or may come from another refining process. The co-charge may also advantageously be one or more cuts resulting from the process of liquefying coal or biomass, aromatic extracts, or any other hydrocarbon cuts or non-petroleum fillers such as pyrolysis oil. The heavy hydrocarbon feedstock according to the invention may represent at least 50%, preferably 70%, more preferably at least 80%, and even more preferably at least 90% by weight of the total hydrocarbon feedstock treated by the process according to the invention. Hydrotreating step a) Said hydrocarbon feedstock is subjected according to the process of the present invention to a fixed bed hydrotreating step a) in which feedstock and hydrogen are contacted on a hydrotreatment catalyst. According to one variant, the hydrocarbon feedstock is sent to the hydrotreatment step a) in admixture with at least a portion of the deasphalted oil fraction from step e). According to one variant, the hydrocarbon feedstock is sent to the hydrotreating step a) in admixture with at least a portion of the so-called heavy DAO desalted oil fraction from step e). Hydroprocessing, commonly known as HDT, is understood to mean catalytic treatments with hydrogen supply which make it possible to refine, that is to say substantially reduce the content of metals, sulfur and other impurities, hydrocarbon feedstocks, while improving the hydrogen to carbon ratio of the load and transforming the load 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, hydodeoxygenation reactions. , hydrodearomatization, hydroisomerization, hydrodealkylation, hydrocracking, hydro-deasphalting and Conradson carbon reduction.
    [0013] According to a preferred variant, the hydrotreatment step a) comprises a first hydrodetallation (HDM) step (a1) carried out in one or more fixed bed hydrodemetallation zones and a second hydrodemétallation 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 step (a2). hydrodesulfurization, the effluent of the first step (a1) of hydrodemetallation is brought into contact with a hydrodesulphurization catalyst, under hydrodesulfurization conditions. This process, known as HYVAHL-FTM, is described, for example, in US Pat. No. 5,417,846. Those skilled in the art readily understand that, in the hydrodemetallization step, hydrodemetallation reactions are carried out but at the same time part of the other hydrotreatment reactions and in particular hydrodesulfurization. Similarly, in the hydrodesulphurization step, hydrodesulphurization reactions are carried out, but also part of the other hydrotreatment reactions and in particular hydrodemetallation reactions. The hydrotreating step a) according to the invention is carried out under hydrotreatment conditions. It may 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 2 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 WH, which is defined as the volumetric flow rate of the feedstock divided by the total catalyst volume, can be in a range from 0.1 h -1 to 5 h -1, preferably 0.1 h -1 to 2 h -1, more preferably 0.1 h -1 to 0.45 h -1, still more preferably 0.1 h -1 to 0 h -1. , 2 h-1. The amount of hydrogen mixed with the feedstock may be between 100 and 5000 normal cubic meters (Nm3) per cubic meter (m3) of liquid feed, preferably between 200 Nm3 / m3 and 2000 Nm3 / m3, and more preferably between 300 Nm3 / m3. m3 and 1500 Nm3 / m3. Step a) of hydrotreatment can be carried out industrially in one or more liquid downflow reactors. The hydrotreatment step a), in particular the hydrodemetallation section (HDM), advantageously comprises reactive reactors which make it possible, inter alia, to extend the cycle time of the process by periodically replacing the catalyst present in the reactive reactors. . According to a variant of the process, the hydrotreating stage a) comprises at least one moving bed reactor, generally located in the hydrodemetallation section (HDM). 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 hydrodehydrogenating 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, 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% may be employed. 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 may for example be selected 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 can be y (gamma) or r (eta) alumina. This catalyst is most often in the form of extrudates. The total content of Group VIB and VIII metal oxides can be from 5% to 40% by weight and generally from 7% to 30% by weight and the weight ratio of the group metal (or metals) to the metal oxide VIB on metal (or metals) of group VIII is generally between 20 and 1, and most often between 10 and 2.
    [0014] In the case of a hydrotreating step including a hydrodemetallation (HDM) step and then a hydrodesulphurization step (HDS), specific catalysts adapted to each step are preferably used.
    [0015] Catalysts that may be used in the hydrodemetallization step are for example indicated in patent documents EP 0113297, EP 0113284, US Pat. No. 5,222,656, US Pat. No. 5,827,421, US Pat. No. 7,110,445, US Pat. No. 5,622,616 and US Pat. No. 5,089,463. Hydrodemetallation catalysts are preferably used in the reactive reactors.
    [0016] Catalysts that can be used in the hydrodesulfurization step are, for example, indicated in patent documents EP 0113297, EP 0113284, US Pat. No. 6589908, US Pat. No. 4,818,743 or US Pat. No. 6,332,976. It is also possible to use a mixed catalyst, active in hydrodemetallation and in hydrodesulphurization, with both for the hydrodemetallation section and for the hydrodesulfurization section as described in patent document FR 2940143. Prior to the injection of the feedstock, the catalysts used in the process according to the present invention are preferably subjected to a sulfurization treatment. in-situ or ex-situ. Separation step b) The effluent obtained at the end of the fixed-bed hydrotreatment step a) advantageously undergoes at least one separation step, possibly completed by further additional separation steps, making it possible to separate at least one separation stage. minus a light fraction and at least one heavy fraction. By "light fraction" is meant a fraction in which at least 80% of the compounds have a boiling point below 350 ° C. By "heavy fraction" is meant a fraction in which at least 80% of the compounds have a boiling point greater than or equal to 350 ° C.
    [0017] At least a portion of the heavy fraction is advantageously sent to the hydroconversion step 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, of which at least a portion is preferably used as fluxing agent. of a fuel oil. The heavy fraction preferably comprises a vacuum distillate fraction and a vacuum residue fraction and / or an atmospheric residue fraction. The separation step b) can be implemented 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, liquid / liquid extraction, and combinations of these different methods that can operate at different pressures and temperatures. According to a first embodiment of the present invention, the effluent from step a) hydrotreatment undergoes a step b) 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 optionally a low temperature high pressure separator (HPBT), optionally followed by low pressure separators and / or an atmospheric distillation section and / or a vacuum distillation section. The effluent of step a) can be sent to a fractionation section, generally in a high temperature high pressure separator (HPHT), having a cutting point between 200 ° C and 400 ° C to obtain a light fraction and a heavy fraction. In general, the separation is not made according to a precise cutting point, rather it is similar to a flash type separation. Preferably, said heavy fraction can then be expanded in a high temperature low pressure separator (BPHT) to obtain a gas fraction and a liquid fraction.
    [0018] The heavy fraction can then be directly sent to the hydroconversion stage c). The light fraction resulting from the high temperature high pressure separator (HPHT) can then be partially condensed in a low temperature high pressure separator (HPBT) which makes it possible to obtain a gas fraction and a liquid fraction. The liquid fraction from the low temperature high pressure separator (HPBT) can then be expanded in a low temperature low pressure separator (BPBT) allowing a gas fraction and a liquid fraction to be obtained. The liquid fractions from low temperature high pressure (BPHT) and low temperature low temperature (BPBT) separators can be fractionated by atmospheric distillation into at least one atmospheric distillate fraction, preferably containing at least one light fraction of naphtha type hydrocarbons. , Kerosene and / or diesel fuel, and an atmospheric residue fraction. At least a part of the atmospheric residue fraction can also be fractionally fractionated by distillation into a vacuum distillate fraction, preferably containing vacuum gas oil, and a vacuum residue fraction. At least a portion of the vacuum distillate fraction is preferably fed to the hydroconversion stage c). Another part of the vacuum distillate may be used as a fuel fluxing agent. Preferably, at least one light hydrocarbon fraction of naphtha, kerosene and / or gas oil or vacuum gas oil is used as a fuel of 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. In the case where part of the vacuum distillate is catalytically cracked conversion products LCO type (Light Cycle Oil according to the English terminology) and HCO (Heavy Cycle Oil according to the English terminology) can be used as a fluxing agent of a fuel oil. Another portion of the atmospheric residue may also be subjected to a conversion process such as catalytic cracking.
    [0019] Part of the vacuum residue may also be recycled in the hydrotreating step a). According to a second embodiment, part of the effluent from step a) hydrotreatment undergoes a step b) separation without decompression. According to this embodiment, the effluent of the hydrotreating stage a) is sent to a separation section, generally in a high temperature high pressure separator (HPHT), having a cutting point between 200 ° C and 400 ° C. C to obtain at least a light fraction and at least a heavy fraction. In general, the separation is preferably not made according to a precise cutting point, it is rather like a flash type separation. The heavy fraction can then be directly sent to the hydroconversion stage c).
    [0020] The light fraction from the high temperature high pressure separator (HPHT) may undergo further separation steps. Advantageously, it may be subjected to atmospheric distillation 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. Preferably, at least a portion of the light fraction of liquid hydrocarbons of the naphtha, kerosene and / or diesel type is used as the fluxing agent of a fuel oil. At least a portion of the vacuum distillate fraction is preferably fed to the hydroconversion stage c).
    [0021] Another part of the vacuum distillate can be upgraded by being subjected to a hydrocracking step and / or catalytic cracking in a fluidized bed. In the case where part of the vacuum distillate is catalytically cracked conversion products LCO type (Light Cycle Oil according to the English terminology) and HCO (Heavy Cycle Oil according to the English terminology) can be used as a fluxant of a fuel oil. Even more advantageously, the light fraction obtained from the high-temperature high-pressure separator (HPHT) may be cooled and then introduced into a low-temperature high-pressure separator (HPBT) in which a hydrogen-containing gas fraction and a hydrogen fraction are separated. liquid containing distillates. This liquid fraction containing distillates can be sent to the hydroconversion stage c) via a pump. Alternatively, this liquid fraction containing distillates can be sent to the final separation step d) which also processes the effluent from the hydroconversion step c). 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 hydroconversion step. Intermediate fractionation without decompression being simpler than fractionation with decompression, the investment cost is therefore advantageously reduced. The gaseous fractions from the separation step preferably undergo a purification treatment to recover the hydrogen and recycle it to the hydrotreating and / or hydroconversion reactors. The presence of the intermediate separation step between the hydrotreatment step a) and the hydroconversion step c) advantageously makes it possible to have two independent hydrogen circuits, one connected to the other. hydrotreatment, the other to hydroconversion, and which, if necessary, can be connected to each other. Hydrogen supplementation may be at the hydrotreatment section, or at the hydroconversion section, or at both. The recycle hydrogen can supply the hydrotreatment section or the hydroconversion section or both. A compressor may optionally be common to both hydrogen circuits. The fact of being able to connect the two hydrogen circuits makes it possible to optimize the hydrogen management 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 30 2957607. The light fraction obtained at the end of the separation step b), which comprises hydrocarbon-type hydrocarbons. naphtha, kerosene and / or diesel or others, especially LPG and vacuum gas oil, can be upgraded according to the methods are well known to those skilled in the art. At least a part of the light fraction resulting from step b) is advantageously sent to the hydroconversion step c). The heavy fraction preferably comprising at least a part of the vacuum distillate fraction, at least a portion of the vacuum residue fraction and / or the atmospheric residue fraction is advantageously sent in the hydroconversion stage. . Hydroconversion step c) At least a portion of the effluent from step a) or at least a portion of the heavy fraction from step b) when said step is carried out and optionally at least a portion the light fraction resulting from the separation step b) is sent according to the process of the present invention to a hydroconversion stage c) which is carried out in at least one reactor containing at least one bubbling bed supported catalyst. Preferably all of the effluent from step a) is sent to step c) of hydroconversion. Said reactor can operate as an upflow of liquid and gas. The main purpose of hydroconversion is to convert the heavy fraction into lighter cuts while partially refining it. Alternatively, the effluent from step a) or at least a portion of the heavy fraction from step b) when said step is carried out and optionally at least a portion of the light fraction from the separation step b) is sent to the hydroconversion step c) in admixture with at least a portion of the deasphalted oil fraction from step e). Alternatively, the effluent from step a) or at least a portion of the heavy fraction from step b) when said step is carried out and optionally at least a portion of the light fraction from the separation step b) is sent to the hydroconversion step c) in mixture with at least a part of the so-called heavy DAO deasphalted oil fraction from step e). The hydrogen necessary for the hydroconversion reaction can be injected at the inlet of the hydroconversion section c) into a bubbling bed. It may be recycling hydrogen and / or make-up hydrogen. In the case where the hydroconversion section has several bubbling bed reactors, hydrogen can be injected at the inlet of each reactor.
    [0022] Bubbling bed technology is well known to those skilled in the art. Only the main operating conditions will be described here. The catalysts remain inside the reactors and are not removed with the products, except during the makeup and catalyst withdrawal phases necessary to maintain the catalytic activity. The temperature levels can be high in order to obtain high conversions while minimizing the amounts of catalysts used. The conditions of ebullated bed hydroconversion step c) may be conventional bubbling bed hydroconversion conditions of a heavy hydrocarbon fraction. 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, still more preferably between 11 MPa and 20 MPa, even more preferably between 13 MPa and 18 MPa, at a temperature between 330 ° C and 550 ° C, preferably between 350 ° C and 500 ° C, more preferably between 390 ° C and 490 ° C. The space velocity (VVH) and the hydrogen partial pressure are parameters that are set according to the characteristics of the product to be treated and the desired conversion. The VVH (defined as the volumetric flow rate of the feedstock divided by the total volume of the bubbling bed reactor) is generally in a range from 0.1 hr -1 to 5 hr -1, preferably 0.15 hr. -1 to 2 h -1 and more preferably 0.15 h -1 to 1 h -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 / m3 at 1200 Nm3 / m3.
    [0023] It is possible to use a conventional granular hydroconversion catalyst of the order of 1 mm. The catalyst is most often in the form of extrudates or beads. Typically, the catalyst comprises a support whose porous distribution is suitable for the treatment of the charge, preferably amorphous and very preferably alumina, a silica-alumina support being also possible in certain cases and at least one metal of the group VIII chosen from nickel and cobalt and preferably nickel, said group VIII element being preferably used in combination with at least one group VIB metal selected from molybdenum and tungsten and preferably the group VIB metal is molybdenum. Preferably, the hydroconversion catalyst comprises nickel as part of group VIII and molybdenum as part of group VIB. The nickel content is advantageously between 0.5 and 15%, expressed by weight of nickel oxide (NiO) and preferably between 1 and 10% by weight, and the molybdenum content is advantageously between 1 and 40% expressed by weight of molybdenum trioxide (MoO 3), and preferably between 4 and 20% by weight. Said catalyst may also advantageously contain phosphorus, the content of phosphorus oxide being preferably less than 20% by weight and preferably less than 10% by weight. The hydroconversion catalyst used according to the process according to the invention can be partially replaced by fresh catalyst by withdrawal, preferably at the bottom of the reactor and by introducing, either at the top or at the bottom of the reactor, fresh or regenerated catalyst or rejuvenated, preferably at regular time interval and preferably by puff or almost continuously. The replacement rate of the spent hydroconversion catalyst with fresh catalyst is advantageously between 0.01 kilograms and 10 kilograms per cubic meter of treated feedstock, and preferably between 0.3 kilograms and 3 kilograms per cubic meter of feedstock treated. This withdrawal and replacement are performed using devices advantageously allowing the continuous operation of this hydroconversion step.
    [0024] It is also advantageously possible to send the spent catalyst withdrawn from the reactor into a regeneration zone in which the carbon and the sulfur contained therein are removed and then to return this regenerated catalyst to the hydroconversion stage a). It is also advantageously possible to send the spent catalyst withdrawn from the reactor to a rejuvenation zone in which the major part of the deposited metals is removed before sending the spent and recycled catalyst to a regeneration zone in which the carbon is removed. and the sulfur contained therein and to return this regenerated catalyst in step a) of hydroconversion.
    [0025] This hydroconversion step c) according to the process of the invention can be carried out under the conditions of the H-OIL® process as described, for example, in US Pat. No. 6,270,654.
    [0026] The hydroconversion catalyst used in the hydroconversion stage c) advantageously makes it possible to ensure both the demetallation and the desulphurization, under conditions making it possible to obtain a low-content liquid feed with metals, with Conradson carbon and with sulfur and to obtain a high conversion to light products, that is to say in particular fuel fractions gasoline and diesel.
    [0027] Step c) is advantageously carried out in one or more three-phase hydroconversion reactors, preferably one or more three-phase hydroconversion reactors with intermediate settling flasks. Each reactor advantageously comprises a recirculation pump for maintaining the catalyst in a bubbling bed by continuously recycling at least a portion of a liquid fraction advantageously withdrawn at the top of the reactor and reinjected at the bottom of the reactor. Step d) of separation The effluent obtained at the end of step c) undergoes at least one separation step d), optionally supplemented by additional separation steps, making it possible to separate at least one gaseous fraction and one gaseous fraction. liquid hydrocarbon fraction.
    [0028] The effluent obtained at the end of the hydroconversion stage c) comprises a liquid hydrocarbon 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 stripping means with steam or hydrogen.
    [0029] The effluent obtained at the end of the hydroconversion stage c) is advantageously separated in at least one separator flask into at least one gaseous fraction and at least one liquid hydrocarbon fraction. These separators may for example be high temperature high pressure separators (HPHT) and / or high temperature low pressure separators (HPBT).
    [0030] 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 hydroconversion reactions. The hydrogen purification means may be an amine wash, a membrane, a PSA (pressure swing adsorption) system, or a plurality of these means arranged in series. The purified hydrogen can then advantageously be recycled in the process according to the invention, after possible recompression. The hydrogen may be introduced at the inlet of the hydrotreatment step a) and / or at the inlet of the hydroconversion stage c).
    [0031] The separation step d) may comprise atmospheric distillation and / or vacuum distillation. Advantageously, the separation step d) firstly comprises an atmospheric distillation, in which the effluent obtained at the end of stage c) is fractionated by atmospheric distillation into at least one atmospheric distillate fraction and at least one atmospheric residue fraction, followed by a vacuum distillation in which at least a portion of the atmospheric residue fraction obtained after atmospheric distillation is fractionated by vacuum distillation into at least one vacuum distillate fraction and at least one vacuum residue fraction. ; the liquid hydrocarbon fraction sent to step e) comprising at least a portion of said vacuum residue fraction and optionally a portion of said vacuum distillate fraction. The vacuum distillate fraction typically contains vacuum-type gas oil fractions. At least a portion of the vacuum distillate fraction may be subjected to a hydrocracking or catalytic cracking step. At least a part of the atmospheric residue fraction is advantageously sent to the hydroconversion step c). At least a portion of the vacuum residue fraction may also be recycled in the hydrotreating step a). At least a portion of the atmospheric distillate fraction may also be recycled in the hydrotreating step a) to lower the viscosity of the feed stream at the inlet of the hydrotreatment step in the case of a very high load treatment. viscous residue type under vacuum. Step e) Deasphalting The effluent obtained at the end of hydroconversion step c), and in particular the heavier liquid hydrocarbon fraction obtained after step d) of separation, may contain sediments and residues. of catalyst from step a) in a fixed bed and / or step c) in a bubbling bed in the form of fines. The liquid hydrocarbon fraction obtained after step d) advantageously comprises at least a part of the fraction under vacuum residue and possibly a part of the vacuum distillate fraction from step d) separation obtained after implementation atmospheric distillation and / or vacuum distillation.
    [0032] The process according to the invention comprises a step d) of selective deasphalting carried out under specific conditions making it possible to obtain a stable deasphalted oil with an improved yield compared to conventional deasphalting. Said deasphalting step can be carried out in one step or at least in two steps.
    [0033] Step e) also makes it possible to separate the sediments and the fines contained in the liquid hydrocarbon fraction resulting from step d) of separation. In the rest of the text and in the foregoing, the expression "solvent mixture according to the invention" is understood to mean a mixture of at least one polar solvent and at least one apolar solvent according to the invention. In the rest of the text and in the foregoing, the expression "deasphalted oil" is understood to mean the deasphalted oil known as DAO obtained when step e) is carried out in one step, but also as meaning the oil deasphalted so-called heavy DAO obtained when step e) is carried out in at least two stages. The deasphalting step e) can be carried out in one step by contacting the liquid hydrocarbon fraction obtained from the separation step d) with a mixture of at least one polar solvent and at least one apolar solvent, so as to obtain an asphalt fraction and a deasphalted oil fraction called DAO, step e) being carried out under subcritical conditions for the solvent mixture used. In a variant, the deasphalting step e) may comprise at least two deasphalting stages in series carried out on the liquid hydrocarbon fraction resulting from step d), making it possible to separate at least one asphalt fraction, at least one deasphalted oil fraction. said heavy DAO and at least a light deasphalted oil fraction said light DAO, at least one of said deasphalting steps being carried out by means of a mixture of solvents, said deasphalting steps being carried out under subcritical conditions for the solvent mixture used. The deasphalting step e) makes it possible to go further in maintaining the solubilization in the oil matrix of all or part of the polar structures of the heavy resins and asphaltenes, which are the main constituents of the asphalt phase. The deasphalting step e) thus makes it possible to choose what type of polar structures remain solubilized in the deasphalted oil matrix. Therefore, it selectively extracts from the liquid hydrocarbon fraction from step d) only part of this asphalt, ie the most polar structures and the most refractory. The extracted asphalt corresponds to the ultimate asphalt composed essentially of refractory polyaromatic and / or heteroatomic molecular structures. The deasphalting step e) carried out in two steps makes it possible to separate the feedstock into three fractions: an ultimate so-called asphalt fraction enriched with impurities and compounds that are refractory to upgrading, a deasphalted oil fraction called heavy DAO enriched in plant structures. resins and non-refractory but non-refractory, but generally remaining in the asphalt fraction in the case of conventional deasphalting in one or more steps, and a light deasphalted oil fraction called light DAO depleted in resins and asphaltenes, and generally in impurities (metals, heteroatoms). Step e) may be carried out in an extraction column or extractor, preferably in a mixer-settler. Preferably, the solvent mixture according to the invention is introduced into the extraction column or a mixer-settler at two different levels. Preferably, the solvent mixture according to the invention is introduced into an extraction column or mixer-settler, at a single introduction level. Step e) is carried out under subcritical conditions for said solvent mixture, that is to say at a temperature below the critical temperature of the solvent mixture. Step e) is carried out at extraction temperature advantageously between 50 and 350 ° C., preferably between 90 and 320 ° C., more preferably between 100 and 310 ° C., even more preferably between 120 and 310 ° C, even more preferably between 150 and 310 ° C and a pressure advantageously between 0.1 and 6 MPa, preferably between 2 and 6 MPa.
    [0034] The volume ratio of the solvent mixture according to the invention (volume of polar solvent + volume of apolar solvent) on the mass of liquid hydrocarbon fraction from step d) is generally between 1/1 and 10/1, from preferably between 2: 1 to 8: 1 expressed in liters per kilogram. The polar solvent used can be chosen from pure aromatic or naphtho-aromatic solvents, polar solvents comprising heteroelements, or their mixture. The aromatic solvent is advantageously chosen from monoaromatic hydrocarbons, preferably benzene, toluene or xylenes alone or as a mixture; diaromatic or polyaromatic; naphthenocarbon aromatic hydrocarbons such as tetralin or indane; heteroatomic aromatic hydrocarbons (oxygenated, nitrogenous, sulfurous) or any other family of compounds having a more polar character than saturated hydrocarbons such as dimethylsulfoxide (DMSO), dimethylformamide (DMF), tetrahydrofuran (THF). The polar solvent used in the process according to the invention can be a cut rich in aromatics. The aromatic-rich cuts according to the invention can be, for example, sections derived from FCC (Fluid Catalytic Cracking) such as heavy gasoline or LCO (light cycle oil) (LCO) or from petrochemical units of refineries. also the cuts derived from coal, biomass or biomass / coal mixture optionally with a residual petroleum feedstock after thermochemical conversion with or without hydrogen, with or without a catalyst, and preferably the polar solvent used is a pure monoaromatic hydrocarbon or mixture with an aromatic hydrocarbon The apolar solvent used is preferably a solvent composed of saturated hydrocarbon (s) comprising a carbon number greater than or equal to 2, preferably between 2 and 9. These solvents are used pure or in mixture (for example: mixture of alkanes and / or cycloalkanes or light petroleum fractions such as naphtha).
    [0035] Advantageously, the proportion of polar solvent in the mixture of polar solvent and apolar solvent is between 0.1 and 99.9%, preferably between 0.1 and 95%, preferably between 1 and 95%, so more preferably between 1 and 90%, even more preferably between 1 and 85%, and very preferably between 1 and 80%. Advantageously, the boiling point of the polar solvent of the solvent mixture according to the invention is greater than the boiling point of the apolar solvent.
    [0036] The choice of the temperature and pressure conditions of the extraction combined with the choice of the nature of the solvents and the choice of the combination of apolar and polar solvents in the deasphalting stage make it possible to adjust the extraction performance. The deasphalting conditions make it possible to overcome the limitations of the yield of deasphalted oil, as is required in conventional deasphalting by the use of paraffinic solvents. Stage e) makes it possible, thanks to specific deasphalting conditions, to go further in maintaining the solubilization in the oil matrix of all or part of the polar structures of heavy resins and asphaltenes, which are the main constituents of the asphalt phase in the case of conventional deasphalting. Thus, step e) allows a so-called ultimate fraction of asphalt, enriched in impurities and fines, to be extracted selectively while leaving at least a part of the polar structures of the heavy resins and the asphaltenes solubilized in the oil matrix. less polar. This results in an improved yield of stable deasphalted oil having a sediment content after aging of less than or equal to 0.1%.
    [0037] When the deasphalting step e) comprises at least two deasphalting steps in series, this can be carried out according to two different embodiments.
    [0038] In a first embodiment, step e) is carried out in a so-called configuration of decreasing polarity, that is to say that the polarity of the solvent mixture used during the first deasphalting step is greater than that of the solvent mixture used in the second deasphalting step. This configuration makes it possible to extract during the first deasphalting step an ultimate so-called asphalt fraction and a complete deasphalted oil fraction called the complete DAO; the two fractions called deasphalted oil called heavy DAO and mild deasphalted oil called light DAO being extracted from the complete deasphalted oil during the second deasphalting step; said deasphalting steps being carried out under subcritical conditions for the solvent mixture used. In a second embodiment, step e) is carried out in a so-called configuration of increasing polarity, that is to say that the polarity of the solvent mixture used during the first deasphalting step is lower than that of the solvent mixture used in the second deasphalting step. In such a configuration, in the first step, a light deasphalted oil fraction called light DAO is extracted and an effluent comprising an oil phase and an asphalt phase; said effluent being subjected to a second deasphalting step to extract an asphalt fraction and a heavy DAO deasphalted oil fraction; said deasphalting steps being carried out under subcritical conditions for the solvent mixture used. The deasphalted oil from step e) (deasphalted oil known as DAO or deasphalted oil called heavy DAO) with at least a part of the solvent mixture according to the invention is preferably subjected to at least one separation step in which said deasphalted oil is separated from the solvent mixture according to the invention. This deasphalted oil may, at least in part, be used as a base of fuel oil or as fuel oil, especially as a base of bunker oil or as low-sulfur fuel oil, meeting the new recommendations of the International Maritime Organization and the specifications described in ISO 10307-2, namely a lower sulfur content, namely an equivalent 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 % in weight. By "fuel" is meant in the invention a hydrocarbon feedstock used as fuel. By "oil base" is meant in the invention a hydrocarbon feed which, mixed with other bases, constitutes a fuel oil.
    [0039] BACKGROUND OF THE INVENTION An objective of the present invention is to produce marketable fuel oils, especially bunker fuels for maritime transport. It is preferable that this type of fuel meets certain specifications, especially in terms of viscosity.
    [0040] Preferably, a very common type of bunker oil has a viscosity of less than or equal to 380 cSt (at 50 ° C). Other qualities of fuel oil, called "grades", meet different specifications, especially from the point of view of viscosity. Particularly for distillate type fuels, the DMA grade imposes a viscosity of between 2 cSt and 6 cSt at 40 ° C. and the DMB grade has a viscosity of between 2 cSt and 11 cSt at 40 ° C. In order to obtain, among other things, the target viscosity of the desired fuel grade, the deasphalted oil fraction (deasphalted oil called DAO or deasphalted oil called heavy DAO) is used as the oil base and can be mixed, if necessary, with one or more bases. fluxantes or "cutter stocks" according to the English terminology. Fuel specifications are for example described in the IS08217 standard (last version in 2012). The fluxing bases are generally of the kerosene, diesel or vacuum gas oil type. They may be selected from the group consisting of light catalytic cracked (LCO) light cycle oils, heavy catalytic cracked (HCO) heavy oil, the residue of a catalytic cracking, kerosene, gas oil, vacuum distillate and / or decanted oil. In a very particularly preferred manner, said fluxing base is chosen from a part of the light fraction of kerosene and / or gas oil or vacuum gas oil obtained at the end of the separation step b). A particular embodiment could consist in incorporating into the mixture comprising at least one deasphalted oil fraction (deasphalted oil called DAO or deasphalted oil called heavy DAO), a portion of the atmospheric residue and / or vacuum residue from step a) hydrotreating. At the end of this stage of mixing the deasphalted oil resulting from stage e) with one or more fluxing bases, a fuel oil which can be used in maritime transport, also called bunker oil, with a low sulfur content and sediment according to the invention.
    [0041] EXAMPLES Example 1 (non-compliant) A vacuum residue feedstock (RSV Ural) having an initial temperature of 362 ° C. and a final temperature above 615 ° C. (49% distilled at 615 ° C.) is treated. 5% by weight of compounds boiling at a temperature above 540 ° C. The charge density is 9.2 ° API, the sulfur content is 2.7% by weight, the Ni + V metal content is 253 ppm and the C7 asphaltene content is 3.9% by weight.
    [0042] The feedstock is subjected to a hydrotreating step including two permutable reactors. The operating conditions of the hydrotreatment step in fixed bed (s) are given in Table 1. A NiMo catalyst on active alumina in hydrodemetallation (HDM) sold by the company Axens under the reference HF858, is used. and a NiMo catalyst on hydrosulfurization active alumina (HDS) sold by Axens under the reference HT438. Table 1: Operating conditions of the hydrotreatment step in fixed bed (s) (s) HDM catalyst (Axens reference) NiMo on Alumina (HF858) HDS catalyst (Axens reference) NiMo on Alumina (HT438) Temperature (° C) 370 Pressure (MPa) 15 WH (1-1-1, Sm3 / h fresh load / m3 of fixed bed catalyst) 0.19 H2 / input load of the hydrotreating section H2 (N-m3 / m3 load) 1000) The hydrotreating effluent undergoes a separation step to obtain a light fraction and a heavy fraction.The light fraction undergoes other separation steps to recover a hydrogen-rich gas and distillates. The heavy fraction is sent in admixture with a hydrogen-rich gas in a hydroconversion stage comprising a bubbling bed reactor The operating conditions of the boiling bed hydroconversion stage are given in Table 2. A NiMo catalyst is used on Alumine sold by the company Axens under the reference HOC458. Table 2: Operating conditions of the bubbling bed hydroconversion stage Catalyst (Axens reference) NiMo on Alumina (HOC458) Temperature (° C) 420 Pressure (MPa) 15 WH (h-1, Sm3 / h fresh load / m3 boiling bed reactor) 0.4 H2 / heavy fraction at the inlet of the ebullated boiling-water hydroconversion section H2 (Nm3 / m3 fresh feed) 500 The effluent from the boiling bed hydroconversion stage undergoes separation step for recovering at least one hydrogen-rich gas, atmospheric distillates, vacuum distillate and vacuum residue. The yield relative to the fresh feed and the sulfur content of each fraction obtained in the overall hydrotreatment in fixed bed + ebullated bed hydroconversion are given in Table 3. Table 3: Yields (Yield) and feed content sulfur (S) at the output of the overall sequence fixed bed + bubbling bed (% weight I fresh load) Products Yield (% wt) S (% wt) NH3 0.18 0 H2S 2.38 94.12 C1-C4 ( gas) 2.36 0 Naphtha (PI - 180 ° C) 4.73 0.005 Gas oil (180 ° C - 350 ° C) 15.16 0.03 Vacuum distillate (350 ° C - 540 ° C) 37.13 0.25 Vacuum Residue (540 ° C +) 39.6 0.56 The hydrogen consumed over the entire process represents 1.54% by weight of the fresh feed introduced at the inlet of the hydrotreatment section. The overall conversion to the vacuum residue fraction (540 ° C +) is 52%. A mixture A is prepared from the vacuum (350 ° C - 540 ° C) and vacuum (540 ° C +) distillate fractions from the hydroconversion stage in the following proportions: - distillate fraction under (350 ° C. - 540 ° C.): 46% by weight of the mixture A, fraction under vacuum (540 ° C. +): 54% by weight of the mixture A. A bunker oil A having a sulfur content of 0.42% by weight and having a viscosity of 380 cSt at 50 ° C. However, its sediment content after aging is 0.6% by weight, ie 0.5% by weight above the ISO 8217 specification. Example 2 (Compliant) A vacuum void load (RSV Ural) is treated with an initial temperature of 362 ° C. and a final temperature above 615 ° C. (49% distilled at 615 ° C.), ie 82.5% by weight of compounds boiling at a temperature above 540 ° C. The density of this filler is 9.2 ° API, the sulfur content of 2.7% by weight, the Ni + V metal content of 253 ppm and the C7 asphaltene content of 3.9% by weight. The feedstock is firstly subjected to the same steps as above and under the same operating conditions: a fixed bed hydrotreatment step including two permutable reactors, a separation step making it possible to recover at least one heavy fraction, a step of hydroconversion of the heavy fraction mixed with a part of the DAO (DAO recycled) deasphalted oil comprising a bubbling bed reactor and a separation step for recovering at least one hydrogen-rich gas, atmospheric distillates, a distillate Vacuum and a vacuum residue Then the whole of said vacuum residue is sent to a selective deasphalting unit under the operating conditions given in Table 4. A mixture of apolar solvent (heptane) and polar solvent ( toluene).
    [0043] Table 4: Operating conditions for selective deasphalting Ratio of apolar / polar solvents (v / v) 97/3 Ratio of solvent / charge (v / m) 5/1 Pressure (MPa) 4 Temperature (° C) 240 Characteristics of the oil deasphalted DAO obtained and the deasphalted oil yield DAO with respect to the vacuum depressurized feedstock input of the selective deasphalting unit are detailed in Table 5. Table 5: Yields and characteristics of the deasphalted DAO oil obtained Yield DAO (% by weight) 95 Sulfur DAO (wt%) 0.54 Conradson carbon (%) 12 Ni + V (ppm) 8 Viscosity at 100 ° C (Cst) 168 The deasphalted DAO oil is separated into two streams: - 50 % by weight of the DAO deasphalted oil obtained is used to prepare a fuel oil - 50% by weight of the deasphalted DAO oil obtained is recycled to the inlet of the boiling bed hydroconversion unit.
    [0044] The yields and sulfur contents of each fraction obtained at the outlet of the overall hydrotreatment in fixed bed + hydroconversion in bubbling bed + selective deasphalting are given in Table 6.
    [0045] Table 6: Yields (Yield) and sulfur content (S) at the output of the overall sequence fixed bed hydrotreating + boiling bed hydroconversion + selective deasphalting (% w / fresh load) Products Yield (% wt) S (% wt) ) NH3 0.23 0 H2S 3.05 94.12 C1-C4 (gas) 3.03 0 Naphtha (PI - 180 ° C) 6.24 0.005 Gas oil (180 ° C - 350 ° C) 20.14 0, 03 Vacuum distillate (350 ° C - 540 ° C) 39.74 0.24 deasphalted oil DAO (540 ° C +) 26.75 0.54 Asphalt (540 ° C +) 2.82 0.74 Hydrogen consumed on the whole process represents 1.99% by weight of the fresh feed introduced at the inlet of the hydrotreatment section. The overall conversion to DAO deasphalted oil fraction (540 ° C +) is 64%. A mixture B is prepared from the vacuum (350 ° C - 540 ° C) and deasphalted DAO (540 ° C +) distillate fractions in the following proportions: vacuum distillate fraction (350 ° C - 540 ° C) C): 43% by weight of the mixture B - deasphalted oil fraction DAO (540 ° C +): 57% by weight of the mixture B.
    [0046] A bunker fuel oil B having a sulfur content of 0.42% by weight and having a viscosity of 380 cSt at 50 ° C was obtained. In addition, its sediment content after aging equal to 0.05% by weight.
    [0047] The method according to the invention thus makes it possible to produce a fuel oil B stable, low sulfur content and meeting the requirements of IS08217: 2012 in particular. The overall conversion is markedly improved over a process without selective deasphalting which allows the production of high value distillates in addition to low sulfur bunker oil.
    权利要求:
    Claims (20)
    [0001]
    1) A process for treating a hydrocarbon feed having a sulfur content of at least 0.5% by weight, an asphaltene content of at least 1% by weight, an initial boiling temperature of at least 1% by weight 340 ° C and a final boiling point of at least 480 ° C, to obtain at least one deasphalted oil fraction having a sulfur content of less than or equal to 0.5% by weight and a lower sediment content or equal to 0.1% by weight, comprising the following successive steps: a) a fixed bed hydrotreatment stage, in which the hydrocarbon feedstock and hydrogen are brought into contact on at least one hydrotreatment catalyst, b) optionally a step of separating the effluent obtained at the end of the hydrotreatment step a) into at least a light fraction and at least one heavy fraction, c) a hydroconversion step of at least one part of the effluent from step a) or from at least one part ie the heavy fraction resulting from step b) and optionally at least a portion of the light fraction resulting from step b) in at least one reactor containing at least one catalyst supported in a bubbling bed, d) a step separating the effluent from step c) to obtain at least one gaseous fraction and a liquid hydrocarbon fraction, e) at least one selective deasphalting step for separating at least one asphalt fraction and at least one oil fraction deasphalted, the deasphalting step being at least carried out by contacting at least a portion of the liquid hydrocarbon fraction from step d) with a mixture of at least one polar solvent and at least one solvent apolar in subcritical conditions for the solvent mixture used. f) a step of recycling at least a portion of said deasphalted oil fraction from step e) upstream of the hydrotreatment step a) and / or at the entry of step c) of hydroconversion. 30
    [0002]
    2) Process according to claim 1 wherein the step d) of deasphalting comprises at least two deasphalting steps in series for separating at least one asphalt fraction, at least one deasphalted oil fraction called heavy DAO and at least one deasphalted oil fraction light so-called light DAO, at least one of said deasphalting steps being carried out by contacting at least a portion of the liquid hydrocarbon fraction from step d) with a mixture of at least one polar solvent and at least one an apolar solvent under subcritical conditions for the solvent mixture used.
    [0003]
    3) Process according to claim 2 wherein in step f) recycle at least a portion of the heavy DAO oil fraction desughalée from step e) upstream of step a) of hydrotreatment and / or at the entry of the hydroconversion stage c).
    [0004]
    4) Process according to one of the preceding claims wherein step e) is carried out at extraction temperature of between 50 and 350 ° C, and a pressure of between 0.1 and 6 MPa.
    [0005]
    5) Method according to one of the preceding claims wherein the fixed bed hydrotreating step is carried out at a temperature between 300 ° C and 500 ° C, at an absolute pressure between 2 MPa and 35 MPa, with a space velocity of the hydrocarbon feedstock in a range from 0.1 hr-1 to 5 hr-1, and the amount of hydrogen is between 100 Nm3 / m3 and 5000 Nm3 / m3.
    [0006]
    6) Process according to one of the preceding claims wherein the polar solvent used is selected from aromatic solvents pure or naphtho-aromatic, polar solvents comprising hetero-elements, or their mixture or cuts rich in aromatic such cuts FCC (Fluid Catalytic Cracking) derived from coal, biomass or biomass / coal 25
    [0007]
    7) Method according to one of the preceding claims wherein the apolar solvent used comprises a saturated hydrocarbon solvent comprising a carbon number greater than or equal to 2, preferably between 2 and 9.
    [0008]
    8) Method according to one of the preceding claims, wherein the hydroconversion step c) is carried out under an absolute pressure between 2.5 MPa and 35 MPa, at a temperature between 330 ° C and 550 ° C , with a space velocity ranging from 0.1 hr-1 to 5 hr-1, and the amount of hydrogen is from 50 Nm3 / m3 to 5000 Nm3 / m3.
    [0009]
    9) Method according to one of the preceding claims, wherein the separation step d) comprises at least one atmospheric distillation and / or at least one vacuum distillation.
    [0010]
    10) The method of claim 9, wherein the step d) of separation firstly comprises an atmospheric distillation, wherein the effluent obtained at the end of step c) is fractionated by atmospheric distillation into at least an atmospheric distillate fraction and at least one atmospheric residue fraction, followed by a vacuum distillation in which at least a portion of the atmospheric residue fraction obtained after atmospheric distillation is fractionated by vacuum distillation into at least one vacuum distillate fraction and at least one fraction under vacuum; the liquid hydrocarbon fraction sent to step e) comprising at least a portion of said vacuum residue fraction and optionally a portion of said vacuum distillate fraction.
    [0011]
    11) The method of claim 10 wherein at least a portion of the atmospheric residue fraction is sent in the hydroconversion step c).
    [0012]
    12. The process according to claims 10 and 11 wherein at least a portion of the vacuum residue fraction is recycled to the hydrotreating step a).
    [0013]
    13) Method according to one of the preceding claims, wherein the hydrocarbon feedstock is selected from atmospheric residues, vacuum residues from direct distillation, crude oils, crude oils topped, 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, parent rock oils or their derivatives, taken alone or in mixture. 30
    [0014]
    14) The method of claim 13 wherein the hydrocarbon feedstock is diluted by a co-charge selected from a hydrocarbon fraction or a lighter hydrocarbon fraction mixture, which can be selected from the products from a process of fluid catalytic cracking process , a light cutting oilLCO, a heavy cutting oil HCO, a decanted oil, an FCC residue, a gas oil fraction; one or more cuts from the process of liquefying coal or biomass, aromatic extracts, or any other hydrocarbon cuts or non-petroleum fillers such as pyrolysis oil.
    [0015]
    15) deasphalted oil obtainable according to one of the preceding claims.
    [0016]
    16) Deasphalted oil according to claim 15 usable as a base of fuel oil. 10
    [0017]
    17) Method according to one of claims 1 to 14 wherein the obtained deasphalted oil fraction is mixed with one or more fluxing bases selected from the group consisting of light cutting oils (LCO) of a catalytic cracking, oils of heavy cut (HCO) of a catalytic cracking, the residue of a catalytic cracking, kerosene, gas oil, vacuum distillate and / or a decanted oil.
    [0018]
    18) A method according to claim 17 wherein the fluxing base is selected from a part of the light hydrocarbon fraction of kerosene and / or gas oil or vacuum gas oil obtained at the end of step b) of separation .
    [0019]
    19) A fuel oil for use in maritime transport, obtained by the process as defined in one of claims 17 and 18, having a sulfur content of less than or equal to 0.5% by weight. 25
    [0020]
    20. Fuel oil according to claim 19 such that its sediment content is less than or equal to 0.1% by weight.
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    同族专利:
    公开号 | 公开日
    CN105940086A|2016-09-14|
    EA201691264A1|2016-10-31|
    EA032845B1|2019-07-31|
    SA516371316B1|2019-07-18|
    US20160312130A1|2016-10-27|
    US9650580B2|2017-05-16|
    CN105940086B|2019-08-20|
    WO2015091033A1|2015-06-25|
    FR3014897B1|2017-04-07|
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    法律状态:
    2015-12-11| PLFP| Fee payment|Year of fee payment: 3 |
    2016-12-12| PLFP| Fee payment|Year of fee payment: 4 |
    2017-12-14| PLFP| Fee payment|Year of fee payment: 5 |
    2019-12-23| PLFP| Fee payment|Year of fee payment: 7 |
    2021-09-10| ST| Notification of lapse|Effective date: 20210805 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1362748A|FR3014897B1|2013-12-17|2013-12-17|NEW INTEGRATED PROCESS FOR THE TREATMENT OF PETROLEUM LOADS FOR THE PRODUCTION OF LOW SULFUR AND SEDIMENT FIELDS|FR1362748A| FR3014897B1|2013-12-17|2013-12-17|NEW INTEGRATED PROCESS FOR THE TREATMENT OF PETROLEUM LOADS FOR THE PRODUCTION OF LOW SULFUR AND SEDIMENT FIELDS|
    EA201691264A| EA032845B1|2013-12-17|2014-12-05|Novel integrated process for the treatment of oil fractions for the production of fuel oils with a low sulphur and sediments|
    PCT/EP2014/076775| WO2015091033A1|2013-12-17|2014-12-05|Novel integrated process for treating petroleum feedstocks for the production of fuel oils having a low content of sulphur and of sediments|
    US15/105,314| US9650580B2|2013-12-17|2014-12-05|Integrated process for the treatment of oil feeds for the production of fuel oils with a low sulphur and sediment content|
    CN201480068097.8A| CN105940086B|2013-12-17|2014-12-05|For handling oil charging to produce the new integrated approach of the fuel oil with low sulfur content and contents of precipitate|
    SA516371316A| SA516371316B1|2013-12-17|2016-06-14|Process for the treatment of hydrocarbon feed having sulphur content|
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