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    • 专利摘要:
    The invention relates to a method for converting a heavy hydrocarbon feedstock comprising the following steps: a) at least one step of selective deasphalting of the heavy hydrocarbon feedstock by liquid / liquid extraction making it possible to separate at least one asphalt fraction , at least one deasphalted oil fraction, b) a step of hydroconversion of the deasphalted oil fraction in the presence of hydrogen in at least one three-phase reactor, under conditions making it possible to obtain an effluent comprising a gaseous fraction containing predominantly H2 and H2S compounds, and a Conradson carbon reduced liquid fraction, of metals, sulfur and nitrogen, c) a step of separating the effluent from step b) to obtain a gaseous fraction containing predominantly H2 and H2S compounds and a Conradson carbon reduced liquid fraction of metals, sulfur and nitrogen.
    公开号:FR3021326A1
    申请号:FR1454576
    申请日:2014-05-21
    公开日:2015-11-27
    发明作者:Jerome Majcher；Isabelle Merdrignac；Frederic Feugnet
    申请人:IFP Energies Nouvelles IFPEN；
    IPC主号:
    专利说明:

    [0001] FIELD OF THE INVENTION The present invention relates to a new process for the conversion of a heavy hydrocarbon feedstock, in particular resulting from atmospheric distillation or the vacuum distillation of crude oil. It is known that the performance of recovery and conversion processes generally face limitations that are mainly related to the presence of so-called refractory molecular structures. Indeed, these molecular structures (heteroelements, polyaromatic molecules and polar molecules present in the resins and asphaltenes) are responsible for the formation of sediments causing clogging of the equipment of the hydrotreatment units of heavy loads and consequently impairs the operability of the entire process by frequent shutdowns during the operation of this equipment. Also, in order to reduce the frequency of downtime, the heavy-lift hydroconversion units are often operated under milder operating conditions, thus limiting the conversion rate and hence their cost-effectiveness. In order to be free of these constraints, a pretreatment step upstream of the hydroconversion unit is often required, thus making it possible to eliminate the most refractory structures, not only difficult, but also essentially precursors of sediments. These pretreatment steps well known to those skilled in the art may be non-exhaustively a visbreaking, hydroviscoreduction, coking or deasphalting unit (hereinafter referred to as conventional or conventional SDA text). The principle of deasphalting is based on a precipitation separation of a petroleum residue in two phases: i) a so-called "deasphalted oil" phase, also called "oil matrix" or "oil phase" or DAO (De-Asphalted OH according to Anglo-Saxon terminology); and ii) a phase called "asphalt" or sometimes "pitch" (according to the English terminology) containing inter alia refractory molecular structures.
    [0002] Patent FR 2 906 814 of the applicant describes a process comprising the sequencing of a conventional deasphalting step producing a deasphalted oil, a hydroconversion step carried out on said deasphalted oil to produce an effluent, and a distillation step of said effluent to produce a residue which is returned with the feed to the conventional deasphalting step. This patent describes a conventional deasphalting which, by its principle, suffers from a limitation of the yield of DAO deasphalted oil which increases with the molecular weight of the solvent (up to the solvent C6 / C7), then capped at a threshold specific to each charge and each solvent. Furthermore, conventional deasphalting suffers from a very low selectivity resulting in the "extraction of a deasphalted oil of" overquality. "Indeed, a good part of the molecular structures still recoverable remain contained in the asphalt fraction. The present invention is to best maximize the deasphalted oil yield fed into the bubbling bed unit while placing itself at the operability limit of the bubbling bed unit, i.e. C7 asphaltene content specifications present in the feed entering the bubbling bed unit The present invention aims to increase the conversion level of the recoverable feed while minimizing sediment formation in the hydroconversion units, in order to limit frequent stoppages and hence operability, the Applicant in his research has developed a new conversion method for e heavy hydrocarbon load to overcome the aforementioned drawbacks, by integrating at least one selective deasphalting step for separating at least one asphalt fraction, at least one deasphalted oil fraction. It has been found that the implementation of the method according to the invention makes it possible to improve the flexibility and the operability of the charge conversion scheme according to the invention. Object of the Invention The present invention relates to a process for converting a heavy hydrocarbon feedstock having an initial boiling temperature of at least 300 ° C comprising the following steps: a) at least one step of selective deasphalting of the hydrocarbon heavy load by liquid / liquid extraction making it possible to separate at least one asphalt fraction, at least one deasphalted oil fraction, at least one of said deasphalting steps being carried out using a mixture of at least one solvent polar and at least one apolar solvent, the proportions of said polar solvent and of said apolar solvent of the solvent mixture being adjusted according to the properties of the treated filler and according to the asphalt yield and / or the quality of the desired deasphalted oil ( e) (s), said deasphalting steps being carried out under the subcritical conditions of the mixture of solvents used, b) a step of hydroconversion of the fra deasphalted oil in the presence of hydrogen in at least one three-phase reactor, said reactor containing at least one hydroconversion catalyst and operating as a bubbling bed, with an upward flow of liquid and gas and comprising at least one means for drawing off said catalyst said reactor and at least one fresh catalyst booster means in said reactor, under conditions to obtain an effluent comprising a gaseous fraction containing predominantly H2 and H2S compounds, and a Conradson carbon-reduced liquid fraction, in metals, sulfur and nitrogen, c) a step of separating the effluent from step b) to obtain a gaseous fraction containing predominantly H2 and H2S compounds and a Conradson carbon reduced liquid fraction, of metals , sulfur and nitrogen.
    [0003] Advantageously, the process according to the invention further comprises a step d) of separating the liquid fraction resulting from step c) into a light liquid fraction boiling at a temperature below 360 ° C. and a heavy liquid fraction boiling at a temperature of temperature above 360 ° C. Advantageously according to the invention, the hydroconversion stage b) operates at an absolute pressure of between 2 and 35 MPa, at a temperature of between 300 and 550 ° C., at a space velocity (WH) of between 0.1 h-1 and 10 h-1 and under a quantity of hydrogen mixed with the charge of between 50 and 5000 normal cubic meters (Nm3) per cubic meter (m3) of liquid charge.
    [0004] Advantageously according to the invention, the hydroconversion catalyst is a catalyst comprising an alumina support and at least one group VIII metal chosen from nickel and cobalt, said group VIII element being used in combination with at least one metal of the group VIB selected from molybdenum and tungsten.
    [0005] Advantageously according to the invention, the polar solvent used in step a) of deasphalting is chosen from pure aromatic or naphthoaromatic solvents, polar solvents containing heteroelements, or their mixture or cuts rich in aromatics such cuts from FCC (Fluid Catalytic Cracking), cuts derived from coal, biomass or biomass / coal mixture. Advantageously according to the invention, the apolar solvent used in step a) of deasphalting comprises a solvent composed of saturated hydrocarbon comprising a number of carbon atoms greater than or equal to 2, preferably between 2 and 9. Advantageously according to the invention, step a) is carried out with a volume ratio of the mixture of polar and apolar solvents on the mass of the load of between 1/1 and 10/1 expressed in liters per kilogram.
    [0006] Advantageously according to the invention, the feedstock is crude oil or a feedstock resulting from the atmospheric distillation or the vacuum distillation of crude oil, or a residual fraction resulting from the direct liquefaction of coal or a vacuum or vacuum distillate. still a residual fraction resulting from the direct liquefaction of the lignocellulosic biomass alone or mixed with coal and / or a residual petroleum fraction. The process according to the invention has the advantage of maximizing the yield of deasphalted oil sent to the hydroconversion unit by placing itself as close as possible to the limiting specifications of said unit, namely the asphaltene content. The method according to the invention also makes it possible to improve the flexibility of the process diagram by making it possible to process a wider panel of charges, and consequently its profitability.
    [0007] Detailed description of the invention The feedstock The heavy hydrocarbon feedstock according to the process of the invention is advantageously a heavy feedstock resulting from atmospheric distillation or from the vacuum distillation of crude oil, typically having boiling point temperatures. at least 300 ° C, preferably above 450 ° C, and containing impurities, especially sulfur, nitrogen and metals. The charge can be crude oil.
    [0008] The filler according to the process of the invention may be of petroleum origin of atmospheric residue type or vacuum residue from conventional crude (API degree> 20 °), heavy (API degree between 10 and 20 °) or extra heavy (degree API <10 °).
    [0009] The load may come from different geographical and geochemical origins (type I, II, IIS or III), with a different degree of maturity and biodegradation. The feedstock may also be a residual fraction resulting from the direct liquefaction of coal (atmospheric residue or vacuum residue resulting for example from the H-Coall-m process) or else an H-CoalTM vacuum distillate or a residual fraction obtained from direct liquefaction of the lignocellulosic biomass alone or mixed with coal and / or a residual petroleum fraction.
    [0010] This type of filler is generally rich in impurities with metal levels greater than 20 ppm, preferably greater than 100 ppm. The sulfur content is greater than 0.5%, preferably greater than 1%, and preferably greater than 2% by weight. The level of C 7 asphaltenes is advantageously greater than 1%, preferably the level of C 7 asphaltenes is between 1 and 40% and more preferably between 2 and 30% by weight. C7 asphaltenes are compounds known to inhibit the conversion of residual cuts, both by their ability to form heavy hydrocarbon residues, commonly known as cokes, and by their tendency to produce sediments which severely limit the operability of the units of hydrotreatment and hydroconversion. The Conradson carbon content is greater than 5% or even 35% by weight. The Conradson carbon content is defined by ASTM D 482 and represents for the skilled person a well-known evaluation of the amount of carbon residues produced after combustion under standard conditions of temperature and pressure.
    [0011] Step a) Selective deasphalting of the heavy hydrocarbon feedstock According to step a) of the process according to the invention, the feedstock undergoes at least one step of selective deasphalting by liquid / liquid extraction making it possible to separate at least one asphalt fraction at least one deasphalted oil fraction, at least one of said deasphalting steps being carried out by means of a mixture of at least one polar solvent and at least one apolar solvent, the proportions of said polar solvent and said apolar solvent; of the solvent mixture being adjusted according to the properties of the treated feed and the asphalt yield and / or the quality of the desired deasphalted oil (s), said deasphalting steps being carried out under the subcritical conditions of the mixture of solvents used The proportions of said polar solvent and of said apolar solvent of the solvent mixture are adjusted according to the properties of the treated feedstock and depending on the desired asphalt yield and / or quality of the CAD (s).
    [0012] 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.
    [0013] The selective deasphalting used in step a) makes it possible 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. The invention thus makes it possible to choose which types of polar structures remain solubilized in the oil matrix. Therefore, the selective deasphalting used in the invention selectively extract the load only part of this asphalt, that is to say the most polar structures and the most refractory in the conversion processes and refining. The process according to the invention allows, thanks to specific deasphalting conditions, greater flexibility in the treatment of the feeds according to their nature but also as a function of the quality and / or the yield of deasphalted oil to be treated. in the hydroconversion unit. Furthermore, the deasphalting conditions according to the invention make it possible to overcome the limitations of deasphalted oil yield DAO imposed by the use of paraffinic solvents. The asphalt extracted during deasphalting according to the invention corresponds to the ultimate asphalt composed essentially of refractory polyaromatic and / or heteroatomic molecular structures in refining. This results in an improved deasphalted-upgraded oil yield. The selective deasphalting step a) can be carried out in an extraction column, or in a mixer-settler. Preferably, the solvent mixture according to the invention is introduced into an 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 a mixer-settler, at a single level of introduction. This step is carried out by liquid / liquid extraction in at least one deasphalting step, preferably in two successive deasphalting steps. According to the invention, the liquid / liquid extraction of the deasphalting stage (s) is carried out under subcritical conditions for the mixture of solvents used, that is to say at a temperature below critical temperature of the solvent mixture. When a single solvent, preferably an apolar solvent, is used, the deasphalting step is carried out under subcritical conditions for said solvent, that is to say at a temperature below the critical temperature of said solvent . The extraction temperature is 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, still more preferably between 150 and 310 ° C and the pressure is preferably between 0.1 and 6 MPa, preferably between 2 and 6 MPa. The volume ratio of the solvent mixture according to the invention (volume of polar solvent + volume of apolar solvent) on the mass of filler is generally between 1/1 and 10/1, preferably between 2/1 to 8/1 expressed in liters per kilogram. Advantageously, according to the process of the invention, 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. The polar solvent used may be chosen from pure aromatic or naphtho-aromatic solvents, polar solvents containing 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 also be a cut rich in aromatics. The sections rich in aromatics according to the invention can be, for example, sections derived from FCC (Fluid Catalytic Cracking) such as heavy gasoline or LCO (light cycle oil), as well as cuts derived from coal, biomass or biomass / coal mixture with possibly a residual petroleum charge after thermochemical conversion with or without hydrogen, with or without a catalyst, naphtha-type light petroleum cuts, preferably straight-run naphtha-type petroleum fractions. preferably, the polar solvent used is a pure monoaromatic hydrocarbon or in admixture with another aromatic hydrocarbon The apolar solvent used in the process according to the invention 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 m lange (eg mixing of alkanes and / or cycloalkanes or of 'light petroleum fractions like naphtha, preferably light petroleum fractions like naphtha straight-run).
    [0014] The choice of the temperature and pressure conditions of the extraction according to the invention combined with the choice of the nature of the solvents and the choice of the combination of apolar and polar solvents in at least one of the deasphalting stages make it possible to adjust the performances the method according to the invention to access in particular a selectivity range hitherto inaccessible with conventional deasphalting. In the case of the present invention, the optimization of these adjustment keys (nature of the solvents, relative proportions of polar and apolar solvents and subcritical conditions of the solvent or of the solvent mixture used) enables the charge to be separated into at least two fractions: a so-called ultimate asphalt fraction enriched in impurities and in compounds that are refractory to recovery, a deasphalted oil fraction enriched in non-refractory resins and non-polar asphaltene structures. As a result, it is possible to impose more severe operating conditions in the hydroconversion step, thereby achieving higher conversions while reducing the frequency of downtime during operation of the hydroconversion units.
    [0015] Advantageously, the proportion of polar solvent in the mixture of polar solvent and apolar solvent is between 0.1 and 99.9% volume / volume, preferably between 0.1 and 95%, preferably between 1 and 95%. more preferably between 1 and 90%, even more preferably between 1 and 85%, and very preferably between 1 and 80%. The proportion of polar solvent in the mixture of polar and apolar solvent is a function of the nature of the heavy load of hydrocarbons, the molecular structures composing said charge varying from one charge to another. All the charges do not have the same refractory character. The rate of asphalt to be extracted is therefore not necessarily the same depending on the nature of the load. The nature of the load also depends on its origin which can be petroleum, of origin of the coal or of biomass origin.
    [0016] The selective deasphalting step a) has the advantage of allowing a considerable improvement in the total yield of DAO deasphalted oil over a range hitherto unexplored by conventional deasphalting. For a given charge whose total yield of deasphalted oil obtained is capped at 75% (extraction with normal heptane), the selective deasphalting makes it possible to cover by adjustment of the proportion polar solvent and apolar solvent, combined with the conditions of extraction, the 75-99.9% range of deasphalted oil yield. The total deasphalted oil yield of step a) is preferably from 50 to 99.9%, preferably from 75 to 99.9%, more preferably from 80 to 99.9%. Another advantage according to the invention is to allow, thanks to the selective deasphalting according to step a), the reduction of the asphalt fraction, the yield of which can be considerably lower compared to a conventional deasphalting operation, for given charge. According to the process according to the invention, this yield is reduced to the range 0.1 to 30% as a function of the apolar / polar solvent ratio. It is all the smaller as the proportion of polar solvent in the mixture is high. Accordingly, the asphalt extraction range with a yield in the range of 0.1-50%, particularly 0.1-30%, more preferably 0.1-25%, more preferably 0.1 -15% is now covered. It is a function of the selectivity desired for a given load as well as the nature of the load. This is a point of interest knowing the valorization of the asphalt (penalizing fraction) is always a real limitation for the schemes including this type of process. According to the method of the invention, step a) can be carried out in two steps. Indeed, the nature of the solvent and / or the proportion and / or the intrinsic polarity of the polar solvent in the solvent mixture can be adjusted according to whether it is desired to extract the asphalt during a first deasphalting step or when a second deasphalting step. In a first embodiment, step a) of the process according to the invention is carried out in a so-called decreasing polarity configuration, that is to say that the polarity of the solvent mixture used during the first deasphalting step is greater than that of the solvent or solvent mixture used in the second deasphalting step. This configuration makes it possible to extract during the first deasphalting step a so-called ultimate asphalt phase fraction and a complete deasphalted oil fraction called complete DAO; two so-called heavy deasphalted oil and light deasphalted oil fractions being extracted from the complete DAO during the second deasphalting step. In a second embodiment, step a) of the process according to the invention is carried out in a so-called configuration of increasing polarity, that is to say that the polarity of the solvent or mixture of solvents used during the first deasphalting step is less than that of the solvent mixture used in the second deasphalting step. In such a configuration, in the first step, a so-called light deasphalted oil fraction and an effluent comprising an oil phase and an asphalt phase are extracted; said effluent being subjected to a second deasphalting step to extract an asphalt phase fraction and a heavy deasphalted oil fraction called heavy DAO.
    [0017] First Embodiment According to this embodiment, the process according to the invention comprises at least: a1) a first step of selective deasphalting comprising bringing the heavy hydrocarbon feedstock into contact with a mixture of at least one polar solvent and at least one apolar solvent, the proportions of said polar solvent and said apolar solvent being adjusted so as to obtain at least an asphalt phase fraction and a complete deasphalted oil fraction called complete DAO; and a2) a second deasphalting step comprising contacting the complete deasphalted oil fraction called complete DAO resulting from step a1) with either an apolar solvent or a mixture of at least one polar solvent and from at least one apolar solvent, the proportions of said polar solvent and of said apolar solvent in the mixture being adjusted so as to obtain at least a fraction of light deasphalted oil called light DAO and a heavy deasphalted oil fraction called heavy DAO, in which said deasphalting steps are carried out under the subcritical conditions of the solvent or solvent mixture used and in which the heavy deasphalted oil fraction called heavy DAO is sent in step b).
    [0018] The first step of deasphalting thus makes it possible to selectively extract, in an optimal manner and adapted to each load, an ultimate so-called asphalt phase fraction, enriched with impurities and compounds which are refractory to recovery, while leaving solubilized in the oil fraction. complete deasphalted so-called DAO completes all or part of the polar structures of heavy resins and less polar asphaltenes, which they are not refractory for the downstream conversion and refining steps. Thus, depending on the proportion of apolar / polar solvent, the deasphalted DAO oil yield can be considerably improved and thus the asphalt yield greatly minimized. This is a point of interest knowing that the recovery of asphalt (penalizing fraction) is still a real limitation for schemes including this type of process. The deasphalted DAO complete oil resulting from step a1) with at least partly the solvent mixture is preferably subjected to at least one separation step in which the complete deasphalted oil called complete DAO is separated by at least one part of the solvent mixture, or at least one separation step in which the complete deasphalted oil called complete DAO is separated only from the apolar solvent or only the polar solvent, before being sent to step a2). In a variant of the process, the complete deasphalted oil called complete DAO resulting from step a1) with at least partly the solvent mixture according to the invention is subjected to at least two successive separation stages for separating the solvents individually. in each step. Thus, for example, in a first separation step the apolar solvent is separated from the complete deasphalted oil mixture called complete DAO and polar solvent; and in a second separation step the polar solvent is separated from the complete deasphalted oil called complete DAO.
    [0019] The separation steps are advantageously carried out under supercritical or subcritical conditions. At the end of the separation step, the complete deasphalted oil, called complete DAO, separated from the solvents, can be sent beforehand to at least one stripping column before being sent to the second step (step a2) of deasphalting. The mixture of polar and apolar solvents or the individually separated solvents are advantageously recycled in the process as a mixture or by means of two tanks individually containing the polar solvent and the apolar solvent. In a variant of the process, only the nonpolar solvent is recycled in its auxiliary container. When the recycled solvents are in a mixture, the polar / polar proportion is verified online in the process and readjusted as necessary via the fillers 30 individually containing the polar solvent and the apolar solvent. When the solvents are individually separated, said solvents are individually recycled to the respective booster tanks.
    [0020] The asphalt phase separated from the first deasphalting step is preferably in the liquid state and is generally diluted at least in part with a portion of the solvent mixture according to the invention, the amount of which can be up to 200%, of preferably between 30 and 80% of the asphalt volume withdrawn. Asphalt extracted with at least a portion of the mixture of polar and apolar solvents at the end of the extraction step may be mixed with at least one fluxing agent so as to be withdrawn more easily. The fluxing agent used may be any solvent or solvent mixture that can solubilize or disperse the asphalt. The axant may be a polar solvent selected from monoaromatic hydrocarbons, preferably benzene, toluene or xylene; diaromatic or polyaromatic; naphthenocarbon aromatic hydrocarbons such as tetralin or indane; heteroatomic aromatic hydrocarbons; polar solvents with a molecular weight corresponding to boiling temperatures of, for example, between 200 ° C. and 600 ° C., such as an LCO (FCC light cycle oil), an HCO (FCC heavy cycle oil), FCC slurry, HCGO (heavy coker gas oil), or an aromatic extract or an extra-aromatic cut extracted from an oil chain, the VGO cuts resulting from a conversion of residual fractions and / or coal and / or biomass. The ratio of the volume of fluxant to the mass of the asphalt is determined so that the mixture can be easily withdrawn.
    [0021] The second deasphalting step can be carried out on at least a portion, preferably all of the complete deasphalted oil called complete DAO resulting from the first deasphalting step in the presence of a mixture of at least one polar solvent and at least one apolar solvent under subcritical conditions for the solvent mixture used. The second deasphalting step may also be carried out on at least a portion, preferably all of the complete deasphalted oil called complete DAO resulting from the first deasphalting step in the presence of an apolar solvent under subcritical conditions for solvent used. The polarity of said solvent or solvent mixture is preferably lower than that of the solvent mixture used in the first deasphalting step. This extraction is performed so as to obtain a heavy deasphalted oil fraction called heavy DAO mainly comprising the family of less polar resins and asphaltenes, and a light deasphalted oil fraction called light DAO mainly comprising the family of saturated hydrocarbons and the family of aromatic hydrocarbons. At least a portion, preferably all of said heavy deasphalted oil fraction called heavy DAO is sent to hydroconversion stage b). At least a portion of the light deasphalted oil fraction, called mild DAO, alone or mixed with at least a portion of said vacuum distillate fraction boiling at a temperature of between 360 and 520 ° C. or even 540 ° C. resulting from the step of separation of the heavy liquid fraction from step d) is advantageously sent to post-treatment units such as a hydrotreatment unit and / or hydrocracking, or catalytic cracking.
    [0022] Second Embodiment In a second embodiment, the method according to the invention comprises at least: a1) a first deasphalting step comprising contacting the heavy hydrocarbon feedstock with either an apolar solvent or a mixture of at least one polar solvent and at least one apolar solvent, the proportions of said polar solvent and of said apolar solvent of the mixture being adjusted so as to obtain at least a light deasphalted oil fraction called light DAO and an effluent comprising an oil phase and an asphalt phase; and a'2) a second deasphalting step comprising contacting the effluent from step a'1) with a mixture of at least one polar solvent and at least one apolar solvent, the proportions of said polar solvent and said apolar solvent being adjusted so as to obtain at least one asphaltic phase fraction and a heavy DAO deasphalted oil fraction, wherein said deasphalting steps are carried out under the subcritical conditions of the solvent or mixture of solvents used and wherein the heavy deasphalted oil fraction called heavy DAO is sent in step b).
    [0023] In the present embodiment, the order of extraction of the product categories is reversed: the polarity of the solvent or solvent mixture used in the first deasphalting step is lower than that of the solvent mixture used in the second step of deasphalting. The first deasphalting step thus makes it possible to extract selectively from the heavy hydrocarbon feedstock a light deasphalted oil fraction called light DAO and an effluent comprising an oil phase and an asphalt phase. The first deasphalting step (step a1) can be carried out both with an apolar solvent and with a solvent mixture according to the invention. The nature, the proportion and / or the polarity of the polar solvent in the solvent mixture is adapted, under the subcritical conditions of the solvent or of the solvent mixture used, so as to extract a fraction of light deasphalted oil mainly comprising the family of solvents. saturated hydrocarbons and the family of aromatic hydrocarbons. At least a portion of the light deasphalted oil fraction, called mild DAO, alone or mixed with at least a portion of said vacuum distillate fraction boiling at a temperature of between 360 and 520 ° C. or even 540 ° C. resulting from the step of Separation of the heavy liquid fraction from step d) is advantageously sent to post-treatment units such as a hydrotreating and / or hydrocracking unit, or catalytic cracking unit. The effluent comprising an oil phase and an asphalt phase, extracted from the first deasphalting stage may contain at least partly the apolar solvent or the solvent mixture according to the invention. Advantageously according to the invention, said effluent is subjected to at least one separation step in which it is separated from at least a part of the apolar solvent or at least a part of the solvent mixture, or at least one separation step wherein said effluent is separated only from the apolar solvent or only the polar solvent contained in the solvent mixture, before being sent to step a'2). In a variant of the process according to the invention, said effluent may be subjected to at least two successive separation stages enabling the solvents to be separated individually in each separation step, before being sent to step a'2). The separation steps are advantageously carried out under supercritical or subcritical conditions. At the end of the separation step, the effluent comprising the oil phase and the asphalt phase separated from the solvent or the solvent mixture according to the invention can be sent beforehand into at least one stripping column before being sent 10 in the second step of deasphalting. The mixture of polar and apolar solvents or the individually separated solvents are advantageously recycled in the process as a mixture or by means of two tanks individually containing the polar solvent and the apolar solvent. In one variant of the process, only the non-polar solvent is recycled to its auxiliary container. When the recycled solvents are in a mixture, the polar / polar proportion is verified online in the process and readjusted as necessary via the booster tanks individually containing the polar solvent and the apolar solvent. When the solvents are individually separated, said solvents are individually recycled to the respective booster tanks. The second deasphalting step is carried out on the effluent comprising an oil phase and an asphalt phase resulting from the first deasphalting step a '1) in the presence of a mixture of at least one polar solvent and at least one an apolar solvent under subcritical conditions for the solvent mixture used. The polarity of said solvent mixture is preferably greater than that of the solvent or solvent mixture used in the first deasphalting step. This extraction is carried out so as to extract selectively from the effluent, an ultimate so-called asphalt fraction, enriched with impurities and compounds that are refractory to recovery, while leaving solubilized in a fraction of heavy deasphalted oil called heavy DAO all or part polar structures of the less polar resins and asphaltenes generally remaining in the asphalt fraction in the case of conventional deasphalting.
    [0024] At least a portion, preferably all of said heavy deasphalted oil fraction called heavy DAO is sent to hydroconversion stage b). Step b) hydroconversion of the deasphalted oil fraction resulting from step = 1a In accordance with step b) of the process according to the invention, the deasphalted oil fraction resulting from step a) undergoes a step b) hydroconversion in the presence of hydrogen in at least one three-phase reactor, said reactor containing at least one hydroconversion catalyst and operating as a bubbling bed, with an upward flow of liquid and gas and comprising at least one means for drawing off said catalyst out of said reactor and at least one fresh catalyst booster means in said reactor, under conditions making it possible to obtain an effluent comprising a gaseous fraction containing predominantly H2 and H2S compounds, and a Conradson reduced carbon liquid fraction. , in metals, sulfur and nitrogen, step b) of hydroconversion of the feedstock according to the invention is generally carried out under conventional hydroconversion conditions in a boiling bed containing a liquid hydrocarbon fraction. The operation is usually carried out under an absolute pressure of between 2 and 35 MPa, preferably between 5 and 25 MPa, and preferably between 6 and 20 MPa, at a temperature of between 300 and 550 ° C. and preferably between 350 and 500. ° C. The hourly space velocity (VVH) and the hydrogen partial pressure are important factors that are chosen according to the characteristics of the product to be treated and the desired conversion. Preferably, the VVH is between 0.1 h -1 and 10 h -1 and preferably between 0.15 h -1 and 5 h -1. The quantity of hydrogen mixed with the feedstock is preferably between 50 and 5000 normal cubic meters (Nm3) per cubic meter (m3) of liquid feed and preferably between 100 and 2000 Nm3 / m3, and very preferably between 200 and 1000 Nm3 / m3.
    [0025] Step b) 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.
    [0026] The hydroconversion catalyst used in step b) of the process according to the invention is advantageously a granular catalyst with a size of about 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. Advantageously, it is possible to inject a catalytic precursor (or catalytic additive) either with the charge of the hydroconversion unit operating in a bubbling bed, or with an inter-stage separator between two reactors, or at the inlet of one of the other reactors. .
    [0027] The term "catalytic precursor or catalytic additive" refers here to a hydroconversion catalyst whose properties of size and density are such that it is driven by the conversion charge in the hydroconversion reaction zones, as opposed to the catalyst. described above not circulating.
    [0028] 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. It is 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 and then to return this regenerated catalyst to the hydroconversion stage b). It is also 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 it contains and then return the regenerated catalyst in step b) of hydroconversion. Step b) of the process according to the invention is advantageously carried out under the conditions of the H-OIITM process as described, for example, in US Pat. No. 4,521,295 or US Pat. No. 4,495,060 or US Pat. US-A-4,354,852 or in the article Aiche, March 19-23, 1995, HOUSTON, Texas, paper number 46d, second generation ebullated bed technology. The hydroconversion catalyst used in the hydroconversion stage b) advantageously makes it possible to ensure both the demetallation and the desulfurization, under conditions making it possible to obtain an effluent comprising a gaseous fraction predominantly containing the compounds H2 and H2S. and a Conradson carbon reduced liquid fraction of metals, sulfur and nitrogen.
    [0029] Stage c) of separation of the effluent resulting from stage b) The effluent resulting from stage b) of hydroconversion then undergoes according to stage c) of the process according to the invention, a separation to obtain a gaseous fraction containing predominantly H2 and H2S compounds and a Conradson carbon reduced liquid fraction of metals, sulfur and nitrogen. This separation comprises any separation means known to those skilled in the art. Preferably, this separation is performed by one or more flash balloons in series, and preferably by a sequence of two successive flash balloons. Step d) optional separation of the liquid fraction from step c) Advantageously according to the invention, the liquid fraction from step c) then undergoes according to step d), a separation step to obtain a light liquid fraction boiling at a temperature below 360 ° C, preferably below 375 ° C and a heavy liquid fraction boiling at a temperature above 360 ° C, preferably above 375 ° C. In step d) of separation, the conditions are chosen so that the cutting point is 360 ° C, preferably 375 ° C allows to obtain two liquid fractions, a so-called liquid fraction, and a so-called heavy liquid fraction. The light liquid fraction directly obtained at the outlet of the separation stage d) alone or in admixture with the gaseous fraction resulting from stage c) is then advantageously separated from the light gases (H2, H2S, NH3 and Cl-04). by any means of separation known to those skilled in the art such as for example by passing through a flash balloon, so as to recover the hydrogen gas which is advantageously recycled after purification in the hydroconversion stage b). Said light liquid fraction, advantageously separated from said light gases and boiling at a temperature below 360 ° C., preferably below 375 ° C., comprises for the most part a fraction boiling at a temperature below 180 ° C. corresponding to the gasoline fraction, a diesel fraction. boiling at a temperature between 180 and 360 ° C or between 180 and 375 ° C.
    [0030] Said light liquid fraction is then advantageously sent to a separation step, preferably in an atmospheric distillation column to separate said fractions. The heavy liquid fraction obtained at the outlet of step d) and boiling at a temperature greater than 360 ° C., preferably greater than 375 ° C., contains at least a portion of the gas oil fraction boiling between 250 and 375 ° C., a fraction boiling between 360 and 520 ° C or 540 ° C, preferably between 375 and 520 ° C or 540 ° C, called vacuum distillate (or VGO according to the English terminology) and a non-converted fraction boiling at a higher temperature at 520 ° C or 540 ° C, called vacuum residue. Said vacuum-vacuum distillate fraction (or VGO according to the English terminology) comprises a so-called light sub vacuum fraction (or light VGO) boiling between 360 and 400 ° C. or even 420 ° C. and a so-called heavy vacuum distillate fraction. (or heavy VGO) boiling between 400 and 520 ° C or 540 ° C and preferably between 420 and 520 ° C or 540 ° C.
    [0031] Said heavy liquid fraction is advantageously sent in a separation step, preferably in a vacuum distillation column to separate said fractions. The low vacuum (or light VGO) and heavy (or heavy VGO) distillate fractions may be individually separated or not during said separation step. In a variant of the process according to the invention, at least part of the vacuum residue boiling at a temperature above 520 ° C or 540 ° C is returned to the deasphalting step a) mixed with the feedstock.
    [0032] In a variant of the process according to the invention, at least a portion of the vacuum distillate fraction (VGO), advantageously derived from the step of separating the heavy liquid fraction from step d), is returned to the hydroconversion step b) in admixture with the deasphalted oil fraction from step a). This has the advantage of improving the diesel selectivity, the desired end product in the process scheme, by subjecting a second pass to the vacuum distillate (VGO) in the hydroconversion stage b). Another advantage of such recycling is to provide additional leverage to go further in the solubilization in the deasphalted oil fraction (DAO) of the polar structures of heavy resins and asphaltenes. The recycling of the vacuum vacuum distillate (VGO) essentially free of asphaltenes makes it possible to dilute the asphaltenes present in the deasphalted oil fraction (DAO) sent in the hydroconversion stage b). As a result, the asphalt phase is reduced and the overall system conversion improved. On the other hand, because of its preponderant aromatic character, the vacuum distillate (VGO) makes it possible, during its recycling in the boiling bed, to stabilize the treated medium by solubilizing and / or peptizing and / or dispersing the molecular structures that are suitable for sediment formation and thus improve the operability of the scheme. When the vacuum distillate fraction (VGO) boiling between 400 and 520 ° C or even 540 ° C is returned to the bubbling bed unit a portion that fraction corresponding to the light vacuum subdivided fraction vaporizes and penalizes the time. of residence of the liquid in the bubbling bed unit. Thus, in another variant of the process according to the invention, only at least a portion of the heavy vacuum sub-vacuum fraction (or heavy VGO) boiling between 400 and 520 ° C. or even 540 ° C. and preferably between 420 and 520 ° C. ° C or 540 ° C, advantageously from the separation step of the heavy liquid fraction from step d), is returned to the hydroconversion stage b) mixed with the deasphalted oil fraction from step a).
    [0033] Examples Example 1 (comparative): conventional SDA followed by a hydroconversion stage The feedstock, an Ural vacuum residue (Ural VR), is sent to a conventional deasphalting unit. The solvent used is pentane. The characteristics of the filler and the deasphalted oil obtained (DA01) are detailed below in Table 1. The deasphalting conditions are: - a solvent / filler ratio of 8/1, - a pressure in the unit deasphalting 3.7 MPa (absolute: abbreviated abs in the following examples) - and an extraction temperature of 180 ° C.
    [0034] Table 1: Composition of the filler and the deasphalted oil DA01 VR Ural DAO 1 Density 1.003 0.972 CCR (% wt) 14.5 9 C7 Asph (% wt) 5.2 0.05 Ni (ppm) 50 12 V (ppm) 170 42 N ( ppm) 5300 4360 S (% wt) 2.72 2.45% wt = weight percentage; ppm = parts per million; C7 Asph = Asphaltenes C7, Ni = Nickel; V = Vanadium; N = Nitrogen; S = Sulfur. The deasphalted oil DA01 is treated in a boiling bed hydroconversion unit under the operating conditions: 15 MPa (abs) of pressure, a temperature of 435 ° C., and in the presence of a NiMo type catalyst on alumina.
    [0035] The yields (Table 2) are shown on a 100% weight basis with respect to the feedstock. 302 132 6 25 Table 2: Yields H2S + NH3 0.15 Gas 2.49 Petrol (PI-180 ° C) 10.87 Diesel (1 80 ° C-360 ° C) 23.56 VGO (360 ° C-540 ° C) 31.25 VR (540 °) C +) 10.83 ODP 0 Asphalt SDA 22.00 Total 101.15 Consumption 112 1.15 The overall conversion of the 540+ fraction of the input load is 67%. Example 2 (according to the invention): Selective SDA followed by a hydroconversation step The same feed as that used in Example 1 is sent to a selective deasphalting unit. The solvent used is a mixture of heptane (C7) / toluene in a ratio of 96/4 volume / volume. The characteristics of the filler and deasphalted oil (DAO 2) obtained are detailed in Table 3. The deasphalting conditions are: a solvent / filler ratio of 8/1, a pressure in the deasphalting unit selective 4 MPa (abs) - and an extraction temperature of 240 ° C. Table 3: Composition of the filler and deasphalted oil DAO2 VR Ural DAO 2 Density 1.003 0.988 CCR (% wt) 14.5 10.4 C7 Asph (% wt) 5.2 0.09 Ni (ppm) 50 18 V (ppm) 170 60 N ( ppm) 5300 4611 S (% wt) 2.72 2.54% wt = weight percentage; ppm = parts per million; C7 Asph = Asphaltenes C7, Ni = Nickel; V = Vanadium; N = Nitrogen; S = Sulfur. The deasphalted oil (DAO 2) represents, compared to the deasphalted oil DAO 1 of Example 1, a larger cut of the feedstock (85% by weight vs 78% by weight).
    [0036] This deasphalted oil also contains 0.1% of C7 asphaltenes (C7 Asph) corresponding to the maximum specification imposed at the inlet of the hydroconversion unit. The bubbling bed hydroconversion unit is operated under the operating conditions of: - 15 MPa (abs) pressure, - a temperature of 435 ° C. - and in the presence of a NiMo type catalyst on alumina. Yields are shown on a 100 weight basis relative to the input load. Table 4: Yields H2S + NH3 2.57 Gas 6.98 Petrol (PI-180 ° C) 11.54 Diesel (180 ° C-360 ° C) 39.24 VGO (360 ° C-540 ° C) 20.66 VR (540 ° C +) 6.08 DAO 0 Asphalt SDA 15.00 Total 102.07 Consumption 112 2.07 15 The overall conversion of the 540+ fraction of the input load has been improved to 79%. Example 3 (according to the invention): Selective SDA followed by a hydroconversion step with recycling of the VGO cut The same feed as that used in Example 1 is sent to a selective deasphalting unit. The solvent used is a mixture of heptane (C7) / toluene in a ratio of 95: 5 v / v. The characteristics of the filler and deasphalted oil (DAO3) obtained are detailed below in Table 5. The deasphalting conditions are: a solvent / filler ratio of 8: 1, a pressure in the selective deasphalting unit of 4 MPa (abs) - and an extraction temperature of 240 ° C. The C7 / toluene ratio is decreased to further improve the deasphalted oil (DAO3) yield. The asphaltene content in the selective DAO3 exceeds the maximum specification of 0.1% wt. Set at the inlet of the hydroconversion unit. Part of the vacuum distillate (VGO) from the separation step of the heavy liquid fraction separated from step d) of the process is mixed with the deasphalted oil (DAO3) in the bubbling bed. The VGO / DAO3 weight ratio is set at 20/80 to meet the maximum specification of 0.1% by weight of C7 asphaltenes (C7 Asph). The characteristics of the mixture are shown in Table 5. Table 5: Composition of the filler, deasphalted oil DAO3, VGO and the mixture VGO / DAO3 VR Ural DAO 3 VGO Blend DAO3 / VGO Density 1.003 0.993 0.845 0.959 CCR ( % wt) 14.5 11.9 0.2 9.6 C7 Asph (% wt) 5.2 0.12 0.0 0.10 Ni (ppm) 50 28 0.0 22 V (ppm) 170 94 0.0 75 N (ppm) 5300 4770 518 3920 S (% wt) 2.72 2.61 0.05 2.10 % wt = weight percentage; ppm = parts per million; C7 Asph = Asphaltenes C7, Ni = Nickel; V = Vanadium; N = Nitrogen; S = Sulfur. The VGO / DAO3 mixture is sent to the bubbling bed hydroconversion unit under the operating conditions: 15 MPa (abs) of pressure, a temperature of 435 ° C. and in the presence of a catalyst of the following type: NiMo on alumina. The yields are indicated on a 100 weight basis with respect to the input charge.
    [0037] Table 6: Yields FLS + NH3 2.34 Gas 7.52 Petrol (PI-180 ° C) 12.34 Diesel (180 ° C-360 ° C) 42.00 VGO (360 ° C-540 ° C) 21.69 RP (540 ° C +) 6.33 DAO 0 Asphalt SDA 10 Total 102.22 Conso. 2.22 The overall conversion of the 540+ fraction of the input charge is 84%. The selectivity for diesel and gasoline was improved respectively by 2.76% and 0.80% by weight.
    权利要求:
    Claims (23)
    [0001]
    REVENDICATIONS1. A process for converting a heavy hydrocarbon feedstock having an initial boiling temperature of at least 300 ° C comprising the steps of: a) at least one step of selective deasphalting of the heavy hydrocarbon feedstock by liquid extraction / liquid for separating at least one asphalt fraction, at least one deasphalted oil fraction, at least one of said deasphalting steps being carried out by means of a mixture of at least one polar solvent and at least one apolar solvent, the proportions of said polar solvent and of said apolar solvent of the solvent mixture being adjusted according to the properties of the treated filler and according to the asphalt yield and / or the quality of the desired deasphalted oil (s), said deasphalting steps being carried out under the subcritical conditions of the mixture of solvents used, b) a step of hydroconversion of the deasphalted oil fraction in the presence of hydrogen dan s at least one three-phase reactor, said reactor containing at least one hydroconversion catalyst and operating as a bubbling bed, with an upward flow of liquid and gas and comprising at least one means for withdrawing said catalyst from said reactor and at least one means for adding fresh catalyst to said reactor, under conditions making it possible to obtain an effluent comprising a gaseous fraction containing predominantly H2 and H2S compounds, and a Conradson carbon reduced liquid fraction, of metals, sulfur and nitrogen, c) a step of separating the effluent from step b) to obtain a gas fraction containing predominantly H2 and H2S compounds and a Conradson carbon reduced liquid fraction, metals, sulfur and nitrogen.
    [0002]
    The process according to claim 1 wherein step a) comprises at least: a1) a first step of selective deasphalting comprising contacting the heavy hydrocarbon feedstock with a mixture of at least one polar solvent and at least one apolar solvent, the proportions of said polar solvent and said apolar solvent being adjusted so as to obtain at least one asphalt phase fraction and a complete deasphalted oil fraction called complete DAO; and a2) a second deasphalting step comprising contacting the complete deasphalted oil fraction called complete DAO resulting from step a1) with either an apolar solvent or a mixture of at least one polar solvent and from less an apolar solvent, the proportions of said polar solvent and of said apolar solvent in the mixture being adjusted so as to obtain at least a fraction of light deasphalted oil called light DAO and a heavy deasphalted oil fraction called heavy DAO, in which said deasphalting steps are carried out under the subcritical conditions of the solvent or solvent mixture used and in which the heavy deasphalted oil fraction called heavy DAO is sent in step b).
    [0003]
    3. Method according to claim 2 wherein the complete deasphalted oil fraction called complete DAO from step a1) with at least partly the solvent mixture is subjected to at least one separation step in which the deasphalted oil complete so-called complete DAO is separated from at least a portion of the solvent mixture, or at least one separation step in which the complete deasphalted oil complete said DAO is separated only apolar solvent or only the polar solvent before being sent in step a2).
    [0004]
    4. The method of claim 2 wherein the complete deasphalted oil called complete DAO from step a1) with at least partly the solvent mixture is subjected to at least two successive separation steps to separate the solvents individually in each step, before being sent in step a'2).
    [0005]
    5. The method of claim 1 wherein step a) comprises at least: garlic) a first deasphalting step comprising contacting the heavy hydrocarbon feedstock with either an apolar solvent or a mixture of at least a polar solvent and at least one apolar solvent, the proportions of said polar solvent and of said apolar solvent of the mixture being adjusted so as to obtain at least a fraction of light deasphalted oil called light DAO and an effluent comprising an oil phase and a phase asphalt; and a'2) a second deasphalting step comprising contacting the effluent from step a'1) with a mixture of at least one polar solvent and at least one apolar solvent, the proportions of said polar solvent and said apolar solvent being adjusted so as to obtain at least one fraction of asphalt phase and a deasphalted oil fraction called heavy DAO, in which said deasphalting steps are carried out under the subcritical conditions of the solvent or of the mixture of solvents used and wherein the heavy deasphalted oil fraction called heavy DAO is sent in step b).
    [0006]
    6. The method of claim 5 wherein the effluent from step a'1) is subjected to at least one separation step wherein it is separated from at least a portion of the apolar solvent or at least one part of the solvent mixture, or at least one separation step in which said effluent is separated only from the apolar solvent or only the polar solvent contained in the solvent mixture, before being sent to step a'2).
    [0007]
    7. A process according to claim 5 wherein the effluent is subjected to at least two successive separation steps to separate the solvents individually in each separation step, before being sent to step a'2).
    [0008]
    8. Method according to one of the preceding claims wherein step b) is carried out in one or more three-phase hydroconversion reactors with intermediate settling flasks.
    [0009]
    9. Method according to one of the preceding claims wherein the hydroconversion step b) operates at an absolute pressure of between 2 and 35 MPa, at a temperature between 300 and 550 ° C, at a space velocity hourly (VVH ) Between 0.1 hr -1 and 10 hr -1 and under a quantity of hydrogen mixed with the feedstock of between 50 and 5000 normal cubic meters (Nm3) per cubic meter (m3) of liquid feed.
    [0010]
    10. A method according to rune preceding claims further comprising a step d) separating the liquid fraction from step c) into a light liquid fraction boiling at a temperature below 360 ° C and a heavy liquid fraction boiling at a temperature above 360 ° C.
    [0011]
    11. The method of claim 10 wherein at least a portion of the light liquid fraction from step d) is sent in a separation step to produce a gasoline fraction boiling at a temperature below 180 ° C, a fraction gas oil boiling at a temperature between 180 and 360 ° C or between 180 and 375 ° C.
    [0012]
    The process of claim 10 or 11 wherein at least a portion of the heavy liquid fraction from step d) is sent to a separation step to produce a vacuum distillate fraction boiling at a temperature between 360 and 520 ° C and a vacuum residue boiling above 520 ° C.
    [0013]
    13. A process according to claim 12 wherein at least a portion of the vacuum distillate fraction boiling at a temperature between 360 and 520 ° C is returned to the hydroconversion stage b) in admixture with deasphalted oil from step a).
    [0014]
    14. A process according to claim 12 wherein only at least a portion of the heavy vacuum distillate fraction boiling between 400 and 520 ° C is returned to the hydroconversion stage b) in admixture with the deasphalted oil fraction. from step a).
    [0015]
    15. Process according to one of Claims 2 to 14, in which at least a portion of the light deasphalted oil fraction, called mild DAO, is preferably mixed with at least a portion of said boiling-distillate distillate fraction. a temperature of between 360 and 520 ° C. is sent to post-treatment units such as a hydrotreating and / or hydrocracking or catalytic cracking unit.
    [0016]
    16. A method according to one of claims 12 to 15 wherein at least a portion of the vacuum residue boiling at a temperature above 520 ° C is returned to the step d) of deasphalting mixed with the load.
    [0017]
    17. Method according to one of the preceding claims wherein the hydroconversion catalyst is a catalyst comprising an alumina support and at least one group VIII metal selected from nickel and cobalt, said group VIII element being used in combination with at least one Group VIB metal selected from molybdenum and tungsten.
    [0018]
    18. Method according to one of the preceding claims wherein the polar solvent used in step a) of deasphalting is selected from aromatic solvents pure or naphtho-aromatic polar solvents comprising heteroelements, or their mixture or rich cuts in aromatics such as FCC (Fluid Catalytic Cracking) cuts, coal-derived sections, biomass or biomass / coal mixtures.
    [0019]
    19. A process according to any one of the preceding claims wherein the apolar solvent used in the deasphalting step a) comprises a saturated hydrocarbon solvent comprising a number of carbon atoms greater than or equal to 2, preferably comprised between 2 and 9.
    [0020]
    20. Process according to one of the preceding claims, in which step a) is carried out with a volume ratio of the polar and apolar solvent mixture on the mass of the filler between 1/1 and 10/1 expressed. in liters per kilogram.
    [0021]
    21. The process as claimed in one of the preceding claims, in which the feedstock is crude oil or a feedstock resulting from atmospheric distillation or from the vacuum distillation of crude oil, or a residual fraction resulting from the direct liquefaction of coal or still another vacuum distillate or a residual fraction resulting from the direct liquefaction of the lignocellulosic biomass alone or mixed with coal and / or a residual petroleum fraction.
    [0022]
    22. Process according to one of the preceding claims, in which a catalytic precursor is injected either with the charge of the hydroconversion unit operating in a bubbling bed, or with the inter-stage separator between two reactors, or at the inlet of the reactor. one of the other 5 reactors.
    [0023]
    23. Method according to one of the preceding claims wherein the light fraction obtained at the outlet of the separation step d) alone or in admixture with the gaseous fraction from step c) is separated from the light gases (H2, H2S , NH3 and C1-C4) so as to recover the hydrogen gas which is recycled after purification in the hydroconversion stage b).
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    同族专利:
    公开号 | 公开日
    RU2015119106A|2016-12-10|
    CN105255517A|2016-01-20|
    CA2891872A1|2015-11-21|
    EP2947133A1|2015-11-25|
    RU2015119106A3|2018-12-11|
    RU2687098C2|2019-05-07|
    FR3021326B1|2017-12-01|
    CN105255517B|2019-08-20|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1454576A|FR3021326B1|2014-05-21|2014-05-21|METHOD FOR CONVERTING A HEAVY HYDROCARBON LOAD INTEGRATING SELECTIVE DESASPHALTATION BEFORE THE CONVERSION STEP.|FR1454576A| FR3021326B1|2014-05-21|2014-05-21|METHOD FOR CONVERTING A HEAVY HYDROCARBON LOAD INTEGRATING SELECTIVE DESASPHALTATION BEFORE THE CONVERSION STEP.|
    EP15305574.4A| EP2947133A1|2014-05-21|2015-04-16|Method for converting a heavy hydrocarbon feedstock including selective de-asphalting upstream from the conversion step|
    CA2891872A| CA2891872A1|2014-05-21|2015-05-19|Method for converting a heavy hydrocarbon load integrating selective deasphalting before the conversion step|
    RU2015119106A| RU2687098C2|2014-05-21|2015-05-20|Method of converting a heavy hydrocarbon feedstock, involving selective de-asphalting upstream from conversion step|
    CN201510261592.7A| CN105255517B|2014-05-21|2015-05-21|In the heavy hydrocarbon charge method for transformation of step of converting upstream integrated selection depitching step|
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