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    • 专利摘要:
    The invention describes a method of deasphalting a heavy load by liquid / liquid extraction, said process comprising at least two deasphalting steps in series carried out on the feedstock to be treated, which makes it possible to separate at least one asphalt fraction, at least one fraction of heavy deasphalted oil, called heavy DAO and at least a fraction of light deasphalted oil, called light DAO, at least one of said deasphalting steps being carried out using a mixture of at least one polar solvent and at least one an apolar solvent, said deasphalting steps being carried out under the subcritical conditions of the solvent mixture used.
    公开号:FR3014109A1
    申请号:FR1362028
    申请日:2013-12-03
    公开日:2015-06-05
    发明作者:Isabelle Merdrignac；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 field of crude oil processing. More particularly, the present invention relates to a new process for the selective deasphalting of a heavy batch, in particular of crude oil residues, by liquid / liquid extraction. PRIOR ART Crude oil residues are characterized by a continuum of molecular structures of increasing polarity and molecular weight which can generally be grouped into four families: The family of saturated hydrocarbons comprising saturated and unsaturated hydrocarbons without a nucleus The family of aromatic hydrocarbons comprising essentially aromatic and / or heteroatomic and / or polyaromatic nuclei generally sulfur and / or nitrogenous. This family has a more polar character than that of the family of saturated hydrocarbons. - The family of resins essentially comprising heteroatomic aromatic rings generally sulfur and / or nitrogen and / or metallized with metals such as nickel and vanadium. This family also includes polyaromatic and / or polyaromatic heteroatomic nuclei. This family has an even more polar character than that of the family of aromatic hydrocarbons. The family of asphaltenes comprising the most polar molecular structures of the continuum and which are of the heteroatomic polyaromatic type. Asphaltenes are mainly compounds rich in sulfur impurities, and / or nitrogen and / or oxygenated on which are complexed metals such as nickel and vanadium. The resins are contained in the petroleum fractions whose boiling point is generally above 300 ° C, whereas the asphaltenes are mainly concentrated in high boiling fractions generally above 500 ° C.
    [0002] Among the existing processes, the crude oil residues may be subjected to a prior deasphalting treatment well known to those skilled in the art. The principle of deasphalting is based on a separation by precipitation of a petroleum residue in two phases: i) a phase called "deasphalted oil", also called "oil matrix" or "oil phase" or DAO (De-Asphalted Oil according to the terminology Anglo-Saxon) which can be valorised by means of various refining processes; and ii) a phase called "asphalt" or sometimes "pitch" (according to the English terminology) containing the refractory molecular structures described above. Asphalt, by its poor quality and its variable state which can pass from a solid phase, then pasty and finally liquid according to the conditions of temperature, is a penalizing product for the schemes of refining which should be minimized. Indeed, the performance of the processes of recovery and conversion of heavy loads face limitations that are mainly governed by the presence of such refractory molecular structures contained in the asphalt.
    [0003] This deasphalting, referred to hereinafter as the conventional deasphalting text, is generally carried out using a paraffinic type solvent. US Pat. No. 7,857,964 describes the impact of the nature of the paraffinic solvent used in a deasphalting process on the hydrotreating performance of the residues. US Pat. Nos. 4,305,812 and 4,455,216 disclose deasphalting as countercurrent extraction in a column with several solvents of increasing polarity injected at different heights of the column.
    [0004] US Patent 2008/149534 deals with a method of deasphalting in cascade, in particular in two stages. A first paraffinic solvent with 5 or 7 carbon atoms (C5 or C7) is used to extract the asphalt. The collected DAO deasphalted oil is then treated with another paraffinic solvent containing less carbon (C3 or C4) to separate a fraction comprising the resins from the oil matrix. However, this process has the disadvantage of producing low yields of deasphalted DAO oil related to the use of a paraffinic solvent. The solutions proposed in the prior art are all based on conventional deasphalting which, by its principle, has limitations in terms of yield and flexibility with respect to the recovery envisaged for the oil residues. The use of solvents or mixture of paraffinic type solvents in conventional deasphalting imposes a limitation of the yield of deasphalted oil DAO, said yield increasing with the molecular weight of the solvent (up to the solvent C6 / C7) and then capping at a threshold specific to each load and each solvent. The present invention makes it possible to postpone the limitations described above. It makes it possible to improve separation flexibility as well as the yield of recoverable products. The implementation of such a process comprises at least two stages of deasphalting in series and makes it possible to increase the selectivity of the separation of the charge. It makes it possible to obtain a more varied range of fractions of molecular structures. At least one of the deasphalting steps according to the invention is 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 being adjusted according to the properties of the the filler, depending on the purpose of each deasphalting step, depending on the desired asphalt yield and / or the desired quality of the DAO fractions, said deasphalting steps being carried out under subcritical conditions of the solvent mixture.
    [0005] An object of the method according to the invention is to allow greater flexibility in the treatment of the charges by accessing a range of separation selectivity hitherto inaccessible with conventional deasphalting. The process according to the invention makes it possible to more selectively adjust the properties of the recoverable fractions of the residue feedstock during its recovery while maximizing the final yield of all the different deasphalted DAO oil fractions separated from the process. DESCRIPTION OF THE FIGURES FIG. 1 represents a deasphalting scheme according to the invention.
    [0006] Figure 2 shows a deasphalting diagram incorporating two separators and a recycling of solvents individually in their respective bins. DETAILED DESCRIPTION OF THE INVENTION In the remainder of the text and in the foregoing, the expression "solvent mixture according to the invention" is intended to mean a mixture of at least one polar solvent and at least one apolar solvent. according to the invention. The process according to the invention comprises at least two deasphalting stages in series carried out on the batch to be treated, making it possible to separate at least one asphalt fraction, at least one heavy deasphalted oil fraction, called heavy DAO and at least one d light deasphalted oil, so-called 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 the subcritical conditions of the solvent mixture used.
    [0007] The choice of solvents as well as the proportions of said polar solvent and of said apolar solvent of the solvent mixture are adjusted firstly according to the properties of the feedstock to be treated and according to the asphalt yield and / or the quality of the deasphalted DAO heavy and Lightweight desired CAD (s), and secondly according to the specifications of the subsequent recovery processes envisaged for each of the fractions such as hydrocracking, hydrotreating, hydroconversion, catalytic cracking, thermal cracking, etc. This results in a substantial gain in terms of separation performance, the yields and the quality of the separated fractions being improved and / or optimized according to the objective of the scheme in which the method according to the invention is inserted.
    [0008] The method according to the invention allows, thanks to specific deasphalting conditions, greater flexibility in the treatment of the charges depending on their nature, but also according to the recovery scheme envisaged downstream of said treatment. The deasphalting conditions according to the invention make it possible to overcome the limitations on the yield of DAO deasphalted oil, as is required in conventional deasphalting by the use of paraffinic solvents. The process according to the invention 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. The invention thus makes it possible to choose which type of polar structures remain solubilized in the DAO oil matrix. The asphalt extracted during deasphalting according to the invention corresponds to the ultimate asphalt composed essentially of the most refractory polyaromatic and / or heteroatomic molecular structures in the conversion and refining processes. This results in a total yield of improved deasphalted oil. The invention thus makes it possible to obtain at least three fractions: an asphalt fraction, a heavy deasphalted oil fraction called heavy DAO and a light deasphalted oil fraction called light DAO with a greater flexibility than for conventional deasphalting in terms of optimization of yield and / or quality of each of the fractions obtained. According to the invention, the filler used is chosen from crude oil-type feedstocks, or a residual fraction obtained from crude oils such as an atmospheric residue or a vacuum residue derived from conventional crude oil (API degree> 20). °), heavy crude (API degree between 10 and 20 °) or 3014 109 6 extra heavy crude (degree API <10 °). Said feedstock may also be a residual fraction resulting from any pre-treatment or conversion step, such as, for example, hydrocracking, hydrotreating, thermal cracking, hydroconversion of one of these crudes or one of these atmospheric residues, or one of these residues under vacuum. Said feed may also be a residual fraction resulting from the direct liquefaction of coal (atmospheric or vacuum residue) with or without hydrogen, with or without a catalyst, whatever the method used or a residual fraction resulting from the direct liquefaction of the biomass. lignocellulosic alone or mixed with charcoal and / or a residual petroleum fraction, with or without hydrogen, with or without a catalyst, whatever the method used. The boiling point of the feed according to the process of the invention is generally greater than 300 ° C, preferably greater than 400 ° C, more preferably greater than 450 ° C. The load can come from different geographical and geochemical origin (type I, II, IIS or III), of different degree of maturity and biodegradation. The filler according to the process of the invention may have a sulfur content of greater than 0.5% w / w (percentage expressed by mass of sulfur relative to the mass of filler), preferably greater than 1% w / w. more preferably greater than 2% w / w, even more preferably greater than 4% w / w; a metal content greater than 20 ppm (parts per million expressed as mass of metals relative to the mass of filler), preferably greater than 70 ppm, preferably greater than 100 ppm, more preferably greater than 200 ppm ; an asphalenes content C7 greater than 1% w / w (percentage expressed by weight of C 7 asphaltenes relative to the filler mass, measured according to the NF T60-115 method), preferably greater than 3% w / w, preferred greater than 8% w / w, more preferably greater than 14% w / w; a Conradson carbon content (also called CCR) higher than 5% m / m (percentage expressed by weight of CCR relative to the mass of filler), preferably greater than 7% m / m, preferably greater than 14% m / m, more preferably greater than 20% w / w. Advantageously, the C 7 asphaltenes content is between 1 and 40% and preferably between 2 and 30% by weight.
    [0009] The deasphalting steps of the process according to the invention can 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 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 mixer-settler, at a single level of introduction. According to the invention, the liquid / liquid extraction of the deasphalting steps 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. 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. The solvent mixture used in at least one of the selective deasphalting steps according to the invention is a mixture of at least one polar solvent and at least one apolar solvent.
    [0010] 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 most preferably between 1 and 80% volume. 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 in the process according to the invention may be chosen from aromatic pure or naphtho-aromatic solvents, polar solvents containing hetero-elements, or mixtures thereof. 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, for example, dimethylsulfoxide (DMSO), di-methylformamide (DMF), tetrahydrofuran (THF) . The polar solvent used in the process according to the invention can 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) or from petrochemical plants 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 in the process according to the invention is preferably a solvent composed of saturated hydrocarbon (s) comprising a number of carbon atoms 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 of petroleum fractions light naphtha type).
    [0011] Combined with the temperature and pressure conditions of the extraction according to the invention, the choice of the nature of the solvents, the choice of the combination of apolar / polar solvents in at least one of the stages of deasphalting allows access to at least two adjustment keys adjustable in series that allow access to a selectivity range hitherto inaccessible with conventional deasphalting.
    [0012] In the case of the present invention, the optimization of the two adjustment keys makes it possible to separate the feedstock into three fractions: a so-called ultimate asphalt fraction enriched with impurities and compounds that are refractory to recovery, a heavy deasphalted oil phase called heavy enriched DAO in structures non-refractory resins and less polar asphaltenes, and a light deasphalted oil phase called light DAO depleted in resins and asphaltenes, and generally in impurities (metals, heteroatoms). According to the process of the invention, 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 the first step of deasphalting or during the second deasphalting step. In a first embodiment, the method according to the invention is implemented in a so-called configuration of decreasing polarity, that is to say that the polarity of the solvent mixture used during the first deasphalting stage 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; the two fractions called heavy deasphalted oil and light deasphalted oil being extracted from the complete deasphalted oil called complete DAO during the second deasphalting step.
    [0013] In a second embodiment, the method according to the invention is implemented in a so-called configuration of increasing polarity, that is to say that the polarity of the solvent or solvent mixture used during the first deasphalting step s is lower 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 phase fraction called so-called heavy DAO. First Embodiment According to this embodiment, the method according to the invention comprises at least: a) a first deasphalting step comprising contacting the filler with a mixture of at least one polar solvent and with at least one apolar solvent, the proportions of said polar solvent and of said apolar solvent being adjusted so as to obtain at least one asphaltic phase fraction and a complete deasphalted oil phase fraction called the complete DAO and b) a second desaiphating step comprising the setting in contact with at least a part of the complete deasphalted oil phase called complete DAO resulting from step a) with either an apolar solvent or a mixture of at least one polar solvent and at least one apolar solvent, the proportions said polar solvent and said apolar solvent in the mixture being adjusted so as to obtain at least a fraction of light deasphalted oil and a dice oil fraction. In the case of heavy asphalting, the deasphalting steps a) and b) are carried out under the subcritical conditions of the apolar solvent or of the solvent mixture used. For a given charge, the greater the proportion and / or the intrinsic polarity of the polar solvent in the solvent mixture, the greater the deasphalted oil yield is important, some of the polar structures of the remaining charge solubilized and / or or dispersed in the DAO deasphalted oil phase. Decreasing the proportion of polar solvent in the mixture has the effect of increasing the amount of asphaltenic phase collected.
    [0014] The first step of deasphalting thus makes it possible to extract selectively and optimally and adapted to each load an ultimate so-called asphalt fraction, enriched with impurities and compounds that are refractory to recovery, while leaving solubilized in the matrix. or part of the polar structures of the less polar heavy resins and asphaltenes, which are not refractory for the downstream recovery stages. 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. The range of asphalt yield can range from 0.1 to 50% and more particularly from 0.1 to 25%. 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 complete deasphalted oil called complete DAO resulting from step a) with at least partly the solvent mixture according to the invention during the first extraction step is preferably subjected to at least one separation step in which the complete deasphalted oil called complete DAO is separated from the solvent mixture according to the invention or at least one separation stage in which the complete deasphalted oil called complete DAO is separated only from the apolar solvent.
    [0015] In a variant of the process, the complete deasphalted oil called complete DAO resulting from step a) with at least partly the solvent mixture according to the invention is subjected to two successive separation stages allowing the solvents to be separated 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. The separation steps are performed under supercritical or subcritical conditions. At the end of the separation step, the deasphalted oil DAO complete separated from the solvent mixture according to the invention is advantageously sent to at least one stripping column before being sent to the second deasphalting step. The mixture of polar and apolar solvents or the individually separated solvents are advantageously recycled. In a variant of the process only the apolar solvent is recycled in its respective booster. When the recycled solvents are in a mixture, the polar / polar proportion is checked on-line and readjusted as necessary by means of booster tanks individually containing the polar and apolar solvents. When the solvents are individually separated, said solvents are individually recycled to said respective booster tanks. 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%. preferably between 30 and 80% of the asphalt volume withdrawn. Asphalt extracted with at least a portion of the polar and apolar solvent mixture 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 mixture of solvents that can solubilize or disperse the asphalt. The fluxing agent may be a polar solvent chosen from monoaromatic hydrocarbons, preferably benzene, toluene or xylene; diaromatic or polyaromatic; aromatic naphthenocarbon 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. 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 carried out in such a way as to obtain a heavy deasphalted heavy diene phase called heavy DAO mainly comprising the family of resins and the less polar asphaltenes and a mild deasphalted oil phase called light DAO depleted in resins and asphaltenes, and generally in impurities (metals heteroatoms). The light deasphalted oil phase called light DAO mainly comprising the family of saturated hydrocarbons and the family of aromatic hydrocarbons.
    [0016] According to the invention, the separation selectivity and thus the composition of the heavy deasphalted oil fractions called heavy DAO and light deasphalted oil, so-called mild DAO, can be modified by adjusting the polarity of the solvent mixture by means of the nature and proportion of the solvents apolar / polar in the mixture or the nature of the apolar solvent.
    [0017] Second Embodiment In a second embodiment, the method according to the invention comprises at least a) a first deasphalting step comprising contacting the filler with either an apolar solvent or a mixture of at least one solvent polar and at least one apolar solvent, the proportions of said polar solvent and said apolar solvent of the mixture being adjusted so as to obtain at least a light deasphalted oil phase fraction and an effluent comprising an oil phase and an asphalt phase; and b) a second deasphalting step comprising bringing at least a portion of the effluent from step a) 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 one asphalt phase fraction and a heavy deasphalted oil phase fraction, said deasphalting steps being carried out under the subcritical conditions of the apolar solvent or the mixture of solvents used. 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 deasphalting. The first deasphalting step thus makes it possible to selectively extract from the feed a light deasphalted oil fraction called light DAO and an effluent comprising an oil phase and an asphalt phase. The first deasphalting step may be carried out both on an apolar solvent and on a solvent mixture according to the invention. The nature, proportion and / or polarity of the polar solvent in the solvent mixture is adapted, under the subcritical conditions of the solvent or solvent mixture used, so as to extract a light deasphalted oil fraction mainly comprising the hydrocarbon family. saturated and the family of aromatic hydrocarbons.
    [0018] The effluent comprising a heavy deasphalted oil phase called heavy DAO and an asphalt phase extracted from the first deasphalting step can contain at least partly the apolar solvent or the mixture of solvents according to the invention.
    [0019] Advantageously according to the invention, said effluent is subjected to at least one separation step in which it is separated from the apolar solvent or mixture of solvents according to the invention or at least one separation step in which said effluent is separated only from the solvent apolar contained in the solvent mixture.
    [0020] In a variant of the process according to the invention, said effluent may be subjected to at least two successive separation stages for separating the solvents individually in each separation step (as described in the first embodiment of the invention).
    [0021] The separation steps are performed under supercritical or subcritical conditions. At the end of the separation step, the effluent comprising the heavy deasphalted oil phase called heavy DAO and the asphalt phase separated from the solvent or the solvent mixture according to the invention can be sent to at least one stripping column before to be sent in the second stage of deasphalting. The mixture of polar and apolar solvents or the individually separated solvents are advantageously recycled. In a variant of the process only the apolar solvent is recycled in its respective booster. When the recycled solvents are in a mixture, the proportion of apolar and polar solvents is checked online and readjusted if necessary via booster tanks individually containing said polar and apolar solvents. When the solvents are individually separated, said solvents are individually recycled to said respective booster tanks.
    [0022] The second deasphalting step is carried out on at least a portion, preferably all of the effluent comprising a heavy deasphalted oil phase called heavy DAO and an asphalt phase 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 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, a so-called ultimate asphalt fraction, enriched with impurities and compounds that are refractory to recovery, while leaving solubilized in the matrix heavy deasphalted oil called heavy DAO all or part of the polar structures less polar resins and asphaltenes remaining generally contained in the asphalt fraction in the case of conventional deasphalting. The process according to the invention has the advantage of allowing a considerable improvement in the total yield of light and heavy deasphalted oils called light DAO 15 and heavy DAO over a range hitherto unexplored by conventional deasphalting. For a given feedstock whose total yield of light and heavy deasphalted oils obtained is capped at 75% (extraction with normal heptane in conventional deasphalting), the deasphalting used in the invention makes it possible under specific conditions to cover by adjustment of the The proportion of polar solvent and apolar solvent ranges from 75-99.9% of total yield of light and heavy deasphalted oils called light DAO and heavy DAO. The process according to the invention, by virtue of its separation selectivity and flexibility, makes it possible to obtain an asphalt fraction with an asphalt yield which is much lower than that obtainable by a conventional deasphalting process for a given feedstock. . Said asphalt yield is advantageously between 1 and 50%, preferably between 1 and 25%, more preferably between 1 and 20%. The present invention has the advantage of: i) an improvement in the properties of the treated feeds enabling easier and more efficient recovery while ii) limiting the yield of asphalt in a controlled manner. Due to two adjustable adjustment keys, the method according to the invention has the advantage of improved flexibility in terms of: the nature of the load: the invention is adapted to the treatment of a wider range loading range, - product recovery: depending on the product recovery path sought, the invention makes it possible to direct the selectivity of the separation towards obtaining heavy deasphalted oil fractions called heavy DAO and light deasphalted oil so-called Lightweight CAD optimized in terms of yield and / or chemical composition. The light deasphalted oil fraction, so-called mild DAO, can for example be upgraded as a hydrocracking feedstock, FCC feedstock (for increasing the recovery of gasoline for example) or any other refining treatment process. The heavy deasphalted oil fraction, called heavy DAO, may for example be recovered as a hydrotreatment feedstock, a hydroconversion feedstock or any other refining treatment process, but also by recycling certain refining processes. DESCRIPTION OF THE FIGURES According to one embodiment of the invention described in FIG. 1, the charge (1) previously heated by means of ovens and / or exchangers (not shown) is introduced into an extractor (13). such as an extraction column, preferably a mixer-settler. The mixture of polar solvent (3) and apolar solvent (2) is produced upstream in a mixer (10) fed by two additional containers each filled separately with polar solvent (tray 4) and apolar solvent (tray 5). ). The solvent mixture is for example introduced into the extractor (13) at two different levels. At least a part of the solvent mixture is sent via the pipe 11 in admixture with the feed introduced into the extractor (13) via the pipe 1. At least one other part of the solvent mixture is sent directly into the extractor ( 13) by the pipe 12 in which the extraction is carried out under conditions according to the invention defined above.
    [0023] According to Figure 1, the asphalt (16) also containing at least partly the solvent mixture according to the invention is withdrawn from the extractor (13) in the form of a liquid mixture or in the form of a dispersed solid. The mixture of asphalt, solvent according to the invention and fluxing can then be sent to an additional separation step not shown. The solvents or a part of the solvents or the separated fluxing agent can be reused in the process of the invention.
    [0024] At the end of the first extraction step, the complete deasphalted oil, called complete DAO, extracted in mixture with at least a part of the solvent mixture according to the invention, is sent through line 15 to the separator (17) in which the complete deasphalted oil is separated from the solvent mixture or only the apolar solvent contained in the solvent mixture (22). The process may comprise a second separator (see Figure 2) in the case where the solvents are separated individually. The solvent mixture or the solvents taken individually are advantageously separated in the separator under supercritical or subcritical conditions. The complete deasphalted oil is then preferably sent to a stripping column (19) via the pipe 18, before being recovered by the pipe 20. The solvent from the stripping column is sent to the line 23 by the pipe 21. The solvent from the separator (17) and the stripping column (21) is advantageously recycled internally from the process via the line (23) to the extractor (13). The composition of the polar and apolar solvent mixture is preferably checked in line by a densimeter or a refractometer (24). The proportions of polar solvent and of apolar solvent are, if necessary, readjusted with a supplement of polar solvent and apolar solvent respectively conveyed booster tanks 4 and 5 through lines 6 and 7. The mixture thus readjusted is advantageously homogenized in a static type mixer (25) before being fed into the mixer (10). When the solvents are individually separated, each solvent is recycled to its original tray.
    [0025] The complete deasphalted oil recovered by the pipe 20 is then sent to a second extractor (37) used under the conditions according to the invention and making it possible to separate a light deasphalted oil fraction called light DAO (38) and a deasphalted oil fraction. heavy called heavy CAD (39). The mixture of polar solvent (27) and apolar solvent (26) is produced upstream in a mixer (34) fed by two additional tanks each filled separately with polar solvent (tank 28) and apolar solvent (tray 29). . The polar and apolar solvents may be different from those used in the first extractor. In the case where the polar and apolar solvents used in the two extractors are identical, the mixture of solvents used in the second extractor can be fed by the two additional tanks 4 and 5. In the opposite case, the mixture of solvents used in the second extractor is fed by the two additional tanks 28 and 29. In another case, only the apolar solvent (26) can be implemented.
    [0026] The light deasphalted oil fraction called light DAO (38) extracted in mixture with at least partly the apolar solvent or the solvent mixture according to the invention is sent to a separator (40) in which the light deasphalted oil called light DAO ( 41) is separated in part or not from the solvent according to the invention (45). The process may comprise a second separator in the case where the solvents are separated individually as described above in the case of the solvent mixture. The solvent mixture or the solvents taken individually are advantageously separated in the separator under supercritical or subcritical conditions. The light deasphalted oil, called light DAO (41), is then preferably sent to a stripping column (42), before being recovered by line 43. The solvent from the stripping column is sent to line 46 via The duct 44. The heavy deasphalted oil fraction called heavy DAO (39) extracted in admixture with at least a portion of the apolar solvent or the solvent mixture according to the invention is sent to a separator (49) in which the heavy deasphalted oil said heavy DAO (50) is separated from the apolar solvent or the solvent according to the invention or only the apolar solvent contained in the solvent mixture (53). The solvent mixture or the individual solvents are advantageously separated in the separator under supercritical or subcritical conditions. The heavy deasphalted oil called heavy DAO (50) is then preferably sent to a stripping column (51), before being recovered by line 52. The solvent from the stripping column is sent to line 46 through 54. The solvents from the separators (40, 49), stripping columns (42, 51) are advantageously recycled internally from the process via line 46 to the extractor (37). In the case of solvent mixtures, the composition of the polar and apolar solvent mixture is preferably checked in line by a densimeter or a refractometer (47). The proportions of polar solvent and apolar solvent are, if necessary, readjusted with a supplement of polar solvent and non-polar solvent supplied with the auxiliary tanks 28 and 29 or the auxiliary tanks 4 and 5 depending on the solvents used in the process. second extractor are identical or different from those used in the first extractor. The mixture thus readjusted is advantageously homogenized in a static type mixer (48) before being sent into the mixer (34). When the solvents are individually separated, each solvent is recycled to its original tray.
    [0027] FIG. 2 depicts a diagram of the process according to the invention incorporating two separators (17) and (20) making it possible to separate the solvents individually and to recycle them individually in their respective tanks. Thus according to FIG. 2, the feedstock (1) previously heated by means of ovens and / or exchangers (not shown) is introduced into an extractor (13) such as an extraction column, preferably a mixer. -décanteur. The mixture of polar solvent (3) and apolar solvent (2) is produced upstream in a mixer (10) fed by two additional tanks each filled separately with polar solvent (tray 4) and apolar solvent (tray 5) . The solvent mixture is for example introduced into the extractor (13) at two different levels. At least a part of the solvent mixture is sent via line 11 in mixture with the feed introduced into the extractor (13) via line 1. At least one other part of the solvent mixture is sent directly into the extractor (13). ) by the pipe 12 in which the extraction is carried out under conditions according to the invention defined above. The asphalt (16) also containing at least partly the solvent mixture according to the invention is withdrawn from the extractor (13) in the form of a liquid mixture or in the form of a solid dispersed with the aid of a flowant sent by the pipe 14. The asphalt (16) can be subjected to the same treatment as that described for FIG. 1. At the end of the first extraction step, the complete deasphalted oil, called the complete DAO, is extracted mixing with at least a portion of the solvent mixture according to the invention is sent via line 15 to the separator (17) in which the complete deasphalted oil called complete DAO is preferably separated from the apolar solvent (19). The apolar solvent is advantageously recycled to the tank 5. The complete deasphalted oil, called the complete DAO in a mixture with the polar solvent, is then sent through line 18 to the second separator (20) in which the complete deasphalted oil, called the complete DAO, is separated from the polar solvent (21) sent to line 26. The solvents are advantageously separated in the separators under supercritical or subcritical conditions. The complete deasphalted oil, called complete DAO, is then preferably sent to a stripping column (23) via line 22, before being recovered by line 24. The solvent coming from the stripping column is sent to line 26. by the pipe 25. The polar solvent from the separator 20 and the stripping column 23 is recycled into the tank 4 by the line 26.
    [0028] The complete deasphalted oil called complete DAO recovered by the pipe 24 is then sent to a second extractor (38). The separated desulfated oil fractions are subjected to the same treatment as that described above in FIG. 1. Examples The feedstock selected for the examples is a vacuum residue from Athabasca in northern Canada. Its chemical characteristics are given in Table 1. Example 1 (not in accordance with the invention): Example 1 corresponds to the implementation of a conventional two-stage desalphating procedure as described in patent US2008149534. The selected feed was first deasphalted with the normal paraffinic solvent heptane, and then the collected DAO C7 deasphalted oil was deasphalted with normal propane to obtain the heavy DAO and mild DAO fractions. The properties as well as the extraction yields of each of the fractions are summarized in Table 1. The yield of C7 DAO is 75% for a C7 asphaltenes content (measured according to standard NFT60-115) of 14%. This shows that some of the resins were also extracted with C7 asphaltenes to form the asphalt. Table 1. Properties of the filler as well as yields and properties of fractions from conventional two-stage deasphalting performed with the nC7 solvents for the first step then nC3 for the second step. Initial 1st stage 2nd stage Residue Asphalt DAO DAO heavy DAO light Athabasca nC7 nC7 nC3 nC3 480 ° C + Reach extraction (% charge) 100 25 75 41 34 Analyzes d4, 15 --- 1.044 1.11 1.021 1.059 0.974 Sulfur% m / m 5.72 7.90 5.00 6.22 3.50 Nitrogen ppm 6200 7944 5625 8927 1581 Neither ppm 115 306 52 93 2 V ppm 317 823 150 268 5 CCR% m / m 20.5 45 12.4 20.5 2.5 3014 109 23 In this example, the yields as well as the grades of the various DAO are fixed by the nature of the paraffinic solvent used in each of the two steps. Example 2 (in accordance with the invention): The selected filler is subjected to the selective deasphalting in two stages according to the invention. The first extraction step is carried out with the combination of solvent nC3 (propane) / toluene (36/65; v / v) at a temperature of 130 ° C, the solvent / filler ratio is 5/1 (v / m) ). This first step made it possible to extract 50% of the C7 asphaltenes selectively in the asphalt fraction, while minimizing the asphalt yield (10% w / w) (see Table 2). The first stage makes it possible to recover the residue at 90% (yield of deasphalted DAO oil of 90%). The most polar structures of the feed are concentrated in the asphalt fraction. The deasphalted oil fraction DAO from the first deasphalting step is then separated from the solvent according to the invention before being subjected to the second extraction step. Cases Nos. 1 and 2 illustrate the flexibility of the process depending on the quality or yield envisaged of the separated fractions according to the required specifications of the units placed downstream. Case No. 1: Obtaining a Light Deasphalted Oil of Good Quality The second extraction step is carried out on the deasphalted oil fraction DAO 25 from the first deasphalting step with the same solvents as in the first step of the Example 2 propane (nC3) and toluene. In this case No. 1, the proportions of propane (nC3) and toluene are adjusted to meet the objective of obtaining a light deasphalted oil fraction called light DAO of good quality. The reaction is carried out with a mixture of nC3 / toluene solvent (99.5 / 0.5, v / v), a temperature of 120 ° C. and a solvent / DAO ratio of 5/1 (v / m). A heavy deasphalted oil fraction called heavy DAO and a light deasphalted oil fraction called light DAO are obtained with yields of 54% and 36% respectively (yields calculated with respect to the initial residue load). The overall results are summarized in Table 2. Table 2. Yield and properties of the fractions resulting from the two-stage selective deasphalting carried out in the case of obtaining a light DAO fraction of good quality. Initial 1st step 2nd step Residue Asphalt DAO DAO heavy light DAO Athabasca nC3 / toluene nC3 / toluene nC3 / toluene nC3 / toluene 480 ° C + (35/65; v / v) (35/65; v / v) (99.5 / 0.5 v / v) (99.5 / 0.5; v / v) Yield extraction (% load) 100 10 90 54 36 Analysis d4, 1.044 na 1.029 1.064 0.976 Sulfur A> m / m 5.72 9.32 5.32 6.49 3.56 Nitrogen ppm 6200 8900 5900 8431 2103 Ni ppm 115 511 71 116 3 V ppm 317 1460 190 313 6 CCR ° A> m / m 20.5> 50 16.3 25.4 2.6 * na: not analyzable.
    [0029] It can be seen that the qualities of the light deasphalted oil fraction obtained in Example 1 are very close to those obtained in the light deasphalted oil according to the invention, with the yield of light deasphalted oil according to the invention being identical.
    [0030] The heavy deasphalted oil fraction called heavy DAO obtained according to the invention is enriched with less polar resins and asphaltenes. This fraction has a pronounced aromatic character and concentrates the impurities (metals, heteroatoms) more than the light deasphalted oil fraction called light DAO. If we compare the properties of this fraction with those of the heavy deasphalted oil of Example 1, we note that they are more enriched in heavy structures but recoverable in contrast to Example 1 where these structures remain unvalued because contained in the asphalt fraction. The yield of heavy deasphalted oil, known as heavy recoverable product, is significantly improved (54% as against 41% in the case of the conventional SDA of Example 1).
    [0031] Case 2: obtaining with a better yield of the light deasphalted oil fraction called light DAO The second extraction step is performed on the DAO resulting from the first deasphalting step with the same solvents as in the first step of the example 2 propane (nC3) and toluene. In this case No. 2, the proportions of propane (nC3) and toluene are adjusted to meet the objective of obtaining a light deasphalted oil called light DAO with a high yield. The extraction conditions of the first step of the process remain unchanged. The reaction is carried out with a mixture of nC3 / toluene solvent (72/28 (v / v) The temperature is 125 ° C. and the solvent / DAO ratio is 5/1 (v / m) The results shown in Table 3 show that the light deasphalted oil fraction called light DAO is obtained with a yield of 60% instead of 36% in the case No. 1. On the other hand, this deasphalted oil now contains a part of the less polar resins. the heavy deasphalted oil called heavy DAO is reduced from 54 to 30% (relative to case No. 1) and it concentrates a majority of the less polar asphaltenes and the more polar resins.This heavy deasphalted oil is recoverable and sought after. The advantage of using a combination of apolar / polar solvent is to be able to adjust and optimize as desired and without yield limitation (unlike conventional deasphalting) the torque dement / quality of the fractions extracted from the deasphalting steps for a given load and for a given schema objective. There is no longer a constraint fixed by the nature of the solvents as in the case of conventional deasphalting, which gives the flexibility of the process. Table 3. Yield and Properties of the Fractions Resulting from the Two Stage Selective Deasphalting Achieved in the case of obtaining with a better yield of a light deasphalted oil fraction said light DAO. Initial 1st step 2nd DAO heavy nC3 / toluene (72/28; v / v) step Residue Asphalt DAO DAO light nC3 / toluene (72/28; v / v) Athabasca nC3 / toluene nC3 / toluene 480 ° C ~ (35 / 65; v / v) (35/65; v / v) Yield extraction (% load) 100 10 90 30 60 Analyzes d4, 15 --- 1.044 na 1.029 1.105 0.991 Sulfur% m / m 5.72 9.32 5.32 8.00 3.98 Nitrogen ppm 6200 8900 5900 7496 5102 Neither ppm 115 511 71 151 31 V ppm 317 1460 190 324 123 CCR% m / m 20.5> 50 16.3 33.9 7.5 * na: not analyzable.
    权利要求:
    Claims (15)
    [0001]
    REVENDICATIONS1. Process for the deasphalting of a heavy load by liquid / liquid extraction, said process comprising at least two deasphalting stages in series carried out on the feedstock to be separated into at least one asphalt fraction, at least one heavy deasphalted oil fraction said heavy DAO and at least one fraction of light deasphalted oil, called light DAO, at least one of said deasphalting steps being carried out using 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 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 solvent mixture used. 15
    [0002]
    2. Method according to claim 1 comprising at least: a) a first deasphalting step comprising contacting the filler 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 complete deasphalted oil phase fraction, so-called complete DAO; and b) a second deasphalting step comprising contacting at least a portion of the deasphalted oil phase from step a) 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 apolar solvent in the mixture being adjusted so as to obtain at least a light deasphalted oil fraction and a heavy deasphalted oil fraction, said deasphalting steps being carried out; under the subcritical conditions of the apolar solvent or solvent mixture used. 30
    [0003]
    3. Method according to claim 2, wherein the deasphalted oil phase from step a) is subjected beforehand to at least one separation step in which the deasphalted oil is separated from the solvent mixture or at least one separation step. wherein the complete deasphalted oil called complete DAO is separated only from the apolar solvent.
    [0004]
    4. The method of claim 2, wherein the deasphalted oil phase from step a) is first subjected to at least two successive separation steps in which the polar and apolar solvents are individually separated.
    [0005]
    5. Method according to one of claims 3 to 4 wherein the deasphalted oil separated solvents is sent into at least one stripping column before being sent in the second deasphalting step. 10
    [0006]
    6. Process according to claim 1 comprising at least: a) a first deasphalting step comprising contacting the filler 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 said apolar solvent of the mixture being adjusted so as to obtain at least a light deasphalted oil phase fraction and an effluent comprising an oil phase and an asphalt phase; and b) a second deasphalting step comprising contacting at least a portion of the effluent from step a) with 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 being adjusted so as to obtain at least one asphalt phase fraction and a heavy deasphalted oil phase fraction, said deasphalting stages being carried out under the subcritical conditions of the apolar solvent or of the mixture of solvents used. 25
    [0007]
    7. Method according to claim 6, wherein the effluent from step a) is previously subjected to at least one separation step in which the effluent is separated from the apolar solvent or the solvent mixture or at least one step in which said effluent is separated only from the apolar solvent contained in the solvent mixture.
    [0008]
    8. The method of claim 6 or 7, wherein the effluent from step a) is previously subjected to at least two separation steps in which the polar and apolar solvents are individually separated.
    [0009]
    9. Method according to one of claims 7 to 8 wherein the effluent separated solvents is sent into at least one stripping column before being sent to the second step of deasphalting.
    [0010]
    10. Method according to one of the preceding claims wherein the proportion of polar solvent in the mixture of polar solvent and apolar solvent in at least one of the deasphalting steps is between 0.1 and 99.9% volume.
    [0011]
    11. Method according to one of the preceding claims wherein the polar solvent used is selected from pure aromatic solvents or naphthoaromatic solvents, polar solvents comprising hetero-elements, or their mixture or cuts rich in aromatics such cuts from the FCC. (Fluid Catalytic Cracking) or from refinery petrochemical units, coal-derived sections, biomass or biomass / coal mixture.
    [0012]
    12. Method according to one of the preceding claims wherein the apolar solvent used comprises a solvent composed of saturated hydrocarbon (s) comprising a carbon number greater than or equal to 2, preferably between 2 and 9.
    [0013]
    13. Method according to one of the preceding claims wherein the filler is selected from the charges of petroleum origin type crude oil, atmospheric residue, vacuum residue type of so-called conventional crude oil, heavy crude 25 or extra crude oil. heavy, a residual fraction resulting from any pretreatment or conversion process such as hydrocracking, hydrotreatment, thermal cracking, hydroconversion of one of these crudes or one of these atmospheric residues or one of these residues under vacuum, a residual fraction resulting from the direct liquefaction of the lignocellulosic biomass alone or mixed with coal and / or a residual petroleum fraction.
    [0014]
    14. The method of claims 3 and 7 wherein when the recycled solvents are in a mixture, the apolar / polar proportion is checked in line and readjusted 1'aubesoin through extra bins individually containing the polar and apolar solvents.
    [0015]
    15. A process according to claims 3, 4, 7 and 8 wherein when the solvents are individually separated, said solvents are individually recycled to said respective booster tanks.
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    FR3014109B1|2017-04-07|
    EA201691103A1|2016-09-30|
    WO2015082312A1|2015-06-11|
    US20170029719A1|2017-02-02|
    CN105765035B|2018-05-18|
    CN105765035A|2016-07-13|
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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 |
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    2020-12-29| PLFP| Fee payment|Year of fee payment: 8 |
    2021-12-27| PLFP| Fee payment|Year of fee payment: 9 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1362028A|FR3014109B1|2013-12-03|2013-12-03|SELECTIVE CASCADE DISASPHALTING METHOD|FR1362028A| FR3014109B1|2013-12-03|2013-12-03|SELECTIVE CASCADE DISASPHALTING METHOD|
    US15/101,004| US20170029719A1|2013-12-03|2014-11-27|Process for selective cascade deasphalting|
    EP14808564.0A| EP3077482A1|2013-12-03|2014-11-27|Method of selective deasphalting in series|
    BR112016011247-4A| BR112016011247B1|2013-12-03|2014-11-27|cascading selective de-asphalting process|
    PCT/EP2014/075850| WO2015082312A1|2013-12-03|2014-11-27|Method of selective deasphalting in series|
    EA201691103A| EA201691103A1|2013-12-03|2014-11-27|CASCADE METHOD FOR SELECTIVE DEASPHALTING|
    CN201480066278.7A| CN105765035B|2013-12-03|2014-11-27|Selectivity cascade deasphalting method|
    TW103142018A| TW201538705A|2013-12-03|2014-12-03|Process for selective cascade deasphalting|
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