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    • 专利摘要:
    The invention relates to a method for treating a hydrocarbon feedstock that makes it possible to obtain a heavy hydrocarbon fraction with a low sulfur content, said process comprising the following steps: a) an optional hydrodemetallation step, b) a hydrotreatment step (c) a step of separating the effluent from step (b) of hydrotreating, (d) a step of catalytic cracking on a portion of the hydrotreated effluent, (e) a step of separating the effluent from step d) of catalytic cracking, f) a mixing step so as to obtain a fuel oil that can be used as marine fuel.
    公开号:FR3057876A1
    申请号:FR1660190
    申请日:2016-10-20
    公开日:2018-04-27
    发明作者:Wilfried Weiss；Pascal CHATRON-MICHAUD；Jerome Majcher
    申请人:IFP Energies Nouvelles IFPEN；
    IPC主号:
    专利说明:

    ® FRENCH REPUBLIC
    NATIONAL INSTITUTE OF INDUSTRIAL PROPERTY © Publication number:
    (to be used only for reproduction orders)
    ©) National registration number
    057 876
    60190
    COURBEVOIE
    ©) Int Cl 8 : C 10 G 69/04 (2017.01), C10G 45/02, 7/00, 11/00, C 10 L 1/04
    A1 PATENT APPLICATION
    ©) Date of filing: 20.10.16. © Applicant (s): IFP ENERGIES NOUVELLES Etablis- (30) Priority: public education - FR. ©) Inventor (s): WEISS WILFRIED, CHATRON- MICHAUD PASCAL and MAJCHER JEROME. (43) Date of public availability of the request: 04.27.18 Bulletin 18/17. (56) List of documents cited in the report preliminary research: Refer to end of present booklet @) References to other national documents ©) Holder (s): IFP ENERGIES NOUVELLES Etablisse- related: public. ©) Extension request (s): @) Agent (s): IFP ENERGIES NOUVELLES.
    FR 3 057 876 - A1
    104 / CONVERSION PROCESS COMPRISING HYDROTREATMENT IN A FIXED BED, A SEPARATION OF A RESIDUE HYDROTRAITATED FRACTION, A CATALYTIC CRACKING STEP FOR THE PRODUCTION OF MARINE FUELS.
    The invention relates to a process for treating a hydrocarbon feedstock making it possible to obtain a heavy hydrocarbon fraction with a low sulfur content, said process comprising the following steps: a) an optional step of hydrodemetallization, b) a step d hydrotreatment, c) a step of separating the effluent from step b) of hydrotreatment, d) a catalytic cracking step on part of the hydrotreated effluent, e) a step of separating the effluent from step d) of catalytic cracking, f) a mixing step so as to obtain an oil usable as marine fuel.
    i
    Context of the invention
    The present invention relates to the refining and conversion of heavy fractions of hydrocarbons containing, inter alia, sulfur impurities.
    It relates more particularly to a process for converting heavy petroleum charges of the atmospheric residue and / or vacuum residue type for the production of heavy fractions usable as fuel oil bases, in particular as bunker oil bases, with a low sediment content.
    The method according to the invention also makes it possible to produce atmospheric distillates (naphtha, kerosene and diesel), vacuum distillates and light gases (C1 to C4).
    Among the processes for converting heavy petroleum charges of the atmospheric residue and / or vacuum residue type, catalytic cracking of residues is today a key process in modern refineries for producing in particular olefins and distillates. Due to the impurity content of certain fillers of the atmospheric residue and / or vacuum residue type, residue hydrotreatment units are often installed so as to reduce the content of impurities, in particular sulfur, metals and Conradson carbon. (CCR). The effluent from the hydrotreatment stage is generally subjected to a separation stage allowing the elimination of gases and atmospheric distillates. The atmospheric residue obtained in the separation step is sent to catalytic cracking.
    Catalytic cracking is also a process for treating lighter fillers, in particular vacuum distillates which can also undergo hydrotreating or mild hydrocracking upstream of the catalytic cracking step.
    Catalytic cracking is known by the acronym FCC (abbreviation of the English terminology Fluid Catalytic Cracking) and RFCC (abbreviation of the English terminology Resid Fluid Catalytic Cracking).
    The FCC and the RFCC are processes for converting vacuum distillates and / or distillation residues which make it possible in particular to obtain the products in particular dry and acid gases (essentially: H2, H2S, C1, C2), liquefied petroleum containing C3-C4 molecules, gasolines containing at least 80% of compounds with a boiling temperature between 30 and 220 ° C (standard cutting point), sometimes separated into light essence known as LCN (Light Cracked Naphtha) and in heavy essence known as HCN (Heavy Cracked Naphtha).
    a light distillate known as LCO (Light Cycle Oil) containing at least 80% of compounds having a boiling temperature of between 220 ° C. and 360 ° C. a heavy distillate known as HCO (Heavy Cycle Oil) containing at least 80% of compounds having a boiling temperature between 360 ° C to 440 ° C possibly, a residue or slurry which is generally purified from the catalyst particles which it contains to obtain a clarified oil (CO) or a decanted oil (DO). This residue contains at least 80% of compounds having a boiling point above 440 ° C.
    It also happens that the term HCO or slurry designates a mixture of “HCO” and “slurry” cuts which may not be separated in the process, this mixture then contains at least 80% of compounds having a boiling point above 360 ° C. In the following text, the dull Heavy Cycle Oil or HCO is used to define any cut resulting from a catalytic cracking step (FCC or RFCC) and containing at least 80% of compounds having a boiling point above 360 °. vs. It is understood that this section can undergo a step of separation of the catalyst particles. The quality requirements for marine fuels are described in the ISO 8217 standard. The sulfur specification now relates to SO X emissions (Annex VI of the MARPOL convention of the International Maritime Organization). It results in a recommendation for sulfur content less than or equal to 0.5% by weight outside of the Sulfur Emission Control Zones (ZCES) for 2020-2025, and lower or equal to 0.1% by weight in the ZCES. According to Annex VI of the MARPOL convention, a ship can therefore use sulfur fuel oil as soon as the ship is equipped with a smoke treatment system making it possible to reduce sulfur oxide emissions. In the absence of smoke treatment on the ship, it is therefore necessary to use low sulfur fuels made from low sulfur bases, generally at least partly from the hydrodesulfurization process. .
    ISO8217 also describes other specifications which vary according to the fuel grade and the type of fuel, the standard distinguishing two families: distillates for the navy (the least viscous) and residual fuels for the navy.
    Fuels used in maritime transport can generally include atmospheric distillates, vacuum distillates, atmospheric residues and vacuum residues from direct distillation or from refining process, in particular hydrotreatment and conversion processes, these cuts can be used alone or mixed in variable proportions so as to comply with the specifications of standard ISO8217.
    For residual type fuels, the characteristic reflecting the quality of combustion is measured by the CCAI (abbreviation for English terminology Calculated Carbon Aromaticity Index). The correlation between the aromatic nature of a fuel and the ignition delay is known to the skilled person. The formula for calculating the aromaticity index, called hereinafter in the CCAI description, is described in the latest revision of ISO8217. This formula notably involves the density and viscosity of the fuel. For “RMG” type fuel grades (such as RMG 380) for the navy, ISO8217 recommends a maximum CCAI of 870.
    Description of the invention
    In the context described above, the applicant has developed a new process incorporating a step for separating the effluent from a step for hydrotreating residues so as not to crack the residual fraction (s) in full. (s) of vacuum residue or hydrotreated atmospheric residue type (s) for use as an oil base, in particular a bunker base with a low sulfur content.
    Surprisingly, it has been demonstrated that the submission of only part of the heavy fraction separated after hydrotreatment in stage d) of catalytic cracking and the sending of the complement in stage f) of mixing makes it possible to '' adjust the characteristics of the fuel oil produced, in particular its sulfur content and its CCAI. More particularly, the invention shows that the control of the flow of residual fractions of the vacuum residue or hydrotreated atmospheric residue type which is not or is not subjected to catalytic cracking, as well as the step of mixing with part of the cuts resulting from catalytic cracking, makes it possible to optimize the specifications of bunker fuel oil, in particular the sulfur content, the viscosity, the density and the CCAI.
    There is an economic advantage in not seeking a higher quality to obtain a particular grade of fuel oil, in particular the grades of marine fuels of the residual type which are less expensive than the grades of the distillary type. It is therefore necessary to get as close as possible to the specification limit values as soon as the production cost of the mixture decreases while maximizing the proportion of the least expensive bases, in particular the residual fractions of the atmospheric residue or vacuum residue type, but also cracked bases like LCO or
    HCO from FCC or RFCC.
    Conversely, there may also be an interest in optimizing the specifications in order to obtain a product of superior or particular quality which can be valued more than a standard product. Mastering the CCAI requires controlling in the residual fuel oil the proportion of aromatic cuts having poor combustion properties in a diesel engine compared to cuts richer in paraffins such as atmospheric residues or vacuum residues, especially hydrotreated residues, which have better combustion properties in a diesel engine. The control of these proportions also has an influence on the flow rate and the quality of the charge of the catalytic cracking stage and therefore of the yield and of the quality, in particular of the sulfur content, of the LCO and HCO cuts which can be integrated into fuel oil. The rate of hydrodesulfurization in the hydrotreatment stage is also a possible adjustment variable.
    Reducing the sulfur content of marine fuels requires in principle new installations in new refineries or in existing refineries. The present invention may be a new unit, but it has the advantage of being able to reuse at least in part existing units, in particular hydrotreating and / or catalytic cracking. Thus, an existing sequence of a residue hydrotreating unit and a residue catalytic cracking unit can be remodeled by modifying the step of separating the effluent from the residue hydrotreating unit. Similarly, a residue hydrotreatment unit followed by a separation unit could be installed upstream of an existing catalytic cracking unit, in particular a catalytic cracking unit initially intended to treat distillates under vacuum, this without remodeling or with a light remodeling.
    One of the objectives of the present invention is to provide a process coupling the conversion and desulphurization of heavy petroleum charges for the production of fuel oils with an optimized CCAI aromaticity index and a low sulfur content.
    Another objective of the present invention is to produce jointly, by the same process, atmospheric distillates (naphtha, kerosene, diesel), vacuum distillates and / or light gases (in C1 to C4). Naphtha and diesel bases can be upgraded in refineries for the production of automotive and aviation fuels, such as super fuels, jet fuels and diesel.
    Summary of the invention
    The invention relates to a process for converting a heavy hydrocarbon feedstock containing at least one hydrocarbon fraction having a sulfur content of at least 0.1% by weight, a metal content of at least 10 ppm, a temperature initial boiling point of at least 340 ° C, and a final boiling point of at least 600 ° C, the process comprising the following steps:
    a) an optional step of hydrodemetallization in permutable reactors in which the hydrocarbon feedstock is brought into contact with hydrogen on a hydrodemetallization catalyst,
    b) a hydrotreatment step in a fixed bed of the effluent from step a) of hydrodemetallization when the latter is used or of the hydrocarbon feedstock in contact with hydrogen and a hydrotreatment catalyst ,
    c) a step of separating the effluent from step b) of hydrotreatment comprising a gas-liquid separation followed by atmospheric distillation allowing at least one cut of the atmospheric residue type to be obtained, said atmospheric distillation possibly being followed by vacuum distillation allowing a vacuum distillate type cut and a vacuum residue type cut to be obtained,
    d) a step of catalytic cracking of a part of the atmospheric residue type cut resulting from step c) and / or a part of the vacuum residue cut resulting from step c), optionally in admixture with at least one part of the vacuum distillate type cut from separation step c),
    e) a step for separating the effluent from step d) of catalytic cracking, making it possible to obtain at least one light diesel fraction with a standard boiling range of between 220 and 360 ° C. called LCO and at least one heavy cutting with a boiling point higher than 360 ° C called HCO,
    f) a step of mixing a part of the atmospheric residue type cut from step c) and / or a part of the vacuum residue cut from step c) of separation with at least one part diesel cuts with standard boiling range between 220 and 360 ° C called LCO and loirde with a boiling point greater than 360 ° C called HCO from step e) of separation so as to obtain a fuel oil usable as marine fuel with a sulfur content less than or equal to 0.5% by weight and a CCAI aromaticity index calculated according to ISO8217 standard less than 870.
    Separation step c) may include vacuum distillation after atmospheric distillation and at least a portion of the atmospheric residue is sent to vacuum distillation to produce a vacuum distillate and a vacuum residue.
    According to one embodiment, the vacuum distillate cut obtained at the end of the separation step c) is not sent entirely to step d) of catalytic cracking and the process allows the joint production of fuel oil and distillates atmospheric, vacuum distilled, and light gases (C1 to C4).
    The hydrodemetallization stage a) can be carried out at a temperature between 300 ° C and 500 ° C, under an absolute pressure between 5 MPa and
    35 MPa, with a space velocity of the hydrocarbon charge WH in a range from 0.1 h ' 1 to 5 h' 1 and an amount of hydrogen mixed with the charge between 100 and 5000 normal cubic meters (Nm3) per cubic meter (m3) of liquid charge.
    The hydrotreatment stage can be carried out at a temperature between 300 ° C and 500 ° C, and under an absolute pressure between 5 MPa and 35 MPa, with a space velocity of the hydrocarbon feed, commonly called WH, in a range from 0.1 h ' 1 to 5 h' 1 , with a quantity of hydrogen mixed with the charge between 100 and 5000 normal cubic meters (Nm3) per cubic meter (m3) of liquid charge.
    The catalytic cracking step can be implemented in at least one reactor operating in upward or downward flow containing a catalytic cracking catalyst, operating with a catalyst to charge ratio of between 4 and 15, and with an outlet temperature of or reactor (s) between 450 and 600 ° C.
    The fraction resulting from the separation step c) sent directly as the fuel oil base to the mixing step f) can consist only of atmospheric residue and represent between 40 and 95% by mass of the fuel oil obtained.
    The fraction resulting from the separation step c) sent directly as the fuel oil base to the mixing step f) can consist only of vacuum residue and represent between 40 and 90% by mass of the fuel oil obtained.
    The fraction resulting from the separation step c) sent directly as the fuel oil base to the mixing step f) can consist of atmospheric residue and vacuum residue and represent between 40 and 95% by mass of the fuel oil obtained.
    At least one other fuel oil base chosen from a kerosene cut or a gas oil cut obtained from step c) of separation or a fluxing base external to the process chosen from a kerosene, a diesel fuel can be added to the mixing step f). , a vacuum distillate from direct distillation or from a conversion process.
    In this case, the fluxing base fraction is less than 10% by mass of the fuel oil obtained, preferably less than 5% by mass of the fuel oil obtained.
    The hydrocarbon feedstock can be chosen from atmospheric residues, vacuum residues from direct distillation, crude oils, headless crude oils, deasphalting resins, asphalt or deasphalting pitches, residues from conversion processes, aromatic extracts from base production chains for lubricants, oil sands or their derivatives, oil shales or their derivatives, bedrock oils or their derivatives, taken alone or as a mixture, preferably the hydrocarbon feedstock is chosen from atmospheric residues or vacuum residues, or mixtures of these residues.
    The hydrotreatment stage b) can comprise a first hydrodemetallization (HDM) stage b1) carried out in one or more hydrodemetallization zones in fixed beds in which the effluent from stage a), or the feed and hydrogen in the absence of step a), are brought into contact on a hydrodemetallization catalyst, and a second second step b2) subsequent hydrodesulfurization (HDS) carried out in one or more hydrodesulfurization zones in fixed beds in which the effluent from the first hydrodemetallization step b1) is brought into contact with a hydrodesulfurization catalyst.
    The hydrotreatment stage b) can comprise a first hydrodemetallization (HDM) stage b1) carried out in one or more hydrodemetallization zones in fixed beds in which the effluent from stage a), or the feed and hydrogen in the absence of step a), are brought into contact on a hydrodemetallization catalyst, a second step b2) subsequent transition carried out in one or more transition zones in fixed beds in which the effluent from the first step b1) of hydrodemetallization is brought into contact with a transition catalyst, and a third step b3) of subsequent hydrodesulfurization (HDS) carried out in one or more hydrodesulfurization zones in fixed beds, in which the effluent from the second transition step b2) is brought into contact with a hydrodesulfurization catalyst.
    The fuel oil obtained may have a sulfur content of less than or equal to 0.1% by weight.
    The fuel oil obtained may have a density at 15 ° C less than 991 kg / m3 and a viscosity at 50 ° C less than 380 cSt.
    List of Figures
    Figure 1: Figure 1 describes, without limitation, a scheme for implementing the method according to the invention
    Description of Figure 1
    Figure 1 describes a diagram of implementation of the invention without limiting its scope.
    The hydrocarbon feedstock (1) and hydrogen (2) are brought into contact in an optional step a) of hydrodemetallization in permutable reactors, in which the hydrogen (2) can be introduced at the inlet of the first catalytic bed and between two beds from step a).
    ίο
    The effluent (5) from step a) of hydrodemetallization in permutable reactors is sent in a hydrotreatment step in a fixed bed b), in which additional hydrogen (4) can be introduced at the inlet of the first catalytic bed and between two beds of step b).
    In the absence of step a), the hydrocarbon feedstock (3) and the hydrogen (4) are introduced directly into step b) of hydrotreatment.
    An additional charge, called co-charge (6) can optionally be introduced directly at the input of step a) of hydrodemetallization and / or at the input of step b) of hydrotreatment via line (3).
    The effluent (7) from step b) of hydrotreating in a fixed bed is sent to a step
    c) separation, comprising one or more separators (SEP) operating at different temperature and pressure levels making it possible to obtain at least one liquid fraction (25) and one gas fraction (23).
    The gas fraction (23) containing hydrogen, ammonia, hydrogen sulfide of light hydrocarbons comprising 1 to 4 carbon atoms can be treated so as to recover a gas rich in hydrogen and thus recycle it upstream of the hydrodemetallization stage a) and / or of hydrotreatment b).
    The liquid fraction (25) is here subjected to atmospheric distillation (ADU) in order to obtain at least atmospheric distillates of the naphtha, kerosene and gas oil type (24) and a cut of the atmospheric residue type (9). The atmospheric residue type cut (9) can be sent via line (26) to vacuum distillation (VDU) to obtain at least one vacuum distillate type cut (8) and one residue type cut (10) empty.
    The fraction (8) of vacuum distillate type is sent separately or as a mixture with part of the cup (9) of atmospheric residue type via the line (11), or as a mixture with part of the cup (10) residue type under vacuum via line (13) to a step d) of catalytic cracking. An additional charge known as co-charge (15) can optionally be sent to step d).
    A part of the section (9) of the atmospheric residue type via the line (12) and / or a part of the section (10) of the vacuum residue type via the line (14) is or is not subject (s) ) in step d) of catalytic cracking and are sent directly to the mixing step f).
    The effluent (16) from step d) of catalytic cracking is sent to a separation step e) making it possible to obtain at least one light distillate of LCO type (19) and at least one heavy distillate of HCO type ( 20). A cut resulting from step e) of separation, preferably a part of the light distillate and / or of the heavy distillate, can be recycled at the entry of step a) of hydrodemetallization via the line (18) and / or in entry of step b) of hydrotreatment via line (17).
    At least part of the light distillate of the LCO type (19) and / or at least part of the heavy distillate of the HCO type (20) from step e) of separation, optionally supplemented by a number of fluxing bases external to the process ( 22) are mixed during a step f) of mixing with vacuum residue (14) and / or atmospheric residue (12) from step c) of separation, in order to obtain at least one marine fuel (21).
    Detailed description of the invention
    Charges
    The feedstock treated in the process according to the invention is advantageously a hydrocarbon feedstock having an initial boiling temperature of at least 340 ° C and a final boiling temperature of at least 600 ° C.
    The hydrocarbon feedstock according to the invention can be chosen from atmospheric residues, vacuum residues from direct distillation, crude oils, headless crude oils, deasphalting resins, deasphalting asphalts or pitches, residues from processes conversion, aromatic extracts from base production chains for lubricants, oil sands or their derivatives, oil shales or their derivatives, mother rock oils or their derivatives, taken alone or as a mixture. In the present invention, the charges which are treated are preferably atmospheric residues or residues under vacuum, or mixtures of these residues.
    The hydrocarbon feedstock treated in the process may contain, among other things, sulfur impurities. The sulfur content may be at least 0.1% by weight, preferably at least 0.5% by weight, preferably at least 1% by weight, more preferably at least 2% by weight .
    The hydrocarbon feedstock treated in the process may contain, among other things, metallic impurities, at contents greater than 10 ppm, in particular nickel and vanadium. The sum of the nickel and vanadium contents is generally at least 10 ppm, preferably at least 50 ppm.
    These fillers are preferably used as such.
    Alternatively, they can be diluted by an additional charge known as a co-charge. This co-charge can be a hydrocarbon fraction or a mixture of hydrocarbon fractions, which can preferably be chosen from products resulting from a catalytic cracking process in a fluid bed (FCC or "Fluid Catalytic Cracking" according to English terminology). ), a light cut (LCO or "light cycle oil" according to the English terminology), a heavy cut (HCO or "heavy cycle oil >> according to the English terminology), a decanted oil, an FCC residue , a diesel fraction, in particular a fraction obtained by atmospheric distillation or under vacuum, such as for example vacuum diesel, or can also come from another refining process such as coking or visbreaking.
    It can also be a deasphalted oil (DAO or Deasphalted Oil according to Anglo-Saxon terminology).
    The co-charge can also advantageously be one or more cuts resulting from the liquefaction process of coal or biomass, aromatic extracts, or any other hydrocarbon cuts, or else non-petroleum fillers such as pyrolysis oil.
    In the case where one or more additional charges, known as co-charges, are introduced into the process, at any point in the process, the heavy hydrocarbon charge according to the invention nevertheless represents the majority of the charge entering the process according to the invention, preferably at least 50%, very preferably 70%, more preferably at least 80%, and even more preferably at least 90% by weight of the total hydrocarbon charge treated by the process according to the invention.
    In certain cases it is possible to introduce the co-charge downstream of the first bed or of the following, for example at the entry of the hydrodemetallization section in a fixed bed, or even at the entry of the hydrotreatment section in a fixed bed, or still at the entrance to the catalytic cracking section.
    The process according to the invention makes it possible to obtain conversion products, in particular distillates formed during step b) of hydrotreatment and / or d) of catalytic cracking, which can, after separation, be sent to another refining process. or be incorporated into fuel pools. The method also makes it possible to obtain an atmospheric residue type cut and / or a vacuum residue type cut resulting from separation step c), usable as base (s) of fuel oil with low content sulfur during step f) of mixing.
    Step a) optional hydrodemetallization in permutable guard reactors
    During the optional step a) of hydrodemetallization, the charge and hydrogen are brought into contact on a hydrodemetallization catalyst loaded in at least two permutable reactors, under hydrodemetallization conditions. This optional step a) is preferably carried out when the charge contains more than 50 ppm, or even more than 100 ppm of metals and / or when the charge comprises impurities capable of inducing too rapid clogging of the catalytic bed, such as iron or calcium derivatives for example. The aim is to reduce the content of impurities and thus protect from deactivation and clogging the hydrotreatment stage downstream, hence the concept of guard reactors. These hydrodemetallization guard reactors are implemented as permutable reactors ("PRS" technology, for "Permutable Reactor System" according to English terminology) as described in patent FR2681871.
    These swappable reactors are generally fixed beds located upstream of the hydrotreating section in a fixed bed and equipped with lines and valves so as to be swapped between them, that is to say for a system with two swappable reactors Ra and Rb, Ra can be in front of Rb and vice versa. Each Ra, Rb reactor can be taken offline to change the catalyst without shutting down the rest of the unit. This change of catalyst (rinsing, unloading, recharging, sulfurization then restarting) is generally allowed by a conditioning section (set of equipment outside the main high pressure loop). The changeover for catalyst change occurs when the catalyst is no longer sufficiently active (metal poisoning and coking) and / or when the clogging reaches an excessive pressure drop.
    Alternatively, there may be more than 2 swappable reactors in the hydrodemetallization section in swappable reactors.
    During step a) of hydrodemetallization, hydrodemetallization reactions (commonly called HDM) occur, but also hydrodesulfurization reactions (commonly called HDS), hydrodenitrogenation reactions (commonly called HDN) hydrogenation, hydrodeoxygenation, hydrodearomatization, hydroisomerization, hydrodealkylation, hydrocracking, hydrodeasphalting and carbon reduction reactions. Step a) is called hydrodemetallization since it removes the majority of metals from the charge.
    Step a) of hydrodemetallization in permutable reactors according to the invention can advantageously be carried out at a temperature between 300 ° C and 500 ° C, preferably between 350 ° C and 430 ° C, and under absolute pressure included between 5 MPa and 35 MPa, preferably between 11 MPa and 26 MPa, preferably between 14 MPa and 20 MPa. The temperature is usually adjusted according to the desired level of hydrodemetallization and the duration of the targeted treatment. Most often, the space velocity of the hydrocarbon feedstock, commonly called WH, which is defined as the volumetric flow rate of the feedstock divided by the total volume of the catalyst, can be comprised in a range going from 0.1 h ′ 1 at 5 h ' 1 , preferably from 0.15 h' 1 to 3 h ' 1 , and more preferably from 0.2 h' 1 to 2 h ' 1 .
    The quantity of hydrogen mixed with the feed can be between 100 and 5000 normal cubic meters (Nm3) per cubic meter (m3) of liquid feed, preferably between 200 Nm3 / m3 and 2000 Nm3 / m3, and more preferably between 300 Nm3 / m3 and 1000 Nm3 / m3. Step a) of hydrodemetallization in permutable reactors can be carried out industrially in at least two reactors in a fixed bed and preferably with a downdraft of liquid.
    The hydrodemetallization catalysts used are preferably known catalysts. They may be granular catalysts comprising, on a support, at least one metal or metal compound having a hydro-dehydrogenating function. These catalysts can advantageously be catalysts comprising at least one metal from group VIII, generally chosen from the group consisting of nickel and cobalt, and / or at least one metal from group VIB, preferably molybdenum and / or tungsten. It is possible, for example, to use a catalyst comprising from 0.5% to 10% by weight of nickel, preferably from 1% to 5% by weight of nickel (expressed as nickel oxide NiO), and from 1% to 30% by weight. weight of molybdenum, preferably from 3% to 20% by weight of molybdenum (expressed as molybdenum oxide Mo03) on an inorganic support. This support can for example be chosen from the group consisting of alumina, silica, silica-aluminas, magnesia, clays and mixtures of at least two of these minerals. Advantageously, this support can contain other doping compounds, in particular oxides chosen from the group consisting of boron oxide, zirconia, cerine, titanium oxide, phosphoric anhydride and a mixture of these oxides. Most often an alumina support is used and very often an alumina support doped with phosphorus and possibly boron. When phosphoric anhydride P2O5 is present, its concentration is less than 10% by weight. When boron trioxide B2O5 is present, its concentration is less than 10% by weight. The alumina used can be a y (gamma) or η (eta) alumina. This catalyst is most often in the form of extrudates. The total content of metal oxides from groups VIB and VIII can be from 5% to 40% by weight, preferably from 5% to 30% by weight, and the weight ratio expressed as metal oxide between metal (or metals) from group VIB on metal (or metals) of group VIII is generally between 20 and 1, and most often between 10 and 2.
    Catalysts which can be used in step a) of hydrodemetallization in permutable reactors are for example indicated in patent documents EP 0113297,
    EP 0113284, US 5221656, US 5827421, US 7119045, US 5622616 and US 5089463.
    Step b) hydrotreating in a fixed bed
    The effluent from the optional step a) of hydrodemetallization is introduced, optionally with hydrogen, in a step b) of hydrotreating in a fixed bed to be brought into contact with at least one hydrotreatment catalyst. In the absence of the optional step a) of hydrodemetallization in permutable guard reactors, the feedstock and the hydrogen are introduced directly into step b) of hydrotreatment in a fixed bed to be brought into contact on at least one hydrotreatment catalyst This or these hydrotreatment catalyst (s) are used in at least one reactor in a fixed bed and preferably with a downdraft of liquid.
    Hydrotreatment, commonly called HDT, is understood to mean catalytic treatments with the addition of hydrogen which makes it possible to refine, that is to say substantially reduce the content of metals, sulfur and other impurities, the hydrocarbon charges, while improving the ratio hydrogen on carbon of the charge and transforming the charge more or less partially into lighter cuts.
    Hydrotreatment includes hydrodesulfurization reactions (commonly called HDS), hydrodesulfurization reactions (commonly called HDN) and hydrodemetallization reactions (commonly called HDM), accompanied by hydrogenation reactions, hydrodeoxygenation, d hydrodearomatization, hydroisomerization, hydrodealkylation, hydrocracking, hydrodeasphalting and carbon reduction Conradson.
    According to a preferred variant, step b) of hydrotreatment comprises a first step b1) of hydrodemetallization (HDM) carried out in one or more hydrodemetallization zones in fixed beds and a second step b2) of subsequent hydrodesulfurization (HDS) carried out in one or more hydrodesulfurization zones in fixed beds. During said first hydrodemetallization step b1), the effluent from step a), or the feedstock and hydrogen in the absence of step a), are brought into contact with a catalyst for hydrodemetallization, under hydrodemetallization conditions known to a person skilled in the art, in particular as described in step a), then during said second hydrodesulfurization step b2), the effluent from the first step b1) d hydrodemetallization is brought into contact with a hydrodesulfurization catalyst, under hydrodesulfurization conditions. This process, known under the name of HYVAHL-F ™, is for example described in the patent US 5417846.
    Those skilled in the art can easily understand that, in step b1) of hydrodemetallization, hydrodemetallization reactions are carried out, but also in parallel also part of the other hydrotreatment reactions, and in particular of hydrodesulfurization and hydrocracking. Similarly, in step b2) of hydrodesulfurization, hydrodesulfurization reactions are carried out, but in parallel also a part of the other hydrotreatment reactions and in particular of hydrodemetallization and hydrocracking.
    Those skilled in the art sometimes define a transition zone in which all types of hydrotreatment reaction occur. According to another variant, step b) of hydrotreatment comprises a first step b1) of hydrodemetallization (HDM) carried out in one or more hydrodemetallization zones in fixed beds, a second transition step b2) subsequent carried out in one or more several transition zones in fixed beds, and a third step b3) subsequent hydrodesulfurization (HDS) carried out in one or more hydrodesulfurization zones in fixed beds. During said first hydrodemetallization step b1), the effluent from step a), or the feedstock and hydrogen in the absence of step a), are brought into contact with a catalyst for hydrodemetallization, under hydrodemetallization conditions, then during said second transition step b2), the effluent from the first hydrodemetallization step b1) is brought into contact with a transition catalyst, under transition conditions, then during said third hydrodesulfurization step b3), the effluent from the second transition step b2) is brought into contact with a hydrodesulfurization catalyst, under hydrodesulfurization conditions.
    Step b1) of hydrodemetallization according to the above variants is particularly necessary in the absence of step a) of hydrodemetallization in permutable guard reactors so as to treat the impurities and protect the downstream catalysts. The need for a step b1) of hydrodemetallization according to the above variants in addition to step a) of hydrodemetallization in permutable guard reactors is also justified when the hydrodemetallization carried out during step a) is not sufficient to protect the catalysts of step b), in particular the hydrodesulfurization catalysts.
    The hydrotreatment stage b) according to the invention is carried out under hydrotreatment conditions. It can advantageously be implemented at a temperature between 300 ° C and 500 ° C, preferably between 350 ° C and 430 ° C and under an absolute pressure between 5 MPa and 35 MPa, preferably between 11 MPa and 26 MPa, preferably between 14 MPa and 20 MPa. The temperature is usually adjusted by a person skilled in the art as a function of the desired level of hydrotreatment and of the nature (hydrodemetallization, hydrodesulfurization, etc.) and duration of the targeted treatment. Most often, the space velocity of the hydrocarbon feedstock, commonly called WH, which is defined as the volumetric flow rate of the feedstock divided by the total volume of the catalyst, can be comprised in a range going from 0.1 h ′ 1 at 5 h ' 1 , preferably from 0.1 h' 1 to 2 h ' 1 , and more preferably from 0.1 h' 1 to 1 h ' 1 . The quantity of hydrogen mixed with the feed can be between 100 and 5000 normal cubic meters (Nm3) per cubic meter (m3) of liquid feed, preferably between 200 Nm3 / m3 and 2000 Nm3 / m3, and more preferably between 300 Nm3 / m3 and 1500 Nm3 / m3. The hydrotreatment stage b) can be carried out industrially in one or more reactors with a downdraft of liquid.
    The hydrotreatment catalysts used are preferably known catalysts. They may be granular catalysts comprising, on a support, at least one metal or metal compound having a hydro-dehydrogenating function. These catalysts can advantageously be catalysts comprising at least one metal from group VIII, generally chosen from the group consisting of nickel and cobalt, and / or at least one metal from group VIB, preferably molybdenum and / or tungsten. It is possible, for example, to use a catalyst comprising from 0.5% to 10% by weight of nickel, preferably from 1% to 5% by weight of nickel (expressed as nickel oxide NiO), and from 1% to 30% by weight. weight of molybdenum, preferably from 3% to 20% by weight of molybdenum (expressed as molybdenum oxide Mo03) on an inorganic support. This support can for example be chosen from the group consisting of alumina, silica, silica-aluminas, magnesia, clays and mixtures of at least two of these minerals.
    Advantageously, this support can contain other doping compounds, in particular oxides chosen from the group consisting of boron oxide, zirconia, cerine, titanium oxide, phosphoric anhydride and a mixture of these oxides. Most often an alumina support is used and very often an alumina support doped with phosphorus and possibly boron. When phosphoric anhydride P2O5 is present, its concentration is less than 10% by weight. When boron trioxide B2O5 is present, its concentration is less than 10% by weight. The alumina used can be a y (gamma) or η (eta) alumina. This catalyst is most often in the form of extrudates. The total content of metal oxides of groups VIB and VIII can be from 3% to 40% by weight and in general from 5% to 30% by weight and the weight ratio expressed as metal oxide between metal (or metals) of group VIB on metal (or metals) of group VIII is generally between 20 and 1, and most often between 10 and 2.
    In the case of a hydrotreatment step including a step b1) of hydrodemetallization (HDM) then a step b2) of hydrodesulfurization (HDS), use is preferably made of specific catalysts and operating conditions of hydrotreatment adapted to each step. Catalysts which can be used in step b1) for hydrodemetallization are for example indicated in patent documents EP 0113297, EP 0113284, US 5221656, US 5827421, US 7119045, US 5622616 and US 5089463. Catalysts which can be used in step b2 ) of hydrodesulfurization are for example indicated in patent documents EP 0113297, EP 0113284, US 6589908, US 4818743 or US 6332976. One can also use a mixed catalyst also called transition catalyst, active in hydrodemetallization and hydrodesulfurization, with the both for the hydrodemetallization section b1) and for the hydrodesulfurization section b2) as described in patent document FR 2940143.
    In the case of a hydrotreatment step including a step b1) of hydrodemetallization (HDM) then a step b2) of transition, then a step b3) of hydrodesulfurization (HDS), use is preferably made of specific catalysts adapted to each stage and / or specific hydrotreatment operating conditions adapted to each stage. Catalysts which can be used in step b1) for hydrodemetallization are for example indicated in patent documents EP 0113297, EP 0113284, US 5221656, US 5827421, US 7119045, US 5622616 and US 5089463. Catalysts which can be used in step b2 ) of transition, active in hydrodemetallization and in hydrodesulfurization are for example described in patent document FR 2940143. Catalysts which can be used in step b3) of hydrodesulfurization are for example indicated in patent documents EP 0113297, EP 0113284, US 6589908, US 4818743 or US 6332976. It is also possible to use a transition catalyst as described in patent document FR 2940143 for sections b1), b2) and b3).
    Step c) of separation of the hydrotreatment effluent
    The method according to the invention comprises a separation step c) makes it possible to obtain at least one gaseous fraction and at least one cut of the atmospheric residue type, as well as possibly at least one cut of vacuum distillate type and at least one vacuum residue cutting.
    The effluent obtained at the end of step b) of hydrotreatment comprises a liquid fraction of hydrocarbons and a gaseous fraction. This effluent is advantageously separated in at least one separator flask into at least one gaseous fraction and at least one heavy liquid fraction. This effluent can be separated using separation devices well known to those skilled in the art, in particular using one or more separating flasks which can operate at different pressures and temperatures, possibly associated with a stripping means to steam or hydrogen and one or more distillation columns. These separators can for example be high temperature high pressure separators (HPHT) and / or low temperature high pressure separators (HPBT).
    The gaseous fraction contains gases, in particular H2, H2S, NH3, and C1-C4 hydrocarbons. After possible cooling, this gaseous fraction is preferably treated in a hydrogen purification means so as to recover the hydrogen not consumed during the hydrotreatment and hydrocracking reactions. The hydrogen purification means can be an amine wash, a membrane, a PSA type system, or several of these means arranged in series. The purified hydrogen can then advantageously be recycled in the process according to the invention, after possible recompression. Hydrogen can be introduced at the input of step a) of hydrodemetallization and / or at different locations during step b) of hydrotreatment.
    Step c) of separation also comprises an atmospheric distillation optionally followed by a vacuum distillation.
    In a first embodiment, the separation step c) comprises, in addition to the simple gas-liquid separation, at least one atmospheric distillation, in which the liquid hydrocarbon fraction (s) obtained. ) after separation is (are) fractionated by atmospheric distillation into at least one atmospheric distillate fraction and at least one atmospheric residue fraction. The atmospheric distillate fraction (s) may contain fuel bases (naphtha, kerosene and / or diesel) which can be commercially recovered, for example in a refinery for the production of automotive and aviation fuels. The kerosene and / or diesel type fractions can also be used as bases in a marine distillate type pool or as fluxes in a residual type fuel oil or bunker oil pool (according to TISO8217) as for example during the step f) mixing.
    In a second embodiment, the separation step c) of the process according to the invention also comprises at least one vacuum distillation in which the liquid hydrocarbon fraction (s) obtained after separation and / or the atmospheric residue fraction obtained after atmospheric distillation is (are), in part or in whole, fractionated by vacuum distillation into at least one vacuum distillate fraction and at least one vacuum residue fraction.
    Very preferably, step d) of separation comprises first of all an atmospheric distillation, in which the liquid hydrocarbon fraction (s) obtained after separation is (are) fractionated ( s) by atmospheric distillation into at least one atmospheric distillate fraction and at least one atmospheric residue fraction, then vacuum distillation in which part or all of the atmospheric residue fraction obtained after atmospheric distillation is fractionated by vacuum distillation into at least a vacuum distillate fraction and at least one vacuum residue fraction. The vacuum distillate fraction typically contains vacuum type diesel fractions. The vacuum distillate fraction can partly be recovered as a distillate-type marine fuel (according to ISO8217) with very low sulfur content or else be incorporated into a residual bunker fuel oil pool (according to ISO8217), for example during step f) of mixing. The vacuum distillate fraction is sent in part and preferably entirely in step d) of catalytic cracking.
    Part of the heavy fraction consisting of the atmospheric residue fraction and / or the vacuum residue fraction is sent to step d) of catalytic cracking. At least part of the atmospheric residue fraction and / or the vacuum residue fraction can be used as fuel oil or as fuel oil base, optionally as bunker fuel base with low sulfur content during the mixing step f).
    According to a very preferred mode, step c) of separation is implemented under specific conditions allowing optimization of the CCAI by routing the atmospheric residue and / or vacuum residue fractions to step d) of catalytic cracking and / or step e) of mixing.
    Thus, in the absence of vacuum distillation, this routing must allow the hydrotreated atmospheric residue fraction leaving the atmospheric distillation and going directly to step f) of mixing to represent between 40 and 95% by mass, preferably between 45 and 90% by mass of the fuel oil constituted in step f) of mixing.
    The remaining atmospheric residue not going to step f) of mixing is sent to step d) of catalytic cracking.
    Similarly, in a scheme comprising vacuum distillation and where there is no routing of hydrotreated atmospheric residue fraction to step f) of mixing at the outlet of atmospheric distillation, this routing must allow the fraction residue under hydrotreated vacuum going directly to step f) of mixing represents between 40 and 90%, preferably between 50 and 85% by mass of the fuel oil constituted in step f) of mixing. The remainder of vacuum residue not going to step f) of mixing is sent to step d) of catalytic cracking in mixture with at least a part and preferably all of the vacuum distillate from distillation under empty.
    In a diagram comprising vacuum distillation and allowing the simultaneous routing of an atmospheric residue fraction and a vacuum residue fraction to the mixing step f), the sum of the atmospheric residue and vacuum residue fractions must represent between 40 and 95%, preferably between 45 and 85% by mass of the fuel oil constituted in step f) of mixing.
    Stage d) of catalytic cracking
    In accordance with the invention, at the end of step c) of separation, part of the section with atmospheric residue type and / or part of the section with vacuum residue mixed with at least part of the section with type vacuum distillate optionally obtained in step c) is (are) sent (s) in step d) of catalytic cracking in at least one reactor operating in upward or downward flow containing a catalytic cracking catalyst, operating with a ratio catalyst on charge between 4 and 15, preferably between 6 and 12 and with an outlet temperature of the reactor (s) between 450 and 600 ° C, preferably between 480 and 580 ° C.
    Optionally, a co-charge can be injected upstream of the catalytic cracking section d).
    In a catalytic cracking unit, the heat balance is ensured by the combustion of the coke deposited on the catalyst during the reaction step. This combustion takes place in the regeneration zone by air injection via a compressor called the main air compressor (abbreviated to MAB, abbreviation of the English air hand blower terminology).
    Typically, the catalyst enters the regeneration zone with a coke content (defined as the mass of coke on the mass of catalyst) of between 0.5% and 1%, and leaves said zone with a coke content of less than 0.01%. During this step, combustion fumes are generated and leave the regeneration zone at temperatures between 640 ° C and 800 ° C. This smoke will then, depending on the configurations of the unit, undergo a certain number of post-treatments. The regeneration zone can be carried out in two different regenerators as in the R2R ™ process marketed by Axens.
    The Conradson carbon content of the feed (abbreviated as CCR and defined for example by standard ASTM D 482) provides an assessment of the production of coke during catalytic cracking. Depending on the Conradson carbon content of the feed, the coke yield requires specific sizing of the unit to satisfy the thermal balance.
    Thus, when the charge has a CCR leading to a coke content higher than that required to ensure the thermal balance, the excess heat must be removed. This can be done for example, and in a non-exhaustive manner, by the installation of a "catcooler", well known to those skilled in the art, which constitutes an external cooling of a section of the catalyst of the regenerator by exchange with water, thus leading to the production of high pressure steam.
    The catalyst of the catalytic cracking reactor typically consists of particles with an average diameter generally between 40 and 140 micrometers, and most often between 50 and 120 micrometers.
    The catalytic cracking catalyst contains at least one suitable matrix such as alumina, silica or silica-alumina with or without the presence of a type Y zeolite dispersed in this matrix.
    The catalyst can also comprise at least one zeolite having a shape selectivity of one of the following structural types: MEL (for example ZSM11), MFI (for example ZSM-5), NES, EUO, FER, CHA (for example SAPO-34), MFS, MWW. It can also include one of the following zeolites: NU-85, NU-86, NU-88 and IM-5, which also have shape selectivity.
    The advantage of these zeolites having a form selectivity is the obtaining of a better propylene / isobutene selectivity, that is to say a higher propylene / isobutene ratio in the cracking effluents.
    The proportion of zeolite exhibiting shape selectivity relative to the total amount of zeolite can vary depending on the fillers used and the structure of the products sought. Often, 0.1% to 60%, preferably 0.1% to 40%, and in particular 0.1% to 30% by weight of zeolite with form selectivity are used.
    The zeolite (s) can be dispersed in a matrix based on silica, alumina or silica alumina, the proportion of zeolite (all zeolites combined) relative to the weight of the catalyst often being between 0.7% and 80% by weight , preferably between 1% and 50% by weight, and more preferably between 5% and 40% by weight.
    In the case where several zeolites are used, they can be incorporated in a single matrix or in several different matrices. The zeolite content exhibiting shape selectivity in the total inventory is less than 30% by weight.
    The catalyst used in the catalytic cracking reactor can consist of an ultra stable Y-type zeolite dispersed in an alumina, silica, or silica-alumina matrix, to which an additive based on zeolite ZSM5, the quantity of crystals of ZSM5 in the total inventory being less than 30% by weight.
    Said catalytic cracking step can be carried out with a reactor operating in upward current (called riser in English terminology), as in units using a reactor operating in downward current (called downer in English terminology).
    hydrocarbon and the unstable nature of the latter with temperature.
    The catalytic cracking process makes it possible to convert heavy hydrocarbon feedstocks into lighter hydrocarbon fractions ranging from dry gases to a conversion residue. We can distinguish among the effluents the following cuts which are defined classically according to their composition or their boiling temperature (standard cutting points given for information):
    dry and acid gases (essentially: H2, H2S, C1, C2), liquefied petroleum gases containing C3-C4 molecules, gasolines containing at least 80% of compounds having a boiling temperature between 30 and 220 ° C (standard cutting point), sometimes separated into light essence known as LCN (Light Cracked Naphtha) and heavy essence known as HCN (Heavy Cracked Naphtha).
    a light distillate known as LCO (Light Cycle Oil) containing at least 80% of compounds having a boiling temperature between 220 ° C to 360 ° C a heavy distillate sometimes known as HCO (heavy Cycle Oil ) containing at least 80% of compounds having a boiling temperature between 360 ° C to 440 ° C optionally, a residue or slurry which is generally purified from the catalyst particles which it contains to obtain a clarified oil or CO) or a decanted oil (DO). This residue contains at least 80% of compounds having a boiling point above 440 ° C.
    The term Heavy Cycle Oil or HCO is used here to define any heavy cut resulting from the step of d) catalytic cracking (FCC or RFCC) and containing at least 80% of compounds having a boiling point above 360 ° C. It is understood that this section can undergo a step of separation of the catalyst particles.
    Step e) of separation of the catalytic cracking effluent
    The effluent separation unit of the catalytic cracking reactor generally comprises a primary effluent separation, a gas compression and fractionation section as well as distillations for the fractionation of the various liquid sections. This type of fractionation unit is well known to those skilled in the art.
    Step e) of separation of the effluent from step d) of catalytic cracking makes it possible to obtain at least one diesel fraction with standard boiling range between 220 and 360 ° C (LCO) and at least a louid section with a boiling point above 360 ° C (HCO). These cups can be incorporated into fuel pools. At least part of the LCO and / or HCO cuts is incorporated into an oil pool, in particular a residual type fuel oil pool, produced during step f) of mixing. Optionally, part of the LCO and / or HCO sections can be recycled upstream of step a) of hydrodemetallization and / or b) of hydrotreatment.
    Step f) of mixing
    A step f) of mixing is carried out using a fraction directly obtained from step c) of separation consisting of a part of the atmospheric residue type cut resulting from step c) and / or a part of the residue cut under vacuum and from another fraction comprising at least part of the LCO and / or HCO cuts from step e) of separation so as to obtain an oil, in particular a bunker oil of residual type.
    By "fuel oil" is meant in the invention a hydrocarbon fraction usable as fuel. By "fuel oil base" is meant in the invention a hydrocarbon fraction which, mixed with other bases, constitutes an oil fuel.
    Other fuel oil bases from the process (a kerosene cut or a diesel cut from the separation step c) for example) or fluxing bases external to the process (a kerosene, a diesel, a vacuum distillate for direct distillation or from a conversion process) can optionally be incorporated into the fuel oil. According to the invention, flow control advantageously makes it possible to limit the contribution of costly fluxing bases. The use of fluxing bases of origin external to the process during step f) of mixing generally represents less than 10% by weight of the fuel oil, preferably less than 5% by weight of the fuel oil. According to a very preferred mode, the use of cuts of origin external to the process is zero.
    The present invention aims to optimize the characteristics of fuel oil by controlling the properties and flows of the various bases. The control of the properties is notably allowed by the operating conditions of the different sections. Control of the flows is notably enabled by the operating conditions via the yields but also by the separation steps and ultimately by the mixing step. This optimization involves in particular the incorporation during step f) of mixing part of the atmospheric residue and / or vacuum residue from step c) of separation. These cuts having been obtained after hydrotreatment, their sulfur content is low and they contain saturated molecules which will give good combustion properties which will compensate for the addition of aromatic cuts LCO and / or HCO. LCO and / or HCO cuts do not have good combustion properties, but they are not very viscous, so they are widely used for their fluxing properties so as to reduce the viscosity of the mixture. The quantity of LCO and HCO available depends in particular on the quantity of the charge of the catalytic cracking stage and therefore indirectly on the quantities of atmospheric residue and / or vacuum residue which are not subjected to catalytic cracking and sent directly to the stage f) of mixing, this being allowed by particular configurations of stage c) of separation defined previously.
    According to a very preferred mode, step c) of separation is implemented under special conditions allowing an optimization of the CCAI aromaticity index by routing the atmospheric residue and / or vacuum residue fractions to the step
    d) catalytic cracking and / or step e) mixing.
    The value of CCAI is calculated according to ISO 8217 using the equation:
    CCAI = p 15 - 81 -141 lg [lg (v + 0.85)] - 483 Ig 7 ^ 73 (F.1)
    Or
    T is the temperature, expressed in degrees Celsius, at which the kinematic viscosity is determined;
    v is the kinematic viscosity at temperature T, expressed in square millimeters per second;
    pis is the density at 15 ° C, expressed in kilograms per cubic meter; l g is the decimal logarithm.
    Thus, in the absence of vacuum distillation, this routing must allow the hydrotreated atmospheric residue fraction going directly to the mixing stage f) to represent between 40 and 95% by mass, preferably between 45 and 90% by mass of the fuel oil constituted in step f) of mixing. The remaining atmospheric residue not going to step f) of mixing is sent to step d) of catalytic cracking.
    Similarly, in a scheme comprising vacuum distillation and where there is no routing of the hydrotreated atmospheric residue fraction to mixing step f), this routing must allow the fraction of the hydrotreated vacuum fraction going directly to step f) of mixing represents between 40 and 90%, preferably between 50 and 85% by mass of the fuel oil constituted in step f) of mixing. The remainder of vacuum residue not going to step f) of mixing is sent to step d) of catalytic cracking in mixture with at least part and preferably all of the vacuum distillate from step b) hydrotreatment.
    This additional vacuum residue going to step d) of catalytic cracking may also not be obtained by vacuum distillation, but be part of an atmospheric residue fraction going directly to step d) of catalytic cracking.
    In a scheme comprising vacuum distillation and allowing the simultaneous routing of an atmospheric residue fraction and a vacuum residue fraction towards the mixing step f), the sum of the atmospheric residue and vacuum residue fractions must represent between 40 and 95%, preferably between 45 and 85% by mass of the fuel oil constituted in step f) of mixing.
    EXAMPLES
    An atmospheric residue of Arabian Medium type (see Table 1) is subjected to a residue hydrotreatment step (see Table 2).
    Table 1: RA Arabian Medium load characteristics
    Density at 15 ° C (g / mL) 0.98 Ni + V content (ppm) 68 Sulfur (% by weight) 3.86 Conradson carbon (% by weight) 11
    Table 2: operating conditions of the residue hydrotreatment step
    HDM catalyst CoMoni on alumina Transition catalyst CoMoni on alumina HDS catalyst CoMoni on alumina Catalytic space velocity (h ' 1 ) 0.2 Weighted average temperature at the start of the cycle (° C) 370 Hydrogen partial pressure (MPa) 15 H2 consumption (% weight / load) 1.65
    These conditions make it possible to achieve a hydrodesulfurization of the load of approximately 93% (HDS).
    The effluent from the hydrotreatment stage is analyzed in order to determine the yields of the different products and different cuts (Table 3).
    Table 3: yields of the hydrotreatment stage
    Product Efficiency (% weight / load) H2S 3.83 NH3 0.19 C1 0.21 C2 0.19 C3 0.21 C4 0.19 Atmospheric distillaries (PI-350 ° C) 10.61 Vacuum distillate (350-520 ° C) 40.51 Vacuum residue (520 ° C +) 45.71 Atmospheric residue (350 ° C +) 86.22
    For the rest of the example, reference will be made to FIG. 1 described above, the numbering of which is used to identify the flows and present the various material balances.
    The effluent from the hydrotreatment step (7) is subjected to a separation step c) according to different variants. The effluent (7) is sent to several separators (SEP) operating at different pressure and temperature levels and making it possible to separate the gas fraction (23) containing hydrogen and light hydrocarbons and the liquid fraction (25). This liquid fraction (25) is subjected to atmospheric distillation (ADU) to recover the atmospheric distillates DA (24) and a cut of atmospheric residue type RA (9). Depending on the variants, the atmospheric residue cut can go to catalytic cracking d) via line (11) and / or to the mixing step f) via line (12) and / or to vacuum distillation (VDU ) via line (26). If vacuum distillation (VDU) is used, a DSV vacuum distillate cut (8) going towards the catalytic cracking is obtained and a RSV vacuum residue cut (10) going towards the catalytic cracking. d) via line (13) and / or the mixing step f) via line (14).
    A separation step e) makes it possible to separate the effluent 16) from the catalytic cracking step d) into different products (not shown in particular LPG and petrol) and in light cutting oil LCO and heavy cutting oil HCO. The part of LCO going to the mixture (19) and the part of HCO going to the mixture (20) are shown but there may also be surpluses of these cuts not shown.
    The mixing step makes it possible to obtain an FO fuel oil (21) having a target viscosity of 380 cSt at 50 ° C. by mixing at least one atmospheric resected cut RA (12) and / or a residue cut under vacuum RSV ( 14) with an LCO cut (19) and / or an HCO cut (20) and / or a fluxing base external to the process EXT (22) which in these examples is a marine distillate MGO ("Marine Gas Oil") having a viscosity of
    2.6 cSt at 40 ° C, a density of 850 Kg / m3 and a sulfur content of 0.096% by mass. The flows expressed in% by weight relative to the load (load flow = 100) of the process (at the hydrotreatment inlet) are presented for the different cases (see Table 4).
    Table 4: material flow according to the different cases (% weight / load)
    flow-> 9 26 11 12 8 10 13 14 19 20 22 21 CasT RA RA->VDU RA ->d) RA -tof) DSVd) RSV RSV-> d) RSV-> f) LCO-> f) HCO-> f) EXT-> f) FO AT 86.22 86.22 0 0 40.51 45.71 0 45.71 5.10 0.68 2.67 54.17 B 86.22 46.86 39.36 0 22.02 24.84 0 24.84 3.24 6.19 0 34.27 B ’ 86.22 86.22 0 0 40.51 45.71 20.87 24.84 3.24 6.19 0 34.27 VS 86.22 23.74 62.48 11.15 12.58 0 12.58 0.52 9.64 0 22.74 VS' 86.22 23.74 62.48 11.15 12.58 0 12.58 0.52 9.64 0.78 23.52 D 86.22 0 86.22 0 0 0 0 0 11.91 4.72 0 16.62 Of 86.22 0 86.22 0 0 0 0 0 11.91 4.72 3.76 20.38 D ” 86.22 0 86.22 0 0 0 0 0 11.91 4.72 15.6 32.22 E 86.22 0 43.11 43.11 0 0 0 0 5.95 2.36 0 51.42 E ’ 86.22 0 43.11 43.11 0 0 0 0 5.95 2.36 3.05 54.47 F 86.22 0 56.41 29.81 0 0 0 0 6.01 3.08 0 38.90 G 86.22 0 69.66 16.56 0 0 0 0 2.97 3.81 0 23.35 H 86.22 0 77.94 8.28 0 0 0 0 1.08 4.26 0 13.62 I 86.22 0 81.25 4.97 0 0 0 0 0.32 4.44 0 9.74 I’m 86.2 0 81.25 4.97 0 0 0 0 0.32 4.44 1.33 11.06
    In case B ’, the entire stream of atmospheric residue is sent to vacuum distillation and vacuum distilled. A vacuum distillate stream (8) and a vacuum residue stream (13) are sent to catalytic cracking. These two flows could therefore have remained combined in the form of an atmospheric residue, we then fall back into case B.
    B and B ’are therefore equivalent in terms of material balances at the output of the unit even if the diagrams of the separation step are different. Similarly, there are variant configurations of step e) of separation in all the cases presented.
    From the flows in Table 4, it is possible to determine the composition of the fuel oils (21), that is to say the content of each constituent (12), (14), (19), (20) and ( 22) introduced in step f) of mixing, expressed as a percentage by weight of the constituent relative to the fuel oil (21).
    Table 5: composition of fuel oils (% mass)
    component 12 14 19 20 22 2 / Case ^ F RA -ï f) RSV - ^ f) LCO-> f) HCO> f) £ 4-I FO AT 0 84.4 9.4 1.3 4.9 100 B 0 72.5 9.4 18.1 0 100 B ’ 0 72.5 9.4 18.1 0 100 VS 0 55.3 2.3 42.4 0 100 VS' 0 53.5 2.2 41.0 3.3 100 D 0 0 71.7 28.3 0 100 Of 0 0 58.4 23.2 18.4 100 D ” 0 0 36.9 14.7 48.4 100 E 83.8 0 11.6 4.6 0 100 E ’ 79.2 0 10.9 4.3 5.6 100 F 76.6 0 15.5 7.9 0 100 G 71.0 0 12.7 16.3 0 100 H 60.8 0 7.9 31.3 0 100 1 51.0 0 3.3 45.7 0 100 1 ’ 45.0 0 2.9 40.1 12.0 100
    The properties of the fuel oils (21) obtained according to the different cases are presented in the following table:
    Table 6: properties of fuel oils (flow (21))
    Density at 15 ° C(Kg / m3) Viscosity at 50 ° C(cSt) CCAI Sulfur (%mass) RMG380 (ISO8217) 991 max 380 max 870max 0.5 max AT 958 379 819 0.41 B 988 379 848 0.45 B ’ 988 379 848 0.45 VS 996 379 857 0.47 VS' 990 305 855 0.45 D 937 4.1 880 0.56 Of 919 3.6 868 0.48 D ” 893 2.8 849 0.34 E 947 581 802 0.32 E ’ 941 379 802 0.30 F 953 379 814 0.34 G 966 379 826 0.38 H 989 379 850 0.46 I 1010 379 873 0.53 I’m 990 181 864 0.47
    For cases A, B, B ’, C, C’, we seek to maximize the CCAI of the fuel oil (21) by optimizing the amount of residue under vacuum RSV going directly to the mixing step f) (14). The CCAI increases when the proportion of RSV (14) in the fuel oil decreases in favor of the LCO (19) and HCO (20) cuts: CCAI fuel oil C> CCAI fuel oil B> CCAI fuel oil A. However, the density of fuel oil C exceeds the maximum value for grade RMG380, so we have to add a small amount of marine distillate
    MGO (22) to lower the density, but the viscosity also decreases, so we obtain a quality above the minimum of the specifications for the fuel oil C ’obtained. There is therefore an optimum RSV content (14) which is between 40 and 90%, preferably between 50 and 85% by mass in the fuel oil (21).
    Cases D, D ’and D” (comparative) correspond to the prior art, that is to say the configuration of the residue hydrotreatment sequences followed by catalytic cracking of the entire hydrotreated RA (11). The fuel oil D obtained has a sulfur content greater than 0.5%. Furthermore, the fuel oils obtained contain very high proportions of LCO (19) and HCO (20), which results in very low viscosities, high densities and therefore high CCAI values. It took about 18% of MGO marine distillate (22) in fuel oil D 'to lower the CCAI below 870, and about 48% of MGO marine distillate (22) in fuel oil D' to lower the CCAI below 850. These mixtures do not constitute a good optimization of the flows, they lead to the introduction of large quantities of MGO marine distillate (22) which greatly increases the cost of producing fuel oil (21).
    In case E, there are as many RAs going to d) as there are RAs going to f) and the mixture is formed without any external flux being added to the process. The viscosity exceeds 380 cSt at 50 ° C, the fuel oil obtained cannot be recovered according to the RMG380 grade. Case E ’aims to lower the viscosity obtained in case E by adding MGO marine distillate. In order not to exceed 380 cSt at 50 ° C, it is necessary that the fuel oil contains 5.6% of MGO marine distillate.
    For cases F, G, H, I, I, we seek to maximize the CCAI of the fuel oil (21) by optimizing the quantity of RA going directly to the step f) (12) of mixing. The CCAI increases when the proportion of RA (12) in the fuel oil decreases in favor of the LCO (19) and HCO (20) cuts: CCAI fuel oil F> CCAI fuel oil G> CCAI fuel oil H> CCAI fuel oil I. However the density of the fuel oil I exceeds the maximum value for the RMG380 grade, we are therefore obliged to add a non-negligible amount of marine distillate MGO (22) to lower the density but the viscosity also decreases, we obtain a quality superior to the minimum sought for the fuel oil I 'got. There is therefore an optimum content of atmospheric residue RA (12) which is between 40 and 95%, preferably between 45 and 90% by mass in the fuel oil (21).
    By comparing case E and case F, we see that by reducing the quantity of RA going directly to step f) of mixing, the viscosity decreases and becomes in accordance with grade RMG380.
    权利要求:
    Claims (15)
    [1]
    1. Method for converting a heavy hydrocarbon feed containing at least one hydrocarbon fraction having a sulfur content of at least 0.1% by weight, a metal content of at least 10 ppm, an initial temperature of boiling at least 340 ° C, and a final boiling temperature of at least 600 ° C, the process comprising the following steps:
    a) an optional step of hydrodemetallization in permutable reactors in which the hydrocarbon feedstock is brought into contact with hydrogen on a hydrodemetallization catalyst,
    b) a hydrotreatment step in a fixed bed of the effluent from step a) of hydrodemetallization when the latter is implemented or of the hydrocarbon feedstock in contact with hydrogen and a hydrotreatment catalyst ,
    c) a step of separating the effluent from step b) of hydrotreatment comprising a gas-liquid separation followed by atmospheric distillation allowing at least one cut of the atmospheric residue type to be obtained, said atmospheric distillation possibly being followed by vacuum distillation allowing a vacuum distillate type cut and a vacuum residue type cut to be obtained,
    d) a step of catalytic cracking of a part of the atmospheric residue type cut resulting from step c) and / or a part of the vacuum residue cut resulting from step c), optionally in admixture with at least one part of the vacuum distillate type cut from separation step c),
    e) a step for separating the effluent from step d) of catalytic cracking, making it possible to obtain at least one light diesel fraction with a standard boiling range of between 220 and 360 ° C. called LCO and at least one heavy cutting with a boiling point higher than 360 ° C called HCO,
    f) a step of mixing a part of the atmospheric residue type cut from step c) and / or a part of the vacuum residue cut from step c) of separation with at least one part diesel cuts of standard boiling range between 220 and 360 ° C called LCO and heavy boiling point greater than 360 ° C called HCO from step e) of separation so as to obtain a fuel oil usable as marine fuel with a sulfur content less than or equal to 0.5% by weight and a CCAI aromaticity index calculated according to ISO8217 standard less than 870.
    [2]
    2. The method of claim 1 wherein the separation step c) comprises vacuum distillation after atmospheric distillation and at least a portion of the atmospheric residue is sent in vacuum distillation to produce a vacuum distillate and a residue empty.
    [3]
    3. The method of claim 2 wherein the vacuum distillate cut obtained at the outlet of the separation step c) is not sent entirely to step d) of catalytic cracking and the method allows the joint production of fuel oil and atmospheric distillates, vacuum distillates, and light gases (C1 to C4).
    [4]
    4. Method according to one of claims 1 to 3 wherein the hydrodemetallization step a) is carried out at a temperature between 300 ° C and 500 ° C, under an absolute pressure between 5 MPa and 35 MPa , with a space velocity of the hydrocarbon charge WH in a range from 0.1 h ' 1 to 5 h' 1 and an amount of hydrogen mixed with the charge between 100 and 5000 normal cubic meters (Nm3) per meter cube (m3) of liquid charge.
    [5]
    5. Method according to one of claims 1 to 4 wherein the hydrotreatment step is carried out at a temperature between 300 ° C and 500 ° C, and under an absolute pressure between 5 MPa and 35 MPa, with a space velocity of the hydrocarbon charge, commonly called WH, included in a range going from 0.1 h 1 to 5 h ' 1 , with an amount of hydrogen mixed with the charge between 100 and 5000 normal cubic meters (Nm3 ) per cubic meter (m3) of liquid charge.
    [6]
    6. Method according to one of claims 1 to 5 wherein the catalytic cracking step is implemented in at least one reactor operating in upward or downward flow containing a catalytic cracking catalyst, operating with a catalyst to charge ratio included between 4 and 15,
    5 and with an outlet temperature of the reactor (s) of between 450 and
    600 ° C.
    [7]
    7. Method according to one of the preceding claims in which the fraction resulting from the separation step c) sent directly as an oil base to the mixing step f) consists only of atmospheric residue and represents
    10 between 40 and 95% by mass of the fuel oil obtained.
    [8]
    8. Method according to one of claims 2 to 6 wherein the fraction from the separation step c) sent directly as an oil base to the mixing step f) consists only of vacuum residue and represents between 40 and 90% by mass of the fuel oil obtained.
    15
    [9]
    9. Method according to one of claims 2 to 6 wherein the fraction from the separation step c) sent directly as an oil base to the mixing step f) consists of atmospheric residue and vacuum residue and represents between 40 and 95% by mass of the fuel oil obtained.
    [10]
    10. The method of claim 7 to 9 wherein is added in step f) of
    20 mixes at least one other fuel base chosen from a kerosene cut or a diesel cut from the separation step c) or a flux base external to the process chosen from a kerosene, a diesel, a vacuum distillate for direct distillation or from a conversion process.
    [11]
    11. The method of claim 10 wherein the fluxing base fraction is less than 10% by mass of the fuel oil obtained, preferably less than 5% by mass of the fuel oil obtained.
    [12]
    12. Method according to one of the preceding claims wherein the charge
    5 hydrocarbon is selected from atmospheric residues, vacuum residues from direct distillation, crude oils, headless crude oils, deasphalt resins, asphalt or deasphalting pitches, residues from conversion processes, aromatic extracts from base production chains for lubricants, oil sands or their
    10 derivatives, oil shales or their derivatives, bedrock oils or their derivatives, taken alone or as a mixture.
    [13]
    13. The method of claim 12 wherein the hydrocarbon feedstock is selected from atmospheric residues or vacuum residues, or mixtures of these residues.
    [14]
    14. Method according to one of the preceding claims, in which step b) of hydrotreatment comprises a first step b1) of hydrodemetallization (HDM) carried out in one or more hydrodemetallization zones in fixed beds in which the effluent of step a), or the feed and hydrogen in the absence of step a), are brought into contact on a hydrodemetallization catalyst, and a
    20 second step b2) subsequent hydrodesulfurization (HDS) carried out in one or more hydrodesulfurization zones in fixed beds in which the effluent from the first step b1) of hydrodemetallization is brought into contact with a hydrodesulfurization catalyst.
    15. Method according to one of claims 1 to 13 wherein step b) of hydrotreatment comprises a first step b1) of hydrodemetallization (HDM) carried out in one or more hydrodemetallization zones in fixed beds in which the effluent from step a), or the charge and hydrogen in the absence of
    5 step a), are brought into contact on a hydrodemetallization catalyst, a second step b2) subsequent transition carried out in one or more transition zones in fixed beds in which the effluent of the first step b1) d ' hydrodemetallization is brought into contact with a transition catalyst, and a third step b3) subsequent hydrodesulfurization (HDS) carried out in a
    10 or more hydrodesulfurization zones in fixed beds, in which the effluent from the second transition step b2) is brought into contact with a hydrodesulfurization catalyst.
    [15]
    16. Method according to one of the preceding claims wherein the fuel oil obtained has a sulfur content less than or equal to 0.1% by weight.
    17. Method according to one of the preceding claims, in which the fuel oil obtained has a density at 15 ° C of less than 991 kg / m3 and a viscosity at 50 ° C of less than 380 cSt.
    1/1
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    引用文献:
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    US5827421A|1992-04-20|1998-10-27|Texaco Inc|Hydroconversion process employing catalyst with specified pore size distribution and no added silica|
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    US6589908B1|2000-11-28|2003-07-08|Shell Oil Company|Method of making alumina having bimodal pore structure, and catalysts made therefrom|
    FR2839902B1|2002-05-24|2007-06-29|Inst Francais Du Petrole|HYDROREFINING AND / OR HYDROCONVERSION CATALYST AND USE THEREOF IN HYDROCARBON CHARGING HYDROCARBON PROCESSES|
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