Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
  • C10G21/003—Solvent de-asphalting
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
  • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
  • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
  • C10G21/12—Organic compounds only
  • C10G21/14—Hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
  • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
  • C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
  • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
  • C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
  • C10G67/0454—Solvent desasphalting
  • C10G67/0463—The hydrotreatment being a hydrorefining
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
  • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
  • C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
  • C10G67/0454—Solvent desasphalting
  • C10G67/049—The hydrotreatment being a hydrocracking
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/44—Solvents

Definitions

• the present invention relates to a novel process for converting a heavy hydrocarbon feedstock, in particular resulting from atmospheric distillation or vacuum distillation of crude oil.
• One of the objectives of the present invention is therefore to increase the level of conversion of the recoverable charge.
• Another objective of the invention is to minimize the formation of such sediments in equipment downstream of the hydroconversion units.
• deasphalting unit hereinafter called conventional or conventional SDA text
• a hydroconversion unit 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); and ii) a phase called “asphalt” or sometimes "pitch” (according to the English terminology) containing inter alia refractory molecular structures.
• Asphalt by its poor quality is a penalizing product for refining schemes, which should be minimized.
• selective SDA selective deasphalting step
• the implementation of selective deasphalting according to the invention makes it possible to selectively remove the so-called ultimate asphalt fraction, that is to say specifically containing the refractory structures, from the feedstock and to obtain a deasphalted oil yield DAO may go beyond the threshold of dependence on the aforementioned solvent.
• the deasphalted oil DAO obtained after the selective deasphalting according to the invention had an aromatic character (that is to say comprising aromatic structures) more pronounced than in the case of deasphalting.
• conventional deasphalting and that its recycling upstream of the hydroconversion stage allowed a better stabilization of the treated medium in bed bubbling by solubilization and / or peptization and / or dispersion of molecular structures conducive to sediment formation.
• the present invention relates to a conversion method of a heavy hydrocarbon feedstock having an initial boiling temperature of at least 300 ° C comprising the following steps: a) a step of hydroconversion of at least a portion of said feedstock in the presence of hydrogen in at least one three-phase reactor, said reactor containing at least one hydroconversion catalyst and operating as a bubbling bed, with an upward flow of liquid and of gas and comprising at least one means for withdrawing said catalyst from said reactor and at least one fresh catalyst booster means in said reactor, under conditions allowing to obtain a Conradson carbon-reduced liquid feedstock, in metals, in sulfur and in nitrogen, b) a step of separation of the effluent from step a) to obtain a light liquid fraction boiling at a temperature below 300 ° C and a heavy liquid fraction boiling at a higher temperature at 300 ° C, c) a step of selective deasphalting of at least a portion of the heavy liquid fraction boiling at a temperature above 300 ° C from step b), by liquid / liquid
• step c) is carried out on at least a portion of the heavy fraction previously subjected to a stripping step with steam and / or hydrogen.
• the hydroconversion stage a) operates at an absolute pressure of between 2 and 35 MPa, at a temperature of between 300 and 550 ° C., at a space velocity (VVH) of between 0.1 h “1 and 10 h “ 1 and under a quantity of hydrogen mixed with the load of between 50 and 5000 normal cubic meters (Nm 3 ) per cubic meter (m 3 ) of liquid charge.
• VVH space velocity
• the hydroconversion catalyst of step a) is a catalyst comprising an alumina support and at least one group VIII metal chosen from nickel and cobalt, said group VIII element being used in combination with at least one Group VIB metal selected from molybdenum and tungsten.
• the polar solvent used in step c) of deasphalting is chosen from aromatic pure or naphtho-aromatic solvents, polar solvents containing heteroelements, or their mixture or cuts rich in aromatics such as FCC (Fluid Catalytic Cracking) cuts, coal, biomass or biomass / coal slices.
• FCC Fluid Catalytic Cracking
• the apolar solvent used in the deasphalting step c) comprises a saturated hydrocarbon solvent comprising a carbon number greater than or equal to 2, preferably between 2 and 9.
• step c) is carried out with a volume ratio of the mixture of polar and apolar solvents on the mass of the load of between 1/1 and 10/1 expressed in liters per kilogram.
• the part of the DAO deasphalted oil cut not recycled upstream of the hydroconversion stage a) and / or at the inlet of the separation step b) is sent, preferably mixed with at least a portion of the light liquid fraction from step b) in post-treatment units.
• the feedstock is crude oil or a feedstock resulting from the atmospheric distillation or the vacuum distillation of crude oil, or a residual fraction resulting from the direct liquefaction of coal or a vacuum distillate or still a residual fraction resulting from the direct liquefaction of the lignocellulosic biomass alone or mixed with coal and / or a residual petroleum fraction
• Figure 1 illustrates the implementation of the method according to a first embodiment.
• FIG. 2 illustrates the implementation of the method according to a second embodiment.
• the heavy hydrocarbon feedstock according to the process of the invention is advantageously a heavy feedstock resulting from atmospheric distillation or from the vacuum distillation of crude oil, typically having boiling temperatures of at least 300.degree. preferably greater than 450 ° C, and containing impurities, including sulfur, nitrogen and metals.
• the charge can be crude oil.
• the filler according to the process of the invention may be of petroleum origin of atmospheric residue type or vacuum residue from conventional crude (API degree> 20 °), heavy (API degree between 10 and 20 °) or extra heavy (degree API ⁇ 10 °).
• the load may come from different geographical and geochemical origins (type I, II, IIS or III), with a different degree of maturity and biodegradation.
• Said feed may also be a residual fraction resulting from the direct liquefaction of coal (atmospheric residue or vacuum residue resulting for example from the H-Coal TM process) or a H-Coal TM vacuum distillate or a residual fraction direct liquefaction of the lignocellulosic biomass alone or mixed with coal and / or a residual petroleum fraction.
• This type of filler is generally rich in impurities with metal levels greater than 20 ppm, preferably greater than 100 ppm.
• the sulfur content is greater than 0.5%, preferably greater than 1%, and preferably greater than 2% by weight.
• the level of C 7 asphaltenes is advantageously greater than 1%, preferably the level of C 7 asphaltenes is between 1 and 40% and more preferably between 2 and 30%.
• C7 asphaltenes are compounds known to inhibit the conversion of residual cuts, both by their ability to form heavy hydrocarbon residues, commonly known as cokes, and by their tendency to produce sediments which severely limit the operability of the units of hydrotreatment and hydroconversion.
• the Conradson carbon content is greater than 5% or even 35% by weight.
• the Conradson carbon content is defined by ASTM D 482 and represents for the skilled person a well-known evaluation of the amount of carbon residues produced after combustion under standard conditions of temperature and pressure.
• step a) of the process according to the invention the feed undergoes a step a) hydroconversion in the presence of hydrogen in at least one three-phase reactor, said reactor containing at least one hydroconversion catalyst and operating in bed bubbling, upflow of liquid and gas and comprising at least one means for withdrawing said catalyst from said reactor and at least one fresh catalyst booster means in said reactor, under conditions making it possible to obtain a liquid feed containing reduced to Conradson carbon, metals, sulfur and nitrogen.
• At least a part of the deasphalted oil DAO cut from step c) is recycled upstream of the hydroconversion stage a), mixed with said feedstock.
• the crude oil feedstock is sent directly to said hydroconversion stage a), preferably after a simple topping of its lighter fraction, the end point is generally between 50 and 250 ° C, and preferably between 100 and 200 ° C.
• the feedstock treated in the process according to the invention is the fraction resulting from the atmospheric distillation of a crude oil, ie a fraction called atmospheric residue (RA)
• said process advantageously comprises a step of atmospheric distillation prior to the distillation. step a) of hydroconversion.
• the feedstock treated in the process according to the invention is the fraction resulting from atmospheric and vacuum distillation of a crude oil, ie a fraction called vacuum residue (RSV)
• said process advantageously comprises a distillation step. followed by a vacuum distillation step prior to step a) of hydroconversion.
• Stage a) of hydroconversion of the feedstock according to the invention is generally carried out under standard bubbling bed hydroconversion conditions of a liquid hydrocarbon fraction.
• the operation is usually carried out under an absolute pressure of between 2 and 35 MPa, preferably between 5 and 25 MPa, and preferably between 6 and 20 MPa, at a temperature of between 300 and 550 ° C. and preferably between 350 and 500. ° C.
• the hourly space velocity (VVH) and the hydrogen partial pressure are important factors that are chosen according to the characteristics of the product to be treated and the desired conversion.
• the VVH is between 0.1 h -1 and 10 h -1 and preferably between
• the amount of hydrogen mixed with the filler is preferably between 50 and 5000 normal cubic meters (Nm 3 ) per cubic meter (m 3 ) of liquid filler and preferably between 100 and 2000 Nm 3 / m 3 and very preferably between 200 and 1000 Nm 3 / m 3 .
• the hydroconversion catalyst used in step a) of the process according to the invention is advantageously a granular catalyst with a size of about 1 mm.
• the catalyst is most often in the form of extrudates or beads.
• the catalyst comprises a support whose porous distribution is suitable for the treatment of the charge, preferably amorphous and very preferably alumina, a silica-alumina support being also possible in certain cases and at least one metal of the group VIII chosen from nickel and cobalt and preferably nickel, said group VIII element being preferably used in combination with at least one group VIB metal selected from molybdenum and tungsten and preferably the group VIB metal is molybdenum.
• the hydroconversion catalyst comprises nickel as part of group VIII and molybdenum as part of group VIB.
• the nickel content is advantageously between 0.5 and 15%, expressed by weight of nickel oxide (NiO) and preferably between 1 and 10% by weight
• the molybdenum content is advantageously between 1 and 40% expressed by weight of molybdenum trioxide (M0O3), and preferably between 4 and 20% by weight.
• the catalyst may also advantageously contain phosphorus, the content of phosphorus oxide being preferably less than 20% by weight and preferably less than 10% by weight.
• the hydroconversion catalyst used according to the process according to the invention can be partially replaced by fresh catalyst by withdrawal, preferably at the bottom of the reactor and by introducing, either at the top or at the bottom of the reactor, fresh or regenerated catalyst or rejuvenated, preferably at regular time interval and preferably by puff or almost continuously.
• the replacement rate of the spent hydroconversion catalyst with fresh catalyst is advantageously between 0.01 kilograms and 10 kilograms per cubic meter of treated feedstock, and preferably between 0.3 kilograms and 3 kilograms per cubic meter of feedstock treated. This withdrawal and replacement are performed using devices advantageously allowing the continuous operation of this hydroconversion step.
• Step a) of the process according to the invention is advantageously carried out under the conditions of the H-Oil TM process as described, for example, in US-A-4,521,295 or US-A-4,495,060 or US-A. -4,457,831 or US-A-4,354,852 or in the article Aiche, March 19-23, 1995, HOUSTON, Texas, paper number 46d, Second generation ebullated bed technology.
• the hydroconversion catalyst used in the hydroconversion stage a) advantageously makes it possible to ensure both the demetallation and the desulphurization, under conditions making it possible to obtain a low-content liquid feed with metals, with Conradson carbon and with sulfur and to obtain a high conversion to light products, that is to say in particular fuel fractions gasoline and diesel.
• Step a) is advantageously carried out in one or more three-phase hydroconversion reactors, preferably one or more three-phase hydroconversion reactors with intermediate settling flasks.
• Each reactor advantageously comprises a recirculation pump for maintaining the catalyst in a bubbling bed by continuously recycling at least a portion of a liquid fraction advantageously withdrawn at the top of the reactor and reinjected at the bottom of the reactor.
• step b) of the process according to the invention is then subjected, according to step b) of the process according to the invention, to a separation step to obtain a light liquid fraction boiling at a temperature below 300 ° C., preferably less than 350 ° C and preferably less than 375 ° C and a heavy liquid fraction boiling at a temperature above 300 ° C, preferably above 350 ° C and preferably above 375 ° C.
• This separation comprises any separation means known to those skilled in the art, with the exception of atmospheric and vacuum distillations.
• this separation is performed by one or more flash balloons in series, and preferably by a sequence of two successive flash balloons.
• the conditions are chosen so that the cutting point is 300 ° C., preferably 350 ° C. and preferably 375 ° C., so as to obtain two liquid fractions, one so-called light fraction, and a so-called heavy fraction.
• the light fraction directly obtained at the outlet of the separation step b) is then advantageously separated from the light gases (H 2 and C 1 -C 4) to obtain the light liquid fraction boiling at a temperature below 300 ° C., by any means separation device known to those skilled in the art such as for example by passing through a flash balloon, so as to recover the hydrogen gas which is advantageously recycled in the hydroconversion stage a).
• Said light liquid fraction advantageously separated from said light gases and boiling at a temperature below 300 ° C., preferably below 350 ° C. and preferably below 375 ° C., contains the dissolved light gases (C 5 +), a boiling fraction at a temperature below 150 ° C corresponding to naphthas, a fraction boiling between 150 and 250 ° C corresponding to the kerosene fraction and at least a portion of the gas oil fraction boiling between 250 and 375 ° C.
• Said light liquid fraction is advantageously sent in a separation step, preferably in a distillation column to separate said naphtha, kerosene and diesel fractions.
• the heavy liquid fraction boiling at a temperature above 300 ° C, preferably above 350 ° C and preferably above 375 ° C contains at least a portion of the gas oil fraction boiling between 250 and 375 ° C, a fraction boiling between 375 and 540 ° C called vacuum distillate and a fraction boiling at a temperature above 540 ° C, called residue unconverted vacuum.
• the heavy liquid fraction therefore comprises at least a portion of the middle distillates and preferably at least a portion of the gas oil fraction boiling at a temperature between 250 and 375 ° C.
• the heavy liquid fraction is advantageously subjected to a stripping step with steam and / or hydrogen before being sent to the deasphalting step c) according to the invention.
• This step makes it possible to eliminate at least partly the fraction vacuum distillate (9) or (VGO according to the English terminology) contained in the heavy liquid fraction.
• Step c) selective deasphalting of the heavy liquid fraction from step b)
• step c) selective deasphalting carried out in one step.
• said step c) is carried out on at least a portion of the heavy fraction previously subjected to a stripping step with steam and / or hydrogen.
• Said step c) of selective deasphalting comprises contacting said heavy liquid fraction with a mixture of at least one polar solvent and at least one apolar solvent in an extraction medium.
• the proportions of polar and apolar solvent are adjusted according to the properties of the filler and the degree of asphalt extraction desired.
• solvent mixture according to the invention is understood to mean a mixture of at least one polar solvent and at least one apolar solvent according to the invention.
• Step c) of selective deasphalting makes it possible to go further in maintaining the solubilization in the DAO oil matrix of all or part of the so-called refractory molecular structures. It makes it possible to go further in maintaining the solubilization in the DAO oil matrix of all or part of the polar structures of heavy resins and asphaltenes, which are the main constituents of the asphalt phase.
• Step c) of selective deasphalting thus makes it possible to choose what type of polar structures remain solubilized in the DAO oil matrix. Consequently, step c) of selective deasphalting makes it possible to extract selectively from the heavy liquid fraction only a part of this asphalt, that is to say the most polar structures and the most refractory in the refining processes.
• the asphalt extracted according to the process of the invention corresponding to the ultimate asphalt composed essentially of polyaromatic molecular structures and / or heteroatomic refractory.
• the asphalt yield is correlated with the DAO oil yield by the following relation:
• the step c) selective deasphalting can be carried out in an extraction column, preferably in a mixer-settler. This step is carried out by liquid / liquid extraction in one step.
• the liquid / liquid extraction of step c) is carried out under subcritical conditions for the solvent mixture, that is to say at a temperature below the critical temperature of the solvent mixture.
• 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.
• volume ratio of the solvent mixture according to the invention (volume of polar solvent + volume of apolar solvent) on the mass of the heavy liquid fraction is generally between 1/1 and 10/1, preferably between 2/1 to 8/1, expressed in liters per kilogram.
• the solvent mixture according to the invention used in stage c) is a mixture of at least one polar solvent and at least one apolar solvent.
• the polar solvent used may be chosen from pure aromatic or naphtho-aromatic solvents, polar solvents containing heteroelements, or their mixture.
• the aromatic solvent is advantageously chosen from monoaromatic hydrocarbons, preferably benzene, toluene or xylenes alone or as a mixture; diaromatic or polyaromatic; naphthenocarbon aromatic hydrocarbons such as tetralin or indane; heteroatomic aromatic hydrocarbons (oxygenated, nitrogenous, sulfurous) or any other family of compounds having a more polar character than saturated hydrocarbons such as, for example, dimethylsulfoxide (DMSO), dimethylformamide (DMF), tetrahydrofuran (THF) .
• DMSO dimethylsulfoxide
• DMF dimethylformamide
• THF tetrahydrofuran
• the polar solvent used in the process according to the invention can also be a cut rich in aromatics.
• the sections rich in aromatics according to the invention can be, for example, sections derived from FCC (Fluid Catalytic Cracking) such as heavy gasoline or LCO (light cycle oil), as well as cuts derived from coal, biomass or biomass / coal mixture with optionally a residual petroleum charge after thermochemical conversion with or without hydrogen, with or without a catalyst
• FCC Fluid Catalytic Cracking
• LCO light cycle oil
• the polar solvent used is a pure monoaromatic hydrocarbon or in admixture with another aromatic hydrocarbon.
• the apolar solvent used is preferably a solvent composed of saturated hydrocarbon, said saturated hydrocarbon comprising a carbon number greater than or equal to 2, preferably between 2 and 9.
• saturated hydrocarbon solvents are used pure or as a mixture (for example mixture of alkanes and / or cycloalkanes or light petroleum fractions such as naphtha).
• 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 variation of the proportion between the polar and apolar solvent constitutes a real key for adjusting the selective deasphalting step c) according to the invention.
• 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, part of the polar structures of the heavy liquid fraction remaining solubilized and / or dispersed in the DAO deasphalted oil phase.
• the decrease in the proportion of polar solvent in the mixture has the effect of increasing the amount of asphaltenic phase collected.
• step c) of selective deasphalting makes it possible to selectively extract, whatever the load, an ultimate so-called asphalt fraction, enriched with impurities and refractory compounds, while leaving solubilized in the matrix oil at least a portion of the polar structures of heavy resins and less polar non-refractory asphaltenes.
• This also makes it possible to increase the aromatic character of the DAO deasphalted oil phase, the recycling of which upstream of the hydroconversion stage allows a better stabilization of the boiling bed-treated medium by a solubilizing and / or peptizing effect and / or dispersing molecular structures conducive to sediment formation. As a result, it is possible to impose more severe operating conditions in the hydroconversion step, and thus achieve higher levels of conversions of the residual fraction.
• the proportion of polar solvent in the mixture of polar solvent and apolar solvent is between 0.1 and 99.9%, preferably between 0.1 and 95%, preferably between 1 and 95%, so more preferably between 1 and 90%, even more preferably between 1 and 85%, and very preferably between 1 and 80%.
• the proportion of polar solvent in the polar and apolar solvent mixture is a function of the nature of the heavy liquid fraction, the molecular structures composing a heavy liquid fraction varying from one heavy liquid fraction to another. All heavy liquid fractions do not have the same refractory character. The rate of asphalt to be extracted is not necessarily the same depending on the nature of the heavy liquid fraction.
• the nature of the heavy liquid fraction also depends on the petroleum origin derived from the coal or the biomass type of the feedstock according to the invention.
• Step c) of selective deasphalting has the advantage of allowing a considerable improvement in the DAO deasphalted oil yield over a range hitherto unexplored by conventional deasphalting.
• the selective deasphalting makes it possible to cover by adjustment of the proportion polar solvent and of nonpolar solvent the range 75- 99.9% of yield in deasphalted oil DAO.
• the deasphalted oil yield DAO at the end of stage c), whatever the heavy liquid fraction, is advantageously between 50 and 99.9%, preferably between 75 and 99.9%, more preferably between 80 and 99.9%. and 99.9%.
• Another advantage according to the invention is to enable, thanks to the selective deasphalting according to step c), the reduction of the asphalt fraction, the yield of which can be much lower compared to the implementation of a conventional deasphalting, for a given charge.
• the asphalt yield obtained with a paraffinic solvent alone (pentane) can be up to 30% or more.
• this yield is reduced to the range 0.1 to 30% depending on the apolar / polar solvent ratio. It is all the smaller as the proportion of polar solvent in the mixture is high.
• the asphalt extraction range with a yield in the range of 0.1 -50% and more preferably 0.1 -30%, preferably 0.1 -15% is now covered. It is a function of the selectivity desired for a given load as well as the nature of the load. This is a point of interest knowing that the very low cost of recovery of asphalt (penalizing fraction) is still a real limitation for schemes including this type of process.
• the more aromatic character of the deasphalted oil DAO from step c) makes it possible to use it for its stabilizing properties of the C7 asphaltenes contained in the feed, in the areas at risk of sedimentation such as the bubbling bed, the separating zone between the bubbling bed and the selective deasphalting step.
• the DAO deasphalted oil can be recycled at the inlet of the first reactor of the bubbling bed unit, but also directly at the inlet of one of the other reactors with operating conditions dissociated between the different reactors.
• the yield of asphalt obtained is advantageously less than 18%, preferably less than 10% and preferably less than 5% by weight.
• At least a portion of said DAO desasphalted oil fraction resulting from step c) is recycled upstream of the hydroconversion stage a) and / or at the inlet of stage b ) of seperation.
• the portion of the deasphalted DAO oil cut not recycled upstream of the hydroconversion stage a) and / or at the inlet of the separation step b) can advantageously be sent, optionally mixed with at least a part and preferably all of the light liquid fraction resulting from step b) in post-treatment units such as, for example, a hydrotreatment and / or hydrocracking or catalytic cracking unit.
• the feedstock from a vacuum distillation column (23) and having an initial boiling temperature of at least 300 ° C. is sent by the pipe (1) in a hydroconversion unit (2) operating as a bubbling bed.
• the effluent obtained at the end of the hydroconversion stage (exiting via line 3) is separated in the separation zone (4) by steam stripping and / or hydrogen.
• the conditions are generally chosen from so that the cutting point is 300 ° C, preferably 350 ° C and preferably 375 ° C, so as to obtain two liquid fractions, a so-called light fraction (line 25), and a so-called heavy fraction ( pipe 6), without atmospheric distillation step and under intermediate vacuum.
• the light liquid fraction is advantageously sent via line 25 to a separator tank (17) to separate a hydrogen-rich fraction (line 24) and a light liquid fraction (line 26). Said liquid fraction is advantageously sent to a dedicated atmospheric column (5) to separate a gasoline fraction (29), a kerosene fraction (30), a gas oil fraction (31).
• the hydrogen-rich fraction (line 24) is advantageously returned to the inlet of the hydroconversion unit (2).
• distillation columns (5), (18) and (23) make it possible to separate the gas, gasoline (19), kerosene (20), gas oil (21), vacuum distillate (9) or (VGO) fractions according to the terminology Anglo-Saxon); and vacuum residue (1) or (VR according to the English terminology).
• the heavy liquid fraction is then sent via the pipe (6) to a selective deasphalting unit (7) according to the invention to obtain a deasphalted DAO oil cut (pipe 8) and residual asphalt (pipe 16).
• the deasphalted oil fraction DAO is advantageously at least partly, preferably wholly returned to the vacuum distillation column (23) or to the inlet of the separation zone (4).
• the stream (9) contains the vacuum distillate fraction (VGO) with possibly a part of the DAO deasphalted oil.
• VGO vacuum distillate fraction
• This mixture is advantageously sent successively into a hydrotreatment unit (10) and then into a hydrocracking or catalytic cracking unit (1 1).
• the DAO deasphalted oil fraction may be optionally sent, at least in part, directly to a hydrotreatment unit (10) and then to a hydrocracking or catalytic cracking unit (1 1) (not shown in FIG. 1).
• the effluent from the hydrocracking or catalytic cracking unit is advantageously sent to an atmospheric distillation column (12) so as to recover the various valued cuts.
• the gasoline cut is recovered by the pipe (13), the middle distillate cut by the pipe (14) and a heavier fraction of hydroconverted charge by the pipe (15).
• the effluent from the hydrocracking or catalytic cracking unit can also at least partly be returned via line 27 to the input atmospheric distillation column (18).
• the flow (28) allows the possible injection of a catalytic precursor.
• This catalytic precursor can be sent either with the charge of the bubbling bed before the first reactor, or with the inter-stage separator between two reactors, or at the inlet of one of the other reactors.
• the catalytic precursor can also be injected in a different manner at these different locations of the reaction section in order to optimize its efficiency and its consumption related to the operating conditions of the medium in which it is used, and in particular the thermal level of the reactors.
• FIG. 2 In a second embodiment of the method according to the invention shown in FIG. 2, the implementation of the invention is identical to that described in FIG. 1 (same legend of flows, pipes and unit), with the difference that the dedicated atmospheric distillation column (5) is removed.
• the liquid fraction (26) leaving the bottom of the separator flask (17) is sent directly to the atmospheric column (18) entering the refinery. This configuration allows a saving of one of the distillation equipment. Examples
• a residue (RA) resulting from the atmospheric distillation of an Athabasca crude is distilled under vacuum under conditions allowing to obtain a residue under vacuum (RSV) whose main characteristics are presented in Table 1 below.
• the charge of the bubbling bed is therefore an extra-heavy vacuum residue (SRV) whose properties are as follows:
• Table 1 Composition of the charge of the bubbling bed hydroconversion unit
• the charge obtained is sent wholly in a hydroconversion unit in the presence of hydrogen, said section comprising at least one triphasic reactor containing a NiMo / alumina hydroconversion catalyst.
• the section operates as a bubbling bed with an upward flow of liquid and gas.
• the unit used has two reactors in series and is provided with an inter-stage separator.
• the conditions applied in the hydroconversion unit are as follows:
• Quantity of hydrogen mixed with the feed in the first reactor 630 Nm 3 / m 3
• Amount of hydrogen mixed with the feed in the second reactor 190 Nm 3 / m 3
• the heavy fraction boiling at a temperature greater than 375 ° C contains a portion of the gas oil fraction boiling between 250 and 375 ° C, a fraction boiling between 375 and 524 ° C called vacuum distillate (DSV) and a fraction boiling at a temperature greater than 524 ° C called atmospheric residue (RA).
• DSV vacuum distillate
• RA atmospheric residue
• Table 2 Composition of the heavy fraction boiling at a temperature greater than 375 ° C.
• the deasphalted oil (DAO) cut and the asphalt have the following characteristics shown in Table 3:
• Table 3 Composition of the DAO deasphalted oil and asphalt cutter
• the deasphalted hydrocarbon fraction (DAO) thus obtained represents a purified fraction with an overall yield of 51.5% by weight relative to the initial Athabasca vacuum residue.
• This cut can then be sent to an after-treatment unit, such as a catalytic cracking unit or a hydrocracking unit.
• the deasphalted oil obtained can then undergo a hydrotreatment step followed by a fixed-bed hydrocracking step under conditions which make it possible to reduce in particular its content of metals, sulfur and Conradson carbon and to obtain after a new separation by atmospheric distillation a gaseous fraction, an atmospheric distillate that can be split into a gasoline fraction and a gas oil fraction and a heavier fraction called atmospheric residue.
• the entire deasphalted oil DAO is then sent to a hydrocracking unit and is completely converted to the 540- fraction.
• a conversion of RSV Athabasca fraction 540+ of 88.4% by weight is obtained.
• the selective deasphalting charge according to the invention is the same as that shown in Table 2 of Example 1.
• the conditions applied in the selective deasphalting unit are as follows:
• a deasphalted oil cut (DAO) and an asphalt are obtained.
• the deasphalted oil (DAO) cut and the asphalt have the following characteristics shown in Table 4:
• Table 4 Composition of the DAO deasphalted oil cup and selective asphalt
• the method according to the invention thus makes it possible to isolate a deasphalted oil fraction with an overall yield of 59.9% by weight with respect to the initial vacuum residue Athabasca.
• the advantage is therefore to produce a larger amount of a heavy fraction which can then be treated by a hydrotreatment and / or fixed bed hydrocracking and / or catalytic cracking post-treatment process.
• the deasphalted oil DAO obtained after the selective deasphalting according to the invention, by its more aromatic character can also be recycled ideally to the bubbling bed to have a stabilizing effect of the treated medium solubilizing and / or peptizing and / or dispersing molecular structures conducive to sediment formation.
• the entire deasphalted oil DAO is then sent to a hydrocracking unit and is completely converted to the 540- fraction.
• a conversion of the 540+ fraction of 96.8% by weight is obtained.
• the conversion of the 540+ fraction is increased by 8.4% by weight.
• the RSV SR cut is first mixed with the DAO C4 deasphalted oil cutter (ie the DAO oil cutter from conventional butane deasphalting) before being sent entirely to a dob hydroconversion in the presence of hydrogen, said section comprising at least one three-phase reactor containing a NiMo / alumina hydroconversion catalyst.
• the reaction section operates as a bubbling bed operating at an upward flow of liquid and gas.
• the unit used has two reactors.
• the conditions applied in the hydroconversion unit are as follows:
• Quantity of hydrogen mixed with the feed in the first reactor 630 Nm 3 / m 3
• Amount of hydrogen mixed with the feedstock in the second reactor 1 90 Nm 3 / m 3
• Table 7 Yields and product grades of heavy products from bubbling bed (LB)
• the net conversion of the 540 ° C + fraction of the feed is 68% by weight per pass.
• the vacuum residue (RSV) from the distillation zone is then advantageously sent to a deasphalting section in which it is treated in an extractor using the butane solvent under deasphalting conditions known to those skilled in the art to obtain a deasphalted hydrocarbon fraction, called DAO and residual asphalt.
• the conditions applied in the deasphalting unit are as follows:
• the deasphalted oil (DAO) cut and asphalt have the following characteristics shown in Table 8:
• the entire DAO C4 oil is then recycled and mixed with RSV SR Athabasca feed, the mixture then being sent to the boiling bed hydroconversion stage.
• This sequence thus makes it possible to obtain 2 heavy cuts at the output, a single DSV conversion cup (DSV LB) and an asphalt cutter.
• the characteristics of these 2 sections are given in Tables 7 and 8.
• the overall conversion of the 540 ° C + fraction is 84.5% by weight relative to the SRV SR Athabasca load.
• the vacuum distillate cut (DSV LB) can then be sent to a post-treatment unit, such as a hydrotreatment unit followed by a hydrocracking unit under conditions which make it possible to reduce in particular its metal content, in sulfur and carbon Conradson and obtain after a new separation by atmospheric distillation a gaseous fraction, an atmospheric distillate that can be split into a gasoline fraction and a gas oil fraction and a heavier fraction called atmospheric residue. It is also possible to treat all DSV sections (DSV SR + DSV LB).
• a post-treatment unit such as a hydrotreatment unit followed by a hydrocracking unit under conditions which make it possible to reduce in particular its metal content, in sulfur and carbon Conradson and obtain after a new separation by atmospheric distillation a gaseous fraction, an atmospheric distillate that can be split into a gasoline fraction and a gas oil fraction and a heavier fraction called atmospheric residue. It is also possible to treat all DSV sections (DSV SR + DSV LB).
• the mixture DSV SR + DSV LB whose composition is also given in Table 9, is sent to a post-treatment unit, such as a hydrotreatment unit followed by a unit hydrocracking under conditions that in particular reduce its content of metals, sulfur and Conradson carbon and obtain after a new separation by atmospheric distillation a gaseous fraction, an atmospheric distillate that can be split into a gasoline fraction and a diesel fraction and a heavier fraction called atmospheric residue.
• a post-treatment unit such as a hydrotreatment unit followed by a unit hydrocracking under conditions that in particular reduce its content of metals, sulfur and Conradson carbon and obtain after a new separation by atmospheric distillation a gaseous fraction, an atmospheric distillate that can be split into a gasoline fraction and a diesel fraction and a heavier fraction called atmospheric residue.
• the deasphalted DAO oil cut produced according to the invention as described in Example 2 is sent with the atmospheric residue of the Athabasca crude described in Table 1 in the primary vacuum distillation column.
• the latter thus produces a DSV cut, which contains the DSV SR present in the original Athabasca crude, as well as the 540 ° C fraction of the DAO oil cut produced in the deasphalting unit.
• the primary vacuum distillation column also produces an RSV vacuum residue, which contains the RSV SR present in the original Athabasca crude, as well as the 540 ° C + fraction of the DAO oil cut produced in the deasphalting unit according to the invention. .
• This vacuum residue from the primary vacuum distillation column is therefore the charge of the boiling bed hydroconversion unit.
• This charge is sent entirely in a hydroconversion unit in the presence of hydrogen, said section comprising at least one triphasic reactor containing a NiMo / alumina hydroconversion catalyst.
• the reaction section operates as a bubbling bed operating at an upward flow of liquid and gas.
• the unit used has two reactors in series. The conditions applied in the hydroconversion unit are as follows:
• Quantity of hydrogen mixed with the feed in the first reactor 630 Nm 3 / m 3
• Quantity of hydrogen mixed with the feedstock in the second reactor 190 Nm 3 / m 3
• the heavy fraction boiling at a temperature above 375 ° C contains a portion of the gas oil fraction boiling between 250 and 375 ° C, a fraction boiling between 375 and 540 ° C called vacuum distillate (DSV) and a fraction boiling at a temperature greater than 540 ° C called vacuum residue (RSV).
• DSV fraction boiling between 375 and 540 ° C
• RSV vacuum residue
• Table 10 Composition of the heavy fraction boiling at a temperature
• the deasphalting unit selectively deasphalces using a solvent mixture under the following conditions:
• a DAO deasphalted oil cutter and an asphalt are obtained.
• the deasphalted DAO oil cutter and the asphalt have the following characteristics indicated in Table 1 1:
• Table 1 1 Composition of the selective CAD and asphalt cut
• the entire deasphalted oil DAO is then recycled in admixture with the atmospheric residue which is then sent to the vacuum distillation column.
• a vacuum residue cut (RSV) constituting the feed of the hydroconversion unit and a vacuum distillate cut (DSV) boiling between 375 and 540 ° C are obtained.
• This configuration makes it possible to separate the selective DAO deasphalted oil cut into a light fraction, which will leave with the vacuum distillate (s) produced during the fractionation under primary vacuum, and a heavy fraction, which will leave with the residue under vacuum of the fractionation column. under a primary vacuum thereby constituting a reduced C7 asphaltenes feed of the boiling bed hydroconversion unit.
• the overall conversion of the 540 ° C + fraction is 98.4% by weight relative to RSV SR Athabasca.
• the vacuum distillate DSV obtained from the primary vacuum fractionation thus contains the vacuum distillate present in the initial crude Athabasca and the light fraction of the deasphalted oil fraction DAO resulting from the selective deasphalting according to the invention.
• This DSV vacuum distillate cut from the primary vacuum fractionation is then sent to post-treatment units such as, for example, a hydrotreatment and / or catalytic cracking section and / or catalytic hydrocracking.
• the DSV vacuum distillate cut from the primary vacuum fractionation is sent to a post-treatment unit, such as a hydrotreating unit followed by a hydrocracking unit under conditions that make it possible to reduce in particular its content in metals, sulfur and carbon Conradson and obtain after a new separation by atmospheric distillation a gaseous fraction, an atmospheric distillate that can be split into a gasoline fraction and a gas oil fraction and a heavier fraction called atmospheric residue.
• a post-treatment unit such as a hydrotreating unit followed by a hydrocracking unit under conditions that make it possible to reduce in particular its content in metals, sulfur and carbon Conradson and obtain after a new separation by atmospheric distillation a gaseous fraction, an atmospheric distillate that can be split into a gasoline fraction and a gas oil fraction and a heavier fraction called atmospheric residue.
• the DSV cut thus obtained represents a purified cut with an overall yield of 43.2% by weight relative to the initial crude Athabasca.
• This cut can then be sent to a post-treatment unit, such as a catalytic cracking unit or a hydrocracking unit.
• a post-treatment unit such as a catalytic cracking unit or a hydrocracking unit.
• the deasphalted oil obtained then undergoes a hydrotreatment step followed by a fixed-bed hydrocracking stage under conditions which make it possible to reduce in particular its content of metals, sulfur and Conradson carbon and to obtain afterwards a further separation by atmospheric distillation of a gaseous fraction, an atmospheric distillate which can be split into a gasoline fraction and a gas oil fraction and a heavier fraction called an atmospheric residue.

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