EP3260520B1 - Procede ameliore d'hydroconversion profonde au moyen d'une extraction des aromatiques et resines avec valorisation de l'extrait a l'hydroconversion et du raffinat aux unites aval - Google Patents

Procede ameliore d'hydroconversion profonde au moyen d'une extraction des aromatiques et resines avec valorisation de l'extrait a l'hydroconversion et du raffinat aux unites aval Download PDF

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EP3260520B1
EP3260520B1 EP17176996.1A EP17176996A EP3260520B1 EP 3260520 B1 EP3260520 B1 EP 3260520B1 EP 17176996 A EP17176996 A EP 17176996A EP 3260520 B1 EP3260520 B1 EP 3260520B1
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vacuum
fraction
hydroconversion
unit
extraction
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German (de)
English (en)
French (fr)
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EP3260520A1 (fr
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Jean-François Le Coz
Frédéric Morel
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Axens SA
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Axens SA
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    • 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
    • C10G67/0409—Extraction of unsaturated 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
    • 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
    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
    • 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
    • C10G67/049—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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking 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
    • C10G7/00—Distillation of hydrocarbon oils
    • 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
    • C10G7/00—Distillation of hydrocarbon oils
    • C10G7/06—Vacuum distillation
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1096—Aromatics or polyaromatics
    • 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 invention relates to the field of deep conversion of heavy hydrocarbon feedstocks which makes it possible to obtain valuable hydrocarbon cuts such as liquified petroleum gas (LPG), gasolines or naphthas, kerosene, diesel and oils.
  • LPG liquified petroleum gas
  • gasolines or naphthas kerosene
  • diesel and oils valuable hydrocarbon cuts
  • the invention provides process schemes for improving the performance of conversion units by introducing aromatics extraction.
  • Refineries typically include a deep hydroconversion unit of the residue, followed by atmospheric fractionation, followed by vacuum fractionation and downstream, a catalytic cracking unit and / or a hydrocracking unit.
  • a deasphalting unit of the unconverted residue during the hydroconversion is also present.
  • Deep hydroconversion processes are used in refineries to convert heavy hydrocarbon mixtures into easily recoverable products. They are usually mainly used to convert heavy loads such as heavy petroleum or synthetic cuts, for example residues from atmospheric distillation and vacuum to convert them to lighter gasoline and gas oil. During hydroconversion, fuel oil, and light cuts such as LPG (liquefied petroleum gas) and naphtha (gasoline cut) are also produced.
  • LPG liquefied petroleum gas
  • naphtha gasoline cut
  • the deep hydroconversion process may be hydrocracking of bubbling bed residue. This technology is marketed under the name of H-OIL ®. The charge is then usually the residue under vacuum.
  • the deep hydroconversion unit produces heavy unconverted residue with high asphaltene content. Asphaltenes are unstable and tend to precipitate in hot spots such as furnaces and column bottoms (especially in the vacuum column). As a result, units and columns are periodically shut down for cleaning, reducing their uptime. Typically, the continuous running times ("runs" in the English terminology) last two years, then the units are stopped and opened for cleaning. The vacuum column is stopped even more frequently (typically every year).
  • Asphaltenes are a family of compounds soluble in aromatic solvents and polyaromatic and insoluble in aliphatic hydrocarbons (N-pentane, N-heptane ). Their structure and composition vary according to the origin of the petroleum charge, but some atoms and groups of said structure are always present in varying proportions. Among these atoms, there may be mentioned oxygen, sulfur, nitrogen, heavy metals such as for example nickel and vanadium. The presence of numerous polycyclic groups gives the asphaltene molecules a highly aromatic character. Because of their insolubility in aliphatic hydrocarbons and depending on the more or less aromatic nature of crude oil or petroleum fractions (also referred to as by-products), asphaltenes can precipitate. This phenomenon leads to deposit formation in production lines and equipment (reactors, balloons, columns and exchangers).
  • the resins are asphaltene-like hydrocarbon compounds, but they are soluble in solvents such as N-pentane or N-heptane in contrast to asphaltenes.
  • the resins typically consist of a condensed polycyclic ring composed of aromatic and cyclanic rings and sulfurous or nitrogenous heterocycles with a lower molecular weight and a less condensed structure than the asphaltenes.
  • a first way to improve the stability of the residue is to play on the conversion in the reaction section by limiting it.
  • the stability of the residue dictates the maximum achievable conversion in the deep hydroconversion units (typically from 60% to more than 80% by weight).
  • diluent 5 to 10% by weight, and typically up to 20% by weight
  • this diluent may be catalytic cracking slurry (ie sludge or heavy residual fraction from the FCC, 360 ° C + predominantly aromatic cut).
  • refiners combine the two means (suitable conversion and dilution of the feedstock) in the hydroconversion unit to limit asphaltene deposits.
  • the possible diluents such as the catalytic cracked heavy slurry fraction, are available in limited quantities and are therefore a factor limiting the maximum achievable conversion in deep hydroconversion units.
  • Licences US 5,980,730 and US 6,017,441 describe a method for deep conversion of a heavy petroleum fraction, said process comprising a three-phase bubbling bed hydroconversion step, an atmospheric distillation of the effluent obtained, a vacuum distillation of the obtained atmospheric residue, a deasphalting of the residue under vacuum obtained and a hydrotreatment of the deasphalted fraction. It is also possible in this process to send at least one heavy liquid fraction resulting from the step hydrotreating in a fluidized catalytic cracking section or recycling a portion of the deasphalted fraction or part of the asphalt to the hydroconversion inlet.
  • the patent FR 2 969 650 B1 describes a hydrocarbon feedstock conversion process comprising a shale oil, said method comprising a bubbling bed hydroconversion stage, an atmospheric distillation of the obtained effluent and a liquid / liquid extraction of the atmospheric residue fraction with a solvent allowing extract aromatics and resins.
  • a fraction of the raffinate to a catalytic cracking section and to recycle a fraction of the extract to the hydroconversion unit. Since the atmospheric residue resulting from the hydroconversion is not deasphalted in the process described in this patent, the extract from the extraction unit is likely to contain asphaltenes, which would lead to a degradation of the hydroconversion performances. in case of recycling it to hydroconversion.
  • the process described in this patent is specifically adapted to the treatment of fillers comprising shale oils whose nature is different from conventional hydrocarbon feeds.
  • the patent FR 2 984 917 B1 discloses a method for optimizing the production of middle distillate in a refinery containing at least one catalytic cracking unit for which one of the variants comprises subjecting the residue under vacuum from a catalytic cracking unit to a solvent extraction of aromatic or alternatively to a propane deasphalting, then send the fuel extract and recycle the raffinate at the inlet of the catalytic cracking unit.
  • the extract of the extraction unit is not upgraded to the hydroconversion unit.
  • FR3014897 discloses a process for treating a hydrocarbon feedstock comprising a hydroconversion step, a separation step by atmospheric distillation followed by a vacuum distillation, a selective deasphalting step carried out in two stages, by contacting with a mixture of at least one polar solvent and at least one apolar solvent, in a so-called decreasing polarity configuration, and a recycling step at the inlet of the hydroconversion stage.
  • the process according to the invention proposes to add, following the deep hydroconversion unit and the fractionation section, a deasphalting unit, followed by a unit for extracting the aromatic hydrocarbons and resins on the residual residue fraction. fractionation under vacuum, and to recover the extract and the raffinate obtained in the aromatics extraction unit.
  • the invention simultaneously improves the performance of the deep hydroconversion unit and those of any downstream units such as hydrocracking or catalytic cracking.
  • the process according to the invention makes it possible to obtain higher yields of hydrocarbon fractions that can be upgraded while guaranteeing the same cycle time to the deep hydroconversion unit, or even increasing it. , and improving the performance of downstream units.
  • the unconverted oil fraction from the hydrocracking and / or the heavy residual fraction from the catalytic cracking can be sent to the aromatics extraction section.
  • the extract may be partly used as a fluxing oil mixed with the residual asphalt produced by the deasphalting step d) to give a liquid fuel or to enter the bitumen composition or to feed a coking unit.
  • the raffinate produced by the aromatics extraction unit can be sent to the hydrocracking unit and / or to the catalytic cracking unit concomitantly with one or more other fillers selected from vacuum gas oil from direct distillation crude oil (Straight Run VGO) and the distillates under light vacuum (LVGO) and heavy distillates (HVGO) obtained at the outlet of the vacuum fractionation (c).
  • one or more other fillers selected from vacuum gas oil from direct distillation crude oil (Straight Run VGO) and the distillates under light vacuum (LVGO) and heavy distillates (HVGO) obtained at the outlet of the vacuum fractionation (c).
  • At least a portion of the light vacuum distillate (LVGO) or heavy vacuum distillate (HVGO) is sent to the extraction section of the aromatics.
  • a part of the atmospheric residue is sent directly into the deasphalting section.
  • the hydroconversion stage a) is preferably carried out under an absolute pressure of between 5 and 35 MPa, at a weighted average temperature of the catalytic bed of 300 to 600 ° C., at an hourly space velocity ranging from 0.1 h . 1 to 10 h -1 and a ratio H 2 / HC hydrogen on charge ranging from 200 to 1000m 3 / m 3 .
  • the hydrocracking step f1) is preferably carried out under an average temperature of the catalytic bed of between 300 and 550 ° C., a pressure of between 5 and 35 MPa and a liquid space velocity of between 0.1 and 10 h -1. .
  • the fluidized catalytic cracking step f 2) is preferably carried out in upward flow with a reactor outlet temperature of between 520 ° C. and 600 ° C., a C / O ratio of between 6 and 14, and a reaction time of residence between 1 and 10 s or in downflow with a reactor outlet temperature between 580 ° C and 630 ° C, a C / O ratio between 15 and 40, and a residence time of between 0.1 and 1 s.
  • the deasphalting step is carried out in an extraction column, the solvent comprising at least 50 percent by weight of hydrocarbon compounds having 3 to 7 carbon atoms, the temperature at the extractor head being between 50 and 250 ° C, the temperature at the bottom of the extractor being between 30 and 220 ° C, the pressure being between 2 and 10 MPa.
  • the solvent is butane.
  • the liquid-liquid extraction is carried out using a solvent selected from furfural, N-methyl-2-pyrrolidone (NMP), sulfolane, dimethylformamide (DMF), dimethylsulfoxide (DMSO) , phenol, or a mixture of these solvents in equal or different proportions, with a solvent / charge ratio of 0.5 / 1 to 3/1, at a temperature between room temperature and 150 ° C, at a pressure of between atmospheric pressure and 2 MPa.
  • NMP N-methyl-2-pyrrolidone
  • DMF dimethylformamide
  • DMSO dimethylsulfoxide
  • the filler is advantageously chosen from heavy hydrocarbon feedstocks of the atmospheric or vacuum residue type obtained, for example by direct distillation of petroleum fraction or by vacuum distillation of crude oil, distillate type feedstocks such as vacuum gas oils or oils. deasphalted, asphalts from solvent deasphalting petroleum residues, coal suspended in a hydrocarbon fraction such as for example gas oil obtained by vacuum distillation of crude oil or distillate from the liquefaction of coal, alone or in mixture .
  • the process according to the invention is preferably applied to hydrocarbon feeds containing refractory asphaltenes.
  • the process according to the invention proposes to insert an additional unit for extracting aromatics in order to improve the performance of the scheme, by enhancing the extract and possibly the raffinate obtained.
  • the figure 2 presents by way of illustration the process according to the invention and its variants.
  • the feedstock 01 composed of hydrocarbons of petroleum origin or of mineral-source synthetic hydrocarbons is sent into the deep hydroconversion section 10 with a diluent fluid 02 which comes from the aromatics extraction unit 50 via the transport 53.
  • the liquid effluent from the deep hydroconversion section is sent via line 11 to an atmospheric fractionation section 20.
  • This fractionation section comprises one or more atmospheric distillation columns equipped with trays and internals making it possible to separate different recoverable cuts. withdrawn by means of the transport lines 21, 22 and 23, plus possibly other lateral withdrawals. These sections have ranges of boiling points located for example in the range of gasoline, kerosene and gas oil. In the bottom of fractionation, a heavier fraction of unconverted atmospheric residue 24 is recovered with a boiling point typically greater than 350 ° C.
  • the atmospheric residue is sent at least in part through line 24 to a vacuum fractionation section 30.
  • This fractionation section comprises at least one vacuum distillation column equipped with trays and internals for separating different recoverable cuts withdrawn at average lines 31 and 32 plus possibly other lateral rackings. These sections have ranges of boiling points located for example in the range of light vacuum distillates (LVGO) and heavy (HVGO). At the bottom of the fractionation section, a heavier fraction of unconverted vacuum residue is recovered, the boiling point of which is typically greater than 540 ° C.
  • the light vacuum distillate (LVGO) 31 and the heavy vacuum distillate (HVGO) 32 can be sent to the hydrocracking units 60 and / or catalytic cracking units 70.
  • the vacuum residue is sent via line 33 to the deasphalting unit 40 which makes it possible to extract the asphaltenes by precipitation in a solvent and to produce the deasphalted oil 41 and the pitch (residual asphalt) 42.
  • the deasphalted oil 41 is sent to the aromatics extraction unit 50; as well as possibly the unconverted oil purge of the hydrocracking unit 62 or the heavy residual fraction of the catalytic cracking (FCC slurry) 72 according to the variants of the invention.
  • the raffinate 51 produced by the aromatics extraction unit 50 is sent to the hydrocracking unit, as well as possibly other charges, such as, for example, vacuum distillate obtained from the direct distillation of the crude oil (Straight Run VGO) 91 and the light vacuum 31 and heavy 32 distillate, products of hydroconversion 10.
  • all or part of the light vacuum distillate 31 or the heavy vacuum distillate 32 may also be sent to the aromatics extraction unit 50.
  • part of the atmospheric residue 24 is sent to the deasphalting unit. It is also possible to envisage the case, in which all the atmospheric residue 24 is sent to the deasphalting unit, there is then no vacuum fractionation section 30 and the recoverable cuts in the ranges of boiling points. light (LVGO) and heavy (HVGO) vacuum distillates are not separated, but are sent to the deasphalting unit.
  • the process according to the invention does not comprise a hydrocracking unit 60 or a catalytic cracking unit 70.
  • the process according to the invention comprises a hydrocracking unit 60.
  • the process according to the invention does not comprise a hydrocracking unit 60, but it comprises a catalytic cracking unit 70.
  • the process according to the invention comprises a hydrocracking unit 60 and a catalytic cracking unit 70.
  • the extract 52 produced by the aromatics extraction unit is used at least in part as a diluent to the hydroconversion unit via line 53 and the excess is valorized with the pitch 42 corresponding to the residual asphalt of the deasphalting unit via line 54.
  • the pitch 42 can be upgraded, for example, into bitumen after appropriate treatment or into heavy fuel oil after dilution or sent to a visbreaking, coking or gasification unit 80.
  • the extraction makes it possible to obtain a raffinate containing at most 10% by weight of resins and preferably at most 5% by weight of resins.
  • the extract obtained contains at least 20% by weight of aromatics and 30% by weight of resins and preferably at least 30% by weight of aromatics and 40% by weight of resins with an asphaltene content of less than 1000 ppm.
  • the advantage of the invention lies in the presence of the deasphalting unit upstream of the aromatics extraction, which makes it possible to obtain an aromatic extract with a low content of impurities, since these are found in the asphalt at the outlet of the deasphalting.
  • the resulting extract is ideally suited as an aromatic diluent for deep hydroconversion.
  • the continuous cycle time of the deep hydroconversion unit is elongated very significantly.
  • the use of the extract as an aromatic diluent in the deep hydroconversion unit, whether this is done at iso-conversion or not, also makes it possible to obtain an increased production of recoverable finished products such as naphtha, diesel and VGO vacuum gas oil.
  • DAO deasphalted hydrocarbon fraction
  • the catalytic performances of the catalytic cracking unit are improved as well as the production of recoverable products compared to a unit fed by the deasphalted hydrocarbon fraction leaving the deasphalting unit.
  • the impurity levels of FCC fluidized catalytic cracking products are reduced.
  • the hydrotreatment units of the downstream finished products operate with reduced costs on catalyst quantities and / or cycle times.
  • Hydroconversion technology bubbling beds of residual type charges is marketed in particular as the H-Oil ® process.
  • the bubbling bed process comprises passing the stream, comprising liquid from the solid and gas, flowing vertically through a reactor containing a catalyst bed.
  • the catalyst in the bed is kept in random motion in the liquid.
  • the gross volume of the catalyst dispersed through the liquid is therefore greater than the volume of the catalyst at standstill.
  • This technology is generally used for the conversion of heavy liquid hydrocarbons or for converting coal into synthetic oils.
  • VVH hourly space velocity
  • hydrogen partial pressure are important factors that are chosen according to the characteristics of the product to be treated and the desired conversion.
  • This catalyst may be a catalyst comprising metals of groups 9 and 10 (former group VIII), for example nickel and / or cobalt most often in combination with at least one metal of group 6 (former group VIB), for example molybdenum and / or tungsten and other promoter elements.
  • the support is for example chosen from the group formed by alumina, silica, silica-aluminas, magnesia, clays and mixtures of at least two of these minerals.
  • the carrier may also contain other compounds. Most often, an alumina support is used.
  • the spent catalyst is partly replaced by fresh (ie new or regenerated) catalyst by withdrawal at the bottom of the reactor and introduction at the top of the reactor.
  • catalyst fresh at regular time interval, that is to say for example by puff or almost continuously.
  • fresh catalyst can be introduced every day.
  • the replacement rate of spent catalyst with fresh catalyst may be, for example, from about 0.01 kilogram to about 10 kilograms per cubic meter of charge.
  • the unit usually comprises a recirculation pump for maintaining the bubbling bed catalyst by continuously recycling at least a portion of the liquid withdrawn at the top of the reactor and reinjected at the bottom of the reactor. It is also possible to send the spent catalyst withdrawn from the reactor into a regeneration zone in which the carbon and the sulfur contained therein are removed and then to return this regenerated catalyst.
  • Deep ebullated bed hydroconversion reduces Conradson's carbon input flux by approximately 50-95% and its nitrogen content by approximately 30-95%.
  • the cutting point of the atmospheric residue is typically set between 300 ° C and 400 ° C, preferably between 340 ° C and 380 ° C.
  • the withdrawn cuts such as naphtha, kerosene and diesel are sent respectively to the gasoline pool, the kerosene pool or the diesel pool.
  • the atmospheric residue is sent at least in part to the vacuum fractionation.
  • the cutting point of the vacuum residue is typically set between 450 ° C and 600 ° C, preferably between 500 ° C and 550 ° C.
  • Squeezed cuts such as Light Vacuum Gasoil (LVGO) or Heavy Vacuum Gasoil (HVGO) are sent at least in part to downstream units such as hydrocracking or catalytic cracking.
  • the atmospheric residue (AR) can be sent partly to the deasphalting unit.
  • the light vacuum distillate (LVGO) is characterized by a distillation range of from 300 ° C to 430 ° C, preferably from 340 ° C to 400 ° C.
  • the heavy vacuum distillate (HVGO) is characterized by a distillation range of from 400 ° C to 600 ° C, preferably from 440 ° C to 550 ° C.
  • the vacuum residue (VR) is sent at least partly, preferably completely, to the deasphalting unit.
  • the deasphalted effluent often referred to as DAO deasphalted oil, has a very low content of asphaltenes and metals.
  • One of the objectives of the deasphalting step is, on the one hand, to maximize the amount of deasphalted oil and, on the other hand, to maintain, or even to minimize, the asphaltene content.
  • This asphaltene content is generally determined in terms of the content of asphaltenes insoluble in heptane, that is to say measured according to a method described in standard NF-T 60-115 of January 2002.
  • the deasphalting makes it possible to obtain a deasphalted oil (DAO) containing at most 10 000 ppm by weight of asphaltenes, preferably at most 2000 ppm by weight of asphaltenes.
  • DAO deasphalted oil
  • the solvent used in the deasphalting step is only a paraffinic solvent.
  • the solvent used comprises at least 50 percent by weight of hydrocarbon compounds (alkanes) having between 3 and 7 carbon atoms, more preferably between 3 and 6 carbon atoms, even more preferably 4 or 5 carbon atoms. carbon.
  • hydrocarbon compounds alkanes
  • the deasphalted oil yield and the quality of this oil may vary.
  • the oil yield increases but, in return, the levels of impurities (asphaltenes, metals, carbon Conradson, sulfur, nitrogen ...) also increase.
  • the deasphalting step may be carried out by any means known to those skilled in the art. This step is generally carried out in a settling mixer or in an extraction column. Preferably, the deasphalting step is carried out in an extraction column.
  • a mixture comprising the hydrocarbon feedstock and a first fraction of a solvent feed is introduced into the extraction column, the volume ratio between the solvent feed fraction and the hydrocarbon feedstock. being called the rate of solvent injected with the charge.
  • This step is intended to mix well the load with the solvent entering the extraction column.
  • a second fraction of the solvent charge the volume ratio between the second solvent loading fraction and the hydrocarbon feed being called the solvent content injected at the bottom of the solvent. extractor.
  • the volume of the hydrocarbon feedstock considered in the settling zone is generally that introduced into the extraction column.
  • the sum of the two volume ratios between each of the solvent feed fractions and the hydrocarbon feed is referred to as the overall solvent level.
  • the decantation of the asphalt consists of the countercurrent washing of the asphalt emulsion in the solvent-oil mixture with pure solvent. It is favored by an increase in the solvent content (it is in fact to replace the solvent-oil environment with a pure solvent environment) and a decrease in temperature.
  • a temperature gradient is established between the head and the bottom of the column to create an internal reflux, which improves the separation between the oily medium and the resins.
  • the mixture of solvent and oil heated at the top of the extractor makes it possible to precipitate a fraction comprising resin which descends into the extractor.
  • the upward countercurrent of the mixture makes it possible to dissolve at a lower temperature the fractions comprising the resin which are the lightest.
  • the pressure inside the extractor is generally adjusted so that all the products remain in the liquid state.
  • the objective of the aromatics extraction unit is to extract the aromatic compounds and resins from the heavy fraction obtained from the deasphalting stage.
  • liquid-liquid extraction using a polar solvent is a known solvent for extracting aromatic compounds preferentially.
  • the liquid / liquid extraction is carried out on the heavy fraction, in order to avoid losses of yield of fuel bases during the recovery of the solvent after extraction.
  • the products which are to be extracted from the heavy fraction preferably have a boiling point higher than the boiling point of the solvent in order to avoid a loss of yield during the separation of the solvent from the raffinate after the extraction. Indeed, during the separation of the solvent and the raffinate, any compound having a boiling point below the boiling point of the solvent will inevitably leave with the solvent and thus lower the amount of the raffinate obtained (and therefore the yield of fuel bases ).
  • a solvent it is possible to use furfural, N-methyl-2-pyrrolidone (NMP), sulfolane, dimethylformamide (DMF), dimethylsulfoxide (DMSO), phenol, or a mixture of these solvents in equal proportions or different.
  • the preferred solvent is furfural, product sufficiently heavy compared to the treated fluid: deasphalted oil DAO.
  • An aromatics extraction unit originally constructed for an oil chain may advantageously be modified for use in the process according to the invention.
  • the operating conditions are in general a solvent / charge ratio of from 0.5: 1 to 3: 1, preferably from 1: 1 to 2: 1, a temperature profile of between room temperature and 150.degree. C., preferably between 50.degree. ° C and 150 ° C.
  • the pressure is between atmospheric pressure and 2 MPa, preferably between 0.1MPa and 1MPa.
  • the liquid / liquid extraction can be carried out generally in a mixer-settler or in an extraction column operating against the current.
  • the extraction is carried out in an extraction column.
  • the chosen solvent has a sufficiently high boiling point in order to be able to thin the heavy fraction resulting from the fractionation without vaporizing, the heavy fraction being typically conveyed at temperatures of between 200 ° C. and 300 ° C.
  • the extract consisting of the parts of the heavy fraction that are not soluble in the solvent (and highly concentrated in aromatics)
  • the raffinate consisting of solvent and soluble parts of the heavy fraction.
  • the solvent is distilled off from the soluble portions and recycled internally to the liquid / liquid extraction process, the solvent management being known to those skilled in the art.
  • the raffinate resulting from the extraction of aromatics is sent to the hydrocracking unit and / or catalytic cracking unit alone or concomitantly with one or more other fillers chosen from vacuum gas oil for direct distillation of crude oil (Straight Run VGO) and the low vacuum (LVGO) and heavy (HVGO) distillates obtained at the outlet of the vacuum fractionation (c).
  • vacuum gas oil for direct distillation of crude oil (Straight Run VGO) and the low vacuum (LVGO) and heavy (HVGO) distillates obtained at the outlet of the vacuum fractionation (c).
  • hydrocracking includes cracking processes comprising at least one charge conversion step using at least one catalyst in the presence of hydrogen.
  • the hydrocracking may be carried out according to one-step diagrams comprising in the first place advanced hydrorefining which is intended to carry out extensive hydrodenitrogenation and desulfurization of the feedstock before the effluent is wholly sent to the hydrocracking catalyst. itself, especially in the case where it comprises a zeolite.
  • It also includes two-step hydrocracking which comprises a first step which aims, as in the "one-step” process, to perform the hydrorefining of the feed, but also to achieve a conversion of the feedstock. order in general from 30 to 60 percent.
  • first step which aims, as in the "one-step” process, to perform the hydrorefining of the feed, but also to achieve a conversion of the feedstock. order in general from 30 to 60 percent.
  • second step of a two-stage hydrocracking process generally only the fraction of the unconverted feedstock in the first step is processed.
  • Conventional hydrorefining catalysts generally contain at least one amorphous support and at least one hydro-dehydrogenating element (generally at least one element of the non-noble groups VIB and VIII, and most often at least one element of group VIB and at least one non-noble group VIII element).
  • the matrices that can be used in the hydrorefining catalyst alone or as a mixture are, by way of example, alumina, halogenated alumina, silica, silica-alumina, clays (chosen by for example, natural clays such as kaolin or bentonite), magnesia, titanium oxide, boron oxide, zirconia, aluminum phosphates, titanium phosphates, phosphate phosphates and the like. zirconium, coal, aluminates. It is preferred to use matrices containing alumina, in all the forms known to those skilled in the art, and even more preferably aluminas, for example gamma-alumina.
  • the operating conditions of the hydrocracking step are adjusted so as to maximize the production of the desired cut while ensuring good operability of the hydrocracking unit.
  • the operating conditions used in the reaction zone (s) are generally an average catalyst bed temperature (WABT) of between 300 and 550 ° C., preferably of between 350 and 500 ° C.
  • the pressure is generally between 5 and 35 MPa, preferably between 6 and 25 MPa.
  • the liquid space velocity (charge rate / volume of catalyst) is generally between 0.1 and 10 h -1, preferably between 0.2 and 5 h -1.
  • An amount of hydrogen is introduced such that the volume ratio in m3 of hydrogen per m3 of hydrocarbon at the inlet of the hydrocracking step is between 300 and 2000 m3 / m3, most often between 500 and 1800 m3 / m3, preferably between 600 and 1500 m3 / m3.
  • This reaction zone generally comprises at least one reactor comprising at least one fixed-bed hydrocracking catalyst.
  • the fixed bed of hydrocracking catalyst may be optionally preceded by at least one fixed bed of a hydrorefining catalyst (hydrodesulfurization, hydrodenitrogenation for example).
  • the hydrocracking catalysts used in the hydrocracking processes are generally of the bifunctional type associating an acid function with a hydrogenating function.
  • the acid function can be provided by supports having a large surface area (generally 150 to 800 m 2 g -1) and having surface acidity, such as halogenated aluminas (chlorinated or fluorinated in particular), combinations of boron oxides and aluminum, amorphous silica-aluminas known as amorphous hydrocracking catalysts and zeolites.
  • the hydrogenating function may be provided either by one or more metals of Group VIII of the Periodic Table of Elements, or by a combination of at least one Group VIB metal of the Periodic Table and at least one Group VIII metal.
  • the hydrocracking catalyst may also comprise at least one crystalline acid function such as a zeolite Y, or an amorphous acid function such as a silica-alumina, at least one matrix and a hydrodehydrogenating function.
  • crystalline acid function such as a zeolite Y
  • amorphous acid function such as a silica-alumina
  • it may also comprise at least one element chosen from boron, phosphorus and silicon, at least one element of group VIIA (chlorine, fluorine for example), at least one element of group VIIB (manganese for example), with least one element of the group VB (niobium for example).
  • group VIIA chlorine, fluorine for example
  • group VIIB manganese for example
  • group VB niobium for example
  • Fluidized catalytic cracking is a well-known process that has undergone many changes since the 1930s (see Avidan A., Shinnar R., "Development of Catalytic Cracking Technology: A Lesson in Chemical Reactor Design", Ind.Eng.Chem.Res, 29, 931-942, 1990 ).
  • This process is characterized by a reaction zone in which the cracking reactions are carried out on a zeolite type catalyst, and a regeneration zone which makes it possible to burn off the coke deposited on the catalyst during the cracking reactions.
  • the main objective of the catalytic cracking unit of a refinery is the production of gasoline bases, ie cuts having a distillation range of between 35 ° C and 250 ° C.
  • Gasoline is produced by cracking the feedstock in the main reactor, called riser, because of the elongated shape of this reactor and its upward flow mode. When the flow is down in the main reactor, it is called “downer”.
  • the conventional feedstock of a fluidized bed catalytic cracking unit of heavy cuts is generally composed of a hydrocarbon or a mixture of hydrocarbons containing essentially (ie at least 80%) of molecules whose boiling is greater than 340 ° C.
  • This main charge also contains limited quantities of metals (Ni + V), in concentration generally less than 50 ppm, preferably less than 20 ppm, and a content of hydrogen in general greater than 11% by weight, typically between 11.5% and 14.5%, and preferably between 11.8% and 14% by weight.
  • the conradson carbon content (abbreviated as CCR) of the feed (defined by ASTM D 482) provides an evaluation of coke production during catalytic cracking.
  • the coke yield requires a specific sizing of the unit to satisfy the heat balance.
  • the C / O ratio is the ratio of the mass flow rate of catalyst circulating in the unit to the mass flow rate at the inlet of the unit.
  • the residence time is defined as the volume of the riser (m3) on the volume flow rate of charge (m3 / s).
  • the feed used in this example has the composition detailed in Table 1. It is a vacuum residue of the "Ural" type (Urals in the English terminus), therefore a vacuum residue obtained from 'a crude oil from Russia.
  • Table 1 ⁇ / u> composition of the load used ("Ural" type vacuum residue)
  • Property Unit Value Density - 1,003 Viscosity at 100 ° C cSt 540 Conradson Carbon %weight 15.0 Asphaltenes in C7 %weight 4.0 Nickel ppm wt 70 Vanadium ppm wt 200 Nitrogen ppm wt 5,800 Sulfur %weight 2.7 Cup 540 ° C - * %weight 10.0 * cup containing products with a boiling point below 540 ° C.
  • the charge is carried out in the process according to the invention ( figure 2 ), without hydrocracking 60 nor catalytic cracking 70 and thus also without the addition of vacuum distillate obtained by the direct distillation of crude oil (SR-VGO) 91 at the inlet of the hydrocracking and / or catalytic cracking steps.
  • SR-VGO crude oil
  • certain products obtained can be subsequently sent to a hydrocracking stage, in particular the raffinate resulting from the extraction stage, alone or as a mixture with other cuts resulting from the process according to the invention.
  • the feedstock is treated in a bubbling bed H-Oil® reactor containing a commercial ebullated bed hydroconversion catalyst (eg TEX2740 or TEX2910, available from Criterion).
  • a commercial ebullated bed hydroconversion catalyst eg TEX2740 or TEX2910, available from Criterion.
  • the liquid products from the reactor are fractionated by atmospheric distillation into a naphtha fraction (C5 + -150 ° C), a gas oil fraction (150-370 ° C) and a residual fraction 370 ° C +.
  • the residual fraction is fractionated by vacuum distillation into a gas fraction which is sent to the fuel, a vacuum distillate fraction VGO (370 ° C.-540 ° C.) and a residual fraction under vacuum at 540 ° C.
  • VGO vacuum distillate fraction
  • the residual fraction under vacuum is subjected to solvent deasphalting C4 with an extraction column.
  • a deasphalted DAO oil and a pitch (residual asphalt) are obtained.
  • the DAO deasphalted oil is subjected to a liquid / liquid furfural extraction to give a raffinate and an extract.
  • the extract is advantageously used in part as a diluent in the deep hydroconversion unit and partly upgraded with the pitch.
  • the solvent used in the SDA unit is a mixture of butanes comprising 60% nC4 and 40% iC4.
  • the DAO yield of the deasphalting unit is increased to 75% in order to maximize the recovery of the deasphalted oil.
  • Table 3 shows that using the extract obtained in the extraction unit as a diluent at the hydroconversion unit doubles the run time of the deep hydroconversion.
  • the associated finished product production gain is just over 3% (1.5 months over 4 years run).
  • the hydroconversion unit produces 5% additional recoverable products, ie 5% Naphtha, 5% Diesel and 5% VGO vacuum gas oil.
  • the properties of the raffinate and the extract at the outlet of the extraction unit are compared with the deasphalted oil DAO in Table 5.
  • Table 5 ⁇ / u> properties of the deasphalted oil (DAO) at the inlet, the raffinate and the extract at the outlet of the extraction unit
  • DAO raffinate Extract Density - 0.97 0,880 0.967 Conradson Carbon %weight 12.6 3.0 19 Asphaltenes in C7 %weight 0.1 ⁇ 0.05 0.2 Nickel + Vanadium ppm wt 20 ⁇ 2 40
  • the raffinate density and the nitrogen and sulfur content of the raffinate are lower than those of the deasphalted DAO oil.
  • the raffinate is therefore a less refractory feedstock to be treated in a fixed bed hydrotreating unit, for example, or in a hydrocracking unit.

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EP17176996.1A 2016-06-23 2017-06-20 Procede ameliore d'hydroconversion profonde au moyen d'une extraction des aromatiques et resines avec valorisation de l'extrait a l'hydroconversion et du raffinat aux unites aval Active EP3260520B1 (fr)

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CN110753744A (zh) * 2017-06-15 2020-02-04 沙特阿拉伯石油公司 将富碳烃转化为贫碳烃
SG11202001629SA (en) 2017-08-29 2020-03-30 Saudi Arabian Oil Co Integrated residuum hydrocracking and hydrofinishing
CN108950229B (zh) * 2018-06-20 2019-11-08 舞阳钢铁有限责任公司 一种低电耗无淤渣化渣炉操作工艺
FR3097229B1 (fr) * 2019-06-12 2021-06-11 Ifp Energies Now Procede de production d’olefines comprenant un hydrotraitement, un desasphaltage, un hydrocraquage et un vapocraquage
FR3098522B1 (fr) 2019-07-10 2021-07-09 Axens Procédé de conversion d’une charge contenant de l’huile de pyrolyse
FR3098824B1 (fr) * 2019-07-17 2021-09-03 Ifp Energies Now Procede de production d’olefines comprenant un hydrotraitement, un desasphaltage, un hydrocraquage et un vapocraquage
US11180701B2 (en) * 2019-08-02 2021-11-23 Saudi Arabian Oil Company Hydrocracking process and system including separation of heavy poly nuclear aromatics from recycle by extraction
FR3101082B1 (fr) * 2019-09-24 2021-10-08 Ifp Energies Now Procédé intégré d’hydrocraquage en lit fixe et d’hydroconversion en lit bouillonnant avec une séparation gaz/liquide améliorée
FR3101637B1 (fr) * 2019-10-07 2021-10-22 Ifp Energies Now Procede de production d’olefines comprenant un desasphaltage, une hydroconversion, un hydrocraquage et un vapocraquage
FR3102772B1 (fr) * 2019-11-06 2021-12-03 Ifp Energies Now Procede de production d’olefines comprenant un desasphaltage, un hydrocraquage et un vapocraquage
CN112920839B (zh) * 2019-12-06 2022-07-08 中国石化工程建设有限公司 一种浆态床加氢裂化反应产物的分离系统及分离方法
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