EP3260520B1 - Improved method for deep hydroconversion by extracting aromatics and resins with recovery of the hydroconversion extract and the raffinate in the downstream units - Google Patents

Description

FIELD OF THE INVENTION :

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.

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. Optionally, 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.

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. In this case, the stability of the residue dictates the maximum achievable conversion in the deep hydroconversion units (typically from 60% to more than 80% by weight).

Another way to obtain an increase in the conversion of the deep hydroconversion units is to mix with the feed a diluent (5 to 10% by weight, and typically up to 20% by weight) consisting of heavy feeds rich in aromatic compounds and resins alone or in a mixture. This makes it possible to operate with longer running times (runs in the English terminology) longer or with a duration of operation equivalent to higher conversion rates. Typically, this diluent may be catalytic cracking slurry (ie sludge or heavy residual fraction from the FCC, 360 ° C ⁺ predominantly aromatic cut).

In practice, refiners combine the two means (suitable conversion and dilution of the feedstock) in the hydroconversion unit to limit asphaltene deposits.

In a typical refinery, 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.

PRIOR ART :

Numerous schemes have been implemented to solve the problems mentioned above, with the aim of improving deep hydroconversion processes by increasing the yields of recoverable products while maintaining an optimal operating cost.

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. Depending on the process variants, it is possible to send 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. In addition, 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. In the process described in this patent, the extract of the extraction unit is not upgraded to the hydroconversion unit.

The patent application US 2013/0026065 A1 discloses a process for producing transportable fuels from heavy hydrocarbons by subjecting them to liquid / liquid extraction of aromatics, then sending the aromatic-enriched fraction to a hydrocracker and the aromatics-depleted fraction to a cracking unit catalytic.
Requirement 14 / 62.715 filed on December 18, 2014 by the Applicant, unpublished, discloses a deep conversion process of residues comprising a hydroconversion step, a separation step, a step of hydrocracking the gas oil fraction under vacuum, a step of fractionation of the hydrocracking effluent and recycling the unconverted vacuum gas oil fraction in the hydroconversion stage, with the aim of maximizing diesel production. 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.

None of the documents of the prior art nevertheless makes it possible to solve all the problems mentioned.

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.

Indeed, compared to the usual refinery scheme, 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.

• pour d'une part, utiliser cette fraction extraite en diluant aromatique à l'hydroconversion,
• d'autre part, utiliser le raffinat issu de cette extraction dans les unités aval éventuelles comme l'hydrocraquage et / ou le craquage catalytique.

Le procédé selon l'invention permet d'atteindre des rendements en produits valorisables plus importants au moyen d'une extraction des aromatiques et résines contenus dans le résidu non converti issu de l'hydroconversion profonde selon les variantes de schémas de procédé détaillées ci-après.The object of the present invention is to overcome the disadvantages of the processes of the prior art by extracting deep hydroconversion effluents from a heavy fraction enriched in aromatic compounds and resins.

• for one hand, use this fraction extracted by aromatic diluent to hydroconversion,
• on the other hand, using the raffinate from this extraction in any downstream units such as hydrocracking and / or catalytic cracking.

The method according to the invention makes it possible to achieve higher yields of valuable products by means of extraction of aromatics and resins. contained in the unconverted residue resulting from the deep hydroconversion according to the variants of the process schemes detailed below.

SUMMARY OF THE INVENTION:

1. a) hydroconversion en lit bouillonnant de la charge, en présence d'hydrogène, dans une section d'hydroconversion comprenant au moins un réacteur triphasique, contenant au moins un catalyseur d'hydroconversion supporté,
2. b) fractionnement atmosphérique d'au moins une partie de l'effluent liquide hydroconverti issu de l'étape a) dans une section de fractionnement atmosphérique pour produire une fraction comprenant une coupe essence et une coupe gazole, et un résidu atmosphérique ;
3. c) fractionnement sous vide d'au moins une partie du résidu atmosphérique issu de l'étape b) dans une section de fractionnement sous vide pour obtenir une fraction gazole sous vide comprenant des distillats sous vide léger (LVGO) et lourd (HVGO), et une fraction résidu sous vide non convertie,
4. d) désasphaltage d'au moins une partie de la fraction résidu sous vide non convertie issue de l'étape c) dans une section de désasphaltage uniquement au moyen d'un solvant paraffinique dans des conditions permettant d'obtenir une coupe hydrocarbonée appauvrie en asphaltènes dite huile désasphaltée et de l'asphalte résiduel.
5. e) extraction liquide-liquide sur la coupe hydrocarbonée appauvrie en asphaltènes dans une section d'extraction des aromatiques au moyen d'un solvant polaire dans des conditions permettant l'extraction des aromatiques pour produire un extrait enrichi en aromatiques et résines et un raffinat appauvri en aromatiques et résines, l'extrait étant envoyé au moins en partie comme diluant aromatique vers l'entrée de la section d'hydroconversion.

The invention relates to a method for deep conversion of a heavy hydrocarbon feedstock comprising the following steps:

1. a) boiling bed hydroconversion of the feed, in the presence of hydrogen, in a hydroconversion section comprising at least one three-phase reactor, containing at least one supported hydroconversion catalyst,
2. b) atmospheric fractionation of at least a portion of the hydroconverted liquid effluent from step a) in an atmospheric fractionation section to produce a fraction comprising a gasoline cut and a gas oil cut, and an atmospheric residue;
3. c) vacuum fractionation of at least a portion of the atmospheric residue from step b) in a vacuum fractionation section to obtain a vacuum gas oil fraction comprising light vacuum (LVGO) and heavy (HVGO) distillates, and an unconverted vacuum residue fraction,
4. d) deasphalting of at least a portion of the unconverted vacuum residue fraction from step c) in a deasphalting section only by means of a paraffinic solvent under conditions making it possible to obtain an asphaltenes-depleted hydrocarbon fraction called deasphalted oil and residual asphalt.
5. e) liquid-liquid extraction on the asphaltene-depleted hydrocarbon fraction in an aromatic extraction section by means of a polar solvent under conditions allowing the extraction of the aromatics to produce an extract enriched in aromatics and resins and a depleted raffinate in aromatics and resins, the extract being at least partly sent as an aromatic diluent to the inlet of the hydroconversion section.

• une étape f1) d'hydrocraquage d'au moins une partie du raffinat issu de l'étape d'extraction e) dans un réacteur comprenant au moins un catalyseur d'hydrocraquage en lit fixe pour produire une fraction essence, une fraction gazole (GO), gazole sous vide (VGO) et une fraction d'huile non convertie (UCO)
• et/ou une étape f2) de craquage catalytique en lit fluidisé d'au moins une partie du raffinat issu de l'extraction e) dans un réacteur en lit fluidisé pour produire une fraction gazeuse, une fraction essence, une fraction gazole et une fraction résiduelle lourde dite slurry.

The method according to the invention may furthermore comprise:

• a step f1) of hydrocracking at least a portion of the raffinate from the extraction step e) in a reactor comprising at least one fixed-bed hydrocracking catalyst to produce a gasoline fraction, a gas oil fraction (GO ), vacuum gas oil (VGO) and an unconverted oil fraction (UCO)
• and / or a fluidized catalytic cracking step f 2) of at least a portion of the raffinate from the extraction e) in a fluidized bed reactor to produce a gaseous fraction, a gasoline fraction, a gas oil fraction and a fraction heavy residual called slurry.

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).

At least a portion of the light vacuum distillate (LVGO) or heavy vacuum distillate (HVGO) is sent to the extraction section of the aromatics.

In a variant, 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.

Preferably, 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.

Very preferably, the solvent is butane.

Preferably, 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.

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 .

DETAILED DESCRIPTION OF THE INVENTION

The process according to the invention is preferably applied to hydrocarbon feeds containing refractory asphaltenes. Compared to the known schemes of the prior art, 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.

List of Figures

• The figure 1 describes the scheme of the process according to the prior art:
  ∘ Scheme 1 (prior art): Sequence of a deep hydroconversion unit, a deasphalting unit SDA and optionally an HCK hydrocracking unit and / or an FCC fluidized catalytic cracking unit.
• The figure 2 describes the process scheme according to the invention.
  ∘ Scheme 2 (Invention): Sequencing of a deep hydroconversion unit, an SDA deasphalting unit, an aromatics extraction unit and optionally sending the obtained raffinate to an HCK hydrocracking unit and / or an FCC fluidized catalytic cracking unit.

Description of figures Figure 1 : Prior Art

• ∘ Au moins une première unité d'hydroconversion profonde de la charge en lit bouillonnant 10. Cette technologie est notamment commercialisée sous le nom de procédé H-Oil® _RC. L'unité d'hydroconversion profonde raffine et craque la charge composée d'hydrocarbures de type résidu sous vide obtenu à partir d'une distillation de pétrole brut VR (vacuum residue, résidu sous vide) en des quantités significatives de gaz 21, naphta léger et lourd (heavy naphta HN et light naphta LN) 22, Gasoil (GO) 23 et distillats sous vide (vacuum gasoil, VGO) en une ou deux fractions Light Vacuum GasOil, LVGO distillat sous vide léger 31 et Heavy Vacuum GasOil, HVGO distillat sous vide lourd 32. Ces différents produits sont séparés dans une section de fractionnement atmosphérique 20 et de fractionnement sous vide 30. En fond de la distillation sous vide, il subsiste un flux de résidu sous-vide (VR) 33 non converti envoyé dans l'unité de désasphaltage 40.
• ∘ L'unité de désasphaltage au solvant (solvent deasphalting, SDA) 40 alimentée par le résidu sous vide (VR) 33 non converti de l'unité d'hydroconversion profonde produit une huile désasphaltée (deasphalted oil, DAO) 41 de bonne qualité, compatible avec le fonctionnement d'une unité d'hydrocraquage ou de craquage catalytique en lit fluidisé (FCC) et un asphalte résiduel 42 concentrant la majeure partie des contaminants du résidu sous-vide VR issu de l'unité d'hydroconversion profonde qui a différentes destinations possibles : par exemple, alimentation d'une unité 80 de cokéfaction, ou de gazéification ou de viscoréduction, ou utilisation en fuel solide (flaker) ou liquide ou utilisation en bitume.
• ∘ L'unité d'hydrocraquage en lit fixe (HCK) 60 peut convertir l'huile désasphaltée (DAO) 41 ainsi que le distillat sous vide (Vacuum Gas Oil VGO) 31 et 32 issu de l'unité d'hydroconversion profonde , ainsi que par exemple du SR-VGO (straight run vacuum gas oil, distillat sous vide obtenu par distillation directe de pétrole brut) 91 et d'autres charges compatibles, pour former un flux 71 comprenant des quantités significatives de naphta, Gas Oil et Vacuum Gas Oil. Il reste un flux de VGO non converti (Unconverted Oil, UCO) 62 dont une partie est purgée (bleed). Ce flux non converti 62 peut être utilisé comme base pour des unités d'huile ou utilisé en diluant pour valoriser l'asphalte en fuel lourd. Optionnellement, le distillat sous vide (VGO) produit dans l'unité d'hydrocraquage (HCK) peut être recyclé dans l'unité d'hydroconversion profonde pour être en partie craqué en Gazole et Naphta sans impact significatif sur le fonctionnement de cette unité. Selon une variante, le schéma de raffinerie ne comprend pas d'unité d'hydrocraquage en lit fixe (HCK), mais une unité de craquage catalytique en lit fluidisé (FCC) 70 qui peut aussi être alimentée par l'huile désasphaltée (DAO) 41 et le distillat sous vide (31 et 32) VGO ex H-Oil _RC. Selon une variante, du distillat sous vide obtenu par distillation directe de pétrole brut (SR VGO) 91 peut être envoyé dans le procédé de manière concomitante avec les deux charges précédentes, ainsi que potentiellement avec d'autres charges externes. L'unité de craquage catalytique en lit fluidisé FCC produit une fraction 71 comprenant des quantités significatives de gaz, essence légère et lourde (Heavy Naphta HN et light naphta LN), Light cycle oil (LCO) et Heavy cycle oil (HCO) et une fraction résiduelle lourde 72 appelée « slurry » selon la terminologie anglo-saxonne. La fraction résiduelle lourde (« slurry ») de cette unité de FCC, disponible en quantité limitée, est utilisée avantageusement comme diluant de la charge de l'unité d'hydroconversionprofonde .
• ∘ Selon une autre variante, le schéma comprend à la fois une unité d'hydrocraquage en lit fixe (HCK) 60 et une unité de craquage catalytique en lit fluidisé (FCC) 70. Les deux unités peuvent traiter le gazole sous vide issu de l'hydroconversion en lit bouillonnant (VGO ex Hydroconversion) 31 et 32, l'huile désasphaltée DAO 41, typiquement du Gazole sous vide de distillation directe (SR-VGO) 91 et d'autres charges pour les convertir en des quantités significatives de naphta, gazole et gazole sous vide.

The diagram according to the prior art integrates the following units:

• ∘ At least one first unit for deep hydroconversion of the ebullated bed charge 10. This technology is marketed in particular as the H-Oil® _{RC process} . The deep hydroconversion unit refines and cracks the charge composed of hydrocarbons of vacuum residue type obtained from a distillation of crude oil VR (vacuum residue, residue under vacuum) in significant quantities of gas 21, light and heavy naphtha (heavy naphtha HN and light naphtha LN) 22, Gasoil (GO) 23 and vacuum distillates (vacuum gasoil, VGO) in one or two fractions Light Vacuum GasOil, LVGO Light vacuum distillate 31 and Heavy Vacuum Gas Oil, HVGO heavy vacuum distillate 32. These different products are separated in an atmospheric fractionation and vacuum fractionation section 30. In the bottom of the vacuum distillation, there is a residue stream unconverted vacuum (VR) 33 sent to the deasphalting unit 40.
• ∘ The solvent deasphalting (SDA) unit 40 fed by the unconverted vacuum residue (VR) 33 of the deep hydroconversion unit produces a good quality deasphalted oil (DAO) 41, compatible with the operation of a hydrocracking or fluidized catalytic cracking unit (FCC) and a residual asphalt 42 concentrating the majority of the contaminants of the vacuum residue VR from the deep hydroconversion unit which has different possible destinations: for example, feeding a unit 80 of coking, or gasification or visbreaking, or use in solid fuel (flaker) or liquid or use in bitumen.
• ∘ The fixed bed hydrocracking unit (HCK) 60 can convert the deasphalted oil (DAO) 41 as well as the vacuum distillate (Vacuum Gas Oil VGO) 31 and 32 from the deep hydroconversion unit, and that for example SR-VGO (straight run vacuum gas oil, vacuum distillate obtained by direct distillation of crude oil) 91 and other compatible charges, to form a stream 71 comprising significant quantities of naphtha, Gas Oil and Vacuum Gas Oil. There remains a stream of unconverted VGO (Unconverted Oil, UCO) 62 some of which is purged (bleed). This unconverted stream 62 can be used as a base for oil units or used in diluting to upgrade asphalt to heavy fuel oil. Optionally, the vacuum distillate (VGO) produced in the hydrocracking unit (HCK) can be recycled in the deep hydroconversion unit to be partly cracked in Diesel and Naphtha without impact. significant on the operation of this unit. Alternatively, the refinery scheme does not include a fixed bed hydrocracking unit (HCK), but a fluidized catalytic cracking unit (FCC) 70 which can also be fed with the deasphalted oil (DAO). 41 and vacuum distillate (31 and 32) VGO ex H-Oil _RC . Alternatively, vacuum distillate obtained by direct distillation of crude oil (SR VGO) 91 may be fed into the process concurrently with the two previous feeds, as well as potentially with other external feeds. The FCC fluidized catalytic cracking unit produces a fraction 71 comprising significant amounts of gas, light and heavy gasoline (Heavy Naphta HN and light naphtha LN), light cycle oil (LCO) and heavy cycle oil (HCO) and a heavy residual fraction 72 called "slurry" according to the English terminology. The heavy residual fraction ("slurry") of this FCC unit, available in limited quantities, is advantageously used as a feed diluent for the deep hydroconversion unit.
• According to another variant, the scheme comprises both a fixed bed hydrocracking unit (HCK) 60 and a fluidized catalytic cracking unit (FCC) 70. The two units can treat the vacuum gas oil obtained from the boiling-bed hydroconversion (VGO ex Hydroconversion) 31 and 32, deasphalted oil DAO 41, typically straight-run vacuum gas oil (SR-VGO) 91 and other feeds to convert them to significant amounts of naphtha, diesel and diesel under vacuum.

Figure 2 : Process diagram according to the invention

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.

Alternatively, 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.

According to a variant, 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.

According to one variant, the process according to the invention does not comprise a hydrocracking unit 60 or a catalytic cracking unit 70.

According to another variant, the process according to the invention comprises a hydrocracking unit 60.

According to another variant, the process according to the invention does not comprise a hydrocracking unit 60, but it comprises a catalytic cracking unit 70.

According to another variant, 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.

• ∘ La charge est convertie dans la première étape d'hydroconversion profonde de la charge. Les effluents sont séparés dans une section de fractionnement et en fond du fractionnement sous vide une coupe de résidu sous vide (VR) non converti est séparée.
• ∘ L'unité de désasphaltage SDA est alimentée par le résidu sous vide (VR) non converti et produit une coupe hydrocarbonée desasphaltée DAO qui est envoyée à l'unité d'extraction liquide-liquide et de l'asphalte résiduel qui est valorisé comme dans le schéma antérieur. Eventuellement, tout type d'unité permettant de réduire la teneur en asphalte du résidu pourrait être également installée à la place de l'unité de désasphaltage.
• ∘ L'unité d'extraction des aromatiques produit par extraction liquide-liquide un extrait enrichi en aromatiques et résines et un raffinat appauvri en aromatiques et résines. L'unité d'extraction est alimentée par l'huile désasphaltée (DAO). Elle peut également être alimentée par la purge d'huile non convertie (UCO) issue de l'hydrocraquage et/ou la fraction résiduelle lourde de craquage catalytique suivant les variantes du schéma. L'extrait est utilisé en partie comme diluant aromatique pour l'unité d'hydroconversion de résidu et en partie valorisé en tant qu'huile de fluxage avec l'asphalte résiduel produit par le SDA par exemple pour donner un combustible liquide ou pour entrer dans la composition de bitumes ou pour alimenter une unité de cokéfaction. Le raffinat est une fraction hydrocarbonée appauvrie en aromatiques, en résines et en impuretés par comparaison avec l'huile désasphaltée.
• ∘ Le schéma selon l'invention comprend de préférence une unité d'hydrocraquage en lit fixe (HCK) qui est généralement alimentée par le raffinat provenant de l'unité d'extraction et éventuellement en sus par le distillat sous vide léger (light vacuum gasoil, LVGO) et le distillat sous vide lourd (heavy vacuum gasoil, HVGO) issus de l'unité d'hydroconversion profonde. Le raffinat est une charge bien plus favorable que l'huile désasphaltée DAO pour les performances catalytiques de l'hydrocraquage. L'hydrocraquage produit des quantités significatives de naphta, gazole et distillat. Il reste un flux de distillat sous vide VGO non converti (Unconverted Oil, UCO) dont une partie est purgée (bleed) et peut être envoyée vers l'unité d'extraction car cette coupe concentre les composés polynucléaires aromatiques lourds (Heavy Polynuclear Aromatics, HPNA) réfractaires. Typiquement, les composés polynucléaires aromatiques lourds HPNA dits lourds sont définis comme des composés aromatiques polycycliques ou polynucléaires qui comprennent au moins 4 voire 6 cycles benzéniques condensés dans chaque molécule, comme par exemple le coronène (composé à 24 carbones), le dibenzo(e,ghi) pérylène (26 carbones), coronène (30 carbones) et l'ovaléne (32 carbones). Leur récupération dans l'unité d'extraction permet de recycler du flux non converti (UCO) sans composés polynucléaires aromatiques lourds HPNA à l'entrée de l'hydrocraquage et de valoriser les composés polynucléaires aromatiques lourds dans l'extrait.
• ∘ Dans une variante, le schéma ne comprend pas d'unité d'hydrocraquage, mais une unité de craquage catalytique (FCC). Celle-ci peut aussi être alimentée par le distillat sous vide léger (light vacuum gasoil, LVGO) et le distillat sous vide lourd (heavy vacuum gasoil, HVGO) issus de l'unité d'hydroconversion profonde après fractionnement, et par le raffinat provenant de l'unité d'extraction. Le raffinat est une charge plus favorable que l'huile désasphaltée pour les performances catalytiques et en formation de coke du craquage catalytique. D'une part, la teneur réduite en aromatiques de la charge conduit à diminuer la production de coke. D'autre part, la teneur réduite en azote permet d'atteindre un meilleur rendement. De plus, la teneur réduite en impuretés dans la charge conduit à diminuer la consommation de catalyseur. Enfin, les teneurs en impuretés des produits du craquage catalytique sont réduites. En conséquence, les unités d'hytrotraitement des produits finis en aval opèrent avec des coûts réduits en termes de quantités de catalyseur et ou de durées de cycles.
• ∘ Selon une autre variante, du distillat sous vide obtenu par distillation directe de pétrole brut (SR VGO) ou d'autres charges compatibles peuvent être envoyées de manière concomitante à l'hydrocraquage ou au craquage catalytique en lit fluidisé.
• ∘ Selon une autre variante, le schéma comprend à la fois une unité de craquage catalytique en lit fluidisé (FCC) et une unité d'hydrocraquage en lit fixe (HCK). Au global, les deux unités traitent le gazole sous vide VGO ex unité d'hydroconversion profonde, le raffinat de l'unité d'extraction plus éventuellement du distillat sous vide obtenu par distillation directe de pétrole brut (SR-VGO). Le flux non converti issu de l'unité d'hydrocraquage (UCO) purgé et /ou la fraction résiduelle lourde du craquage catalytique (slurry de FCC) sont envoyés au moins en partie à l'unité d'extraction liquide-liquide.
• ∘ Selon une variante de l'invention, une partie du distillat sous vide (vacuum gasoil, VGO) ou une partie du distillat sous vide lourd (HVGO), issus de l' unité d'hydroconversion profonde après fractionnement, peuvent être envoyés soit à l'unité de désasphaltage en plus du résidu non converti, soit directement à l'unité d'extraction liquide-liquide.
• ∘ Selon une autre variante de l'invention, au moins une partie du résidu atmosphérique peut être envoyée directement à l'unité de désasphaltage.
• ∘ Le raffinat permet aussi de produire avantageusement une base d'huile groupe I.

In the process according to the invention, a liquid-liquid extraction unit of the aromatics and resins treats the deasphalted oil from the deasphalting unit of the unconverted residue of the deep hydroconversion:

• ∘ The load is converted in the first stage of deep hydroconversion of the load. The effluents are separated in a fractionation section and in the bottom of the vacuum fractionation an unconverted vacuum residue (VR) section is separated.
• ∘ The SDA deasphalting unit is fed with the unconverted vacuum residue (VR) and produces a DAO desasphalted hydrocarbon fraction which is sent to the liquid-liquid extraction unit and the residual asphalt which is recovered as in the previous scheme. Optionally, any type of unit to reduce the asphalt content of the residue could also be installed in place of the deasphalting unit.
• ∘ The aromatics extraction unit produced by liquid-liquid extraction an extract enriched in aromatics and resins and a raffinate depleted in aromatics and resins. The extraction unit is fed with deasphalted oil (DAO). It can also be fed by the unconverted oil purge (UCO) from the hydrocracking and / or the catalytic cracking heavy residual fraction according to the variants of the scheme. The extract is used in part as an aromatic diluent for the residue hydroconversion unit and partly upgraded as a fluxing oil with the residual asphalt produced by the SDA for example to give a liquid fuel or to enter the composition of bitumens or to feed a unit of coking. The raffinate is a hydrocarbon fraction depleted of aromatics, resins and impurities as compared to the deasphalted oil.
• The scheme according to the invention preferably comprises a fixed bed hydrocracking unit (HCK) which is generally fed by the raffinate from the extraction unit and optionally in addition by the light vacuum distillate (light vacuum gas oil). , LVGO) and the heavy vacuum distillate (heavy vacuum gas oil, HVGO) from the deep hydroconversion unit. The raffinate is a much more favorable feed than DAO deasphalted oil for the catalytic performance of hydrocracking. Hydrocracking produces significant amounts of naphtha, diesel and distillate. There remains an unconverted VGO (Unconverted Oil, UCO) stream a portion of which is purged (bleed) and can be sent to the extraction unit because this section concentrates the heavy aromatic polynuclear aromatic compounds (Heavy Polynuclear Aromatics, HPNA) refractory. Typically, the so-called heavy HPNA heavy aromatic polynuclear compounds are defined as polycyclic or polynuclear aromatic compounds which comprise at least 4 or even 6 fused benzene rings in each molecule, for example coronene (compound with 24 carbons), dibenzo (e, ghi) perylene (26 carbons), coronene (30 carbons) and ovalene (32 carbons). Their recovery in the extraction unit makes it possible to recycle unconverted flux (UCO) without heavy aromatic polynuclear compounds HPNA at the hydrocracking inlet and to valorize the heavy aromatic polynuclear compounds in the extract.
• In a variant, the scheme does not include a hydrocracking unit, but a catalytic cracking unit (FCC). It can also be fed by the light vacuum distillate (LVGO) and the heavy vacuum gasoil (HVGO) from the deep hydroconversion unit after fractionation, and by the raffinate from of the extraction unit. Raffinate is a more favorable feedstock than deasphalted oil for catalytic performance and coke formation of catalytic cracking. On the one hand, the reduced aromatic content of the feed leads to lower coke production. On the other hand, the reduced nitrogen content makes it possible to achieve a better yield. In addition, the reduced content of impurities in the feed leads to decreased catalyst consumption. Finally, the impurity contents of the products of the catalytic cracking are reduced. As a result, the hytrotreatment units of the downstream finished products operate with reduced costs in terms of catalyst amounts and / or cycle times.
• According to another variant, vacuum distillate obtained by direct distillation of crude oil (SR VGO) or other compatible feedstocks may be sent concomitantly with hydrocracking or fluidized catalytic cracking.
• According to another variant, the scheme comprises both a fluidized catalytic cracking unit (FCC) and a fixed bed hydrocracking unit (HCK). On the whole, the two units process the VGO gas oil ex deep hydroconversion unit, the raffinate of the extraction unit plus possibly the vacuum distillate obtained by direct distillation of crude oil (SR-VGO). The unconverted stream from the purged hydrocracking unit (UCO) and / or the heavy residual fraction of the catalytic cracking (FCC slurry) is sent at least in part to the liquid-liquid extraction unit.
• According to a variant of the invention, part of the vacuum distillate (vacuum gas oil, VGO) or part of the heavy vacuum distillate (HVGO), coming from the deep hydroconversion unit after fractionation, can be sent either to the deasphalting unit in addition to the unconverted residue, either directly to the liquid-liquid extraction unit.
• According to another variant of the invention, at least a part of the atmospheric residue can be sent directly to the deasphalting unit.
• ∘ The raffinate also makes it possible to advantageously produce a Group I oil base.

The operating conditions of the hydroconversion and deasphalting units (SDA) are known to those skilled in the art and identical to the operating conditions of the scheme according to the prior art.

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.

By sending part of the extract obtained to the hydroconversion, this being preferably carried out at iso-conversion, the continuous cycle time of the deep hydroconversion unit is elongated very significantly.

In another approach, by sending part of the extract obtained to the hydroconversion, which is operated with a continuous cycle duration unchanged, the maximum conversion obtained at the deep hydroconversion unit is significantly increased.

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.

By sending all or part of the raffinate produced to the extraction unit in the hydrocracking unit, the catalytic performances of the hydrocracking unit are improved as well as the production of products that can be upgraded compared to a unit supplied by the hydrocracking unit. deasphalted hydrocarbon fraction (DAO) output from the deasphalting unit.

By sending all or part of the unconverted residue (UCO) obtained at the outlet of the hydrocracking unit to the extraction unit, part of the unconverted purified residue of the HPNA heavy aromatic polynuclear compounds is recycled to the inlet of the hydrocracking unit. the HCK and the remainder of the stream, containing the HPNA heavy aromatic polynuclear compounds, is recovered in the extract, instead of the unconverted and usually purged residue being recovered as fuel.

By sending all or part of the raffinate produced to the aromatics extraction unit in the catalytic cracking unit, alone or in admixture with other feeds, the catalytic performances of the catalytic cracking unit (consumption of catalysts, conversion, coke production) are improved as well as the production of recoverable products compared to a unit fed by the deasphalted hydrocarbon fraction leaving the deasphalting unit. In addition, the impurity levels of FCC fluidized catalytic cracking products are reduced. As a result, the hydrotreatment units of the downstream finished products operate with reduced costs on catalyst quantities and / or cycle times.
By sending all or part of the heavy residual fraction (FCC slurry) out of the catalytic cracking unit to the extraction unit, part of this stream can be recycled to the inlet of the catalytic cracking unit. fluidized bed FCC.

The general operating conditions of the units used in the method according to the invention are described below.

Hydroconversion in bubbling bed :

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.

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.

Any type of supported hydroconversion catalyst comprising a hydrodehydrogenating function may be used. 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. For example, 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. This withdrawal and replacement are performed using devices for the continuous operation of this hydroconversion step. 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.

• ∘ Pression : la pression est généralement comprise entre 5 et 35 MPa, de manière préférée entre 10 et 25 MPa, typiquement aux environs de 18 MPa.
• ∘ LHSV (« liquid hourly space velocity » ou vitesse spatiale liquide par heure): la vitesse spatiale liquide est généralement comprise entre 0,1 et 10 h^-1, de manière préférée entre 0,15 et 5 h^-1, typiquement environ 0,25 h^-1.
• ∘ Température moyenne du lit catalytique (, c'est-à-dire la moyenne arithmétique des mesures de température dans le lit catalytique) est généralement comprise entre 300 et 600°C, de manière préférée entre 350 et 510°C, typiquement 420°C.
• ∘ H₂/HC : le ratio Hydrogène/Charge est généralement compris entre : 200 et 1000 m³/m³, de manière préférée entre 300 et 800 m³/m³, de manière très préférée entre 300 et 600 m³/m³.

The operating conditions of the bubbling bed hydroconversion are advantageously as follows:

• ∘ Pressure: the pressure is generally between 5 and 35 MPa, preferably between 10 and 25 MPa, typically around 18 MPa.
• ∘ LHSV (liquid hourly space velocity): the liquid space velocity is generally between 0.1 and 10 h ^-1 , preferably between 0.15 and 5 h ^-1, typically about 0. 25 h ^-1 .
• The average temperature of the catalytic bed (that is to say the arithmetic average of the temperature measurements in the catalytic bed) is generally between 300 and 600 ° C., preferably between 350 and 510 ° C., typically 420 ° C. vs.
• ∘ H ₂ / HC: the Hydrogen / Charge ratio is generally between: 200 and 1000 m ³ / m ³ , preferably between 300 and 800 m ³ / m ³ , very preferably between 300 and 600 m ³ / m ³ .

Deep ebullated bed hydroconversion reduces Conradson's carbon input flux by approximately 50-95% and its nitrogen content by approximately 30-95%.

Splitting :

In atmospheric fractionation, 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.

In the vacuum fractionation section (vacuum distillation column), 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.

Solvent deasphalting :

This operation makes it possible to extract a large part of the asphaltenes and to reduce the metal content. During this deasphalting, the latter elements are concentrated in an effluent called asphalt, here called residual asphalt.

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.

According to the invention, 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.

The solvent used in the deasphalting step is only a paraffinic solvent.

Preferably, 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.

Depending on the solvent used, the deasphalted oil yield and the quality of this oil may vary. By way of example, when passing from a solvent containing 3 carbon atoms to a solvent containing 7 carbon atoms, the oil yield increases but, in return, the levels of impurities (asphaltenes, metals, carbon Conradson, sulfur, nitrogen ...) also increase.

Moreover, for a given solvent, the choice of operating conditions, in particular the temperature and the quantity of solvent injected, has an impact on the deasphalted oil yield and on the quality of this oil. The person skilled in the art can choose the optimum conditions for obtaining an asphaltene content of less than 3000 ppm. 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.

According to a preferred embodiment, 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. In the settling zone at the bottom of the extractor, it is possible to introduce 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.

Furthermore, according to a preferred embodiment, 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. Indeed, 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.

• ∘ De manière préférée, le solvant utilisé est un solvant paraffinique en C3,C4 ou C5, de préférence C4 dans l'invention. Le solvant très préféré dans le cadre de l'invention est le butane.
• ∘ Le taux de solvant est généralement compris entre 2,5/1 et 20/1, de manière préférée entre 5/1 et 15/1 et de manière plus préférée entre 5/1 et 10/1, typiquement 6/1 en volume globalement (une partie ajoutée en tête et une partie en fond d'extracteur).
• ∘ La pression est généralement comprise entre 2 et 10 MPa, de manière préférée entre 3 et 6 MPa, de manière très préférée comprise entre 4 et 5 MPa, typiquement 4,5 MPa.
• ∘ La température en tête d'extracteur est généralement comprise entre 50°C et 250°C et la température en fond d'extracteur entre 30°C et 220°C
• ∘ Pour un solvant comprenant 4 atomes de carbone (C4) : la température en tête d'extracteur est généralement comprise entre 70 et 150°C, de manière préférée entre 90 et 130 °C, de manière très préférée 120°C. La température en fond d'extracteur est généralement comprise entre 40 et 120°C, de préférence entre 60 et 100°C.
• ∘ Pour un solvant comprenant 5 atomes de carbone (C5) : la température en tête d'extracteur est généralement comprise entre 120 et 240°C, de manière préférée entre 150 et 210 °C, de manière très préférée 180°C. La température en fond d'extracteur est généralement comprise entre 90 et 210°C, de préférence entre 120 et 180°C.

The operating conditions of the deasphalting unit (SDA) are advantageously as follows:

• Preferably, the solvent used is a C3, C4 or C5 paraffinic solvent, preferably C4 in the invention. The most preferred solvent in the context of the invention is butane.
• The level of solvent is generally between 2.5 / 1 and 20/1, preferably between 5/1 and 15/1 and more preferably between 5/1 and 10/1, typically 6/1 by volume. globally (a part added at the head and a part at the bottom of the extractor).
• The pressure is generally between 2 and 10 MPa, preferably between 3 and 6 MPa, very preferably between 4 and 5 MPa, typically 4.5 MPa.
• ∘ The temperature at the extractor head is generally between 50 ° C and 250 ° C and the temperature at the bottom of the extractor between 30 ° C and 220 ° C
• ∘ For a solvent comprising 4 carbon atoms (C4): the temperature at the extractor head is generally between 70 and 150 ° C, preferably between 90 and 130 ° C, very preferably 120 ° C. The temperature at the bottom of the extractor is generally between 40 and 120 ° C., preferably between 60 and 100 ° C.
• For a solvent comprising 5 carbon atoms (C5): the temperature at the extractor head is generally between 120 and 240 ° C, preferably between 150 and 210 ° C, very preferably 180 ° C. The temperature at the bottom of the extractor is generally between 90 and 210 ° C., preferably between 120 and 180 ° C.

Extraction of aromatics:

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. The solvent used is a known solvent for extracting aromatic compounds preferentially.

It is important to underline that 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 ). For example, in the case of furfural as an extraction solvent, having a boiling point of 162 ° C, the compounds C10-, compounds representative of the gasoline / naphtha fraction, will be lost. By treating only the heavy fraction containing compounds having boiling points above the boiling point of the extraction solvent, there is no loss of these compounds greater than the boiling point of the extraction solvent ( compounds C10-). In addition, it avoids the contamination of the solvent with the compounds C10- as well as possible stages of treatment of the solvent for recycling. Solvent recovery is therefore more efficient and economical.

As 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.

In the context of the invention, 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. Preferably, 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.

After contact of the solvent with the heavy fraction, two phases are formed: (i) the extract, consisting of the parts of the heavy fraction that are not soluble in the solvent (and highly concentrated in aromatics) and (ii) 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.

Downstream units

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).

Hydrocracking

In the context of the present invention, the term "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. In the 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.

Optionally, 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).

Catalytic cracking in a fluidized bed

Fluidized catalytic cracking (FCC) 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. Depending on the conradson carbon content of the feed, the coke yield requires a specific sizing of the unit to satisfy the heat balance.

• Lorsque l'unité de craquage catalytique fonctionne en écoulement ascendant, les conditions opératoires sont les suivantes :
  • Température sortie riser comprise entre 520°C et 600°C,
  • Rapport C/O compris entre 6 et 14, et préférentiellement compris entre 7 et 12,
  • Temps de résidence compris entre 1 et 10 s, et préférentiellement compris entre 2 et 6 s.
• Lorsque l'unité de craquage catalytique fonctionne en écoulement descendant, les conditions opératoires sont les suivantes :
  • Température de sortie du réacteur comprise entre 580°C et 630°C,
  • Rapport C/O compris entre 15 et 40, et préférentiellement compris entre 20 et 30,
  • Temps de résidence compris entre 0,1 et 1 s, et préférentiellement compris entre 0,2 et 0,7 s.

In the context of the invention, the fluidized catalytic cracking unit is supplied with at least a portion of the raffinate produced in the aromatics extraction unit, alone or as a mixture with other fillers. The catalytic performance of the catalytic cracking unit (catalyst consumption, conversion, coke production) as well as the quantity and quality of the recoverable products are improved compared to a unit fed by the deasphalted hydrocarbon fraction leaving the unit of deasphalting. As a result, the hydrotreatment units of the downstream finished products operate with reduced costs on catalyst quantities and / or cycle times.
By sending all or part of the heavy residual fraction (FCC slurry) out of the catalytic cracking unit to the aromatics extraction unit, a part of this residual fraction, which is depleted in aromatics, can moreover be recycled at the same time. inlet of the FCC fluidized catalytic cracking unit.

• When the catalytic cracking unit operates in upward flow, the operating conditions are as follows:
  • Riser outlet temperature between 520 ° C and 600 ° C,
  • C / O ratio between 6 and 14, and preferably between 7 and 12,
  • Residence time between 1 and 10 s, and preferably between 2 and 6 s.
• When the catalytic cracking unit operates in downward flow, the operating conditions are as follows:
  • Reactor outlet temperature between 580 ° C and 630 ° C,
  • C / O ratio between 15 and 40, and preferably between 20 and 30,
  • Residence time between 0.1 and 1 s, and preferably between 0.2 and 0.7 s.

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).

EXAMPLE :

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. <u> 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.

In this example, 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.

However, according to another variant, 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). 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.

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.

In the aromatics extraction section, 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 operating conditions of the H-Oil® conversion units that process the residues, the solvent deasphalting unit (SDA) and the liquid-liquid Aromatic Extraction are summarized in Table 2. <u> Table 2: </ u> Operating conditions of the units Operating parameters H-Oil® SDA Aromatic Extraction VVH Liquid h-1 0.25 - - Pressure MPa 18 4.5 4.5 Average temperature of the catalytic bed * ° C 416 - - Extractor temperature 120 in the lead 100 in the lead 90 in the background 70 in the background H2 / Charge m3 / m3 400 - - Solvent / charge Extractor inlet Extractor bottom m3 / m3 - 2/1 1.8 / 1 m ³ / m ³ 4/1 4/1 catalysts TEX 2731 - - Catalysts composition NiMo / Al ₂ O ₃ - - Solvent - butanes furfural

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.

The use of aromatic diluent in the deep hydroconversion unit makes it possible to improve the duration of continuous operation thereof in a very significant manner as shown in Table 3. <u> Table 3: </ u> impact of the aromatic diluent from the extraction unit on the performance of the H-Oil® hydroconversion unit. Operating conditions Case without aromatic diluent Case with aromatic diluent Flow Rate t / h 100 100 Flow Aromatic Thinner t / h 0 10 H-OIL® _RC Conversion% wt 60 60 Cycle time H-OIL® _RC 2 years Four years

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 use of the aromatic diluent also makes it possible to obtain an increased production of recoverable finished products as shown in Table 4 below. <u> Table 4: </ u> Load and products of the hydroconversion unit with and without aromatic diluent, for a conversion of 60% wt Without aromatic diluent With aromatic diluent Charges for hydroconversion: Load, t / h 100 100 Extract used as thinner, t / h 0 10 Hydrogen, t / h 1.42 1.56 Products of hydroconversion C1-C4, t / h 2.94 3.08 Naphtha, t / h 7.45 7.83 Diesel (GO), t / h 23.23 24.39 Vacuum Diesel (VGO), t / h 28.40 29.82 Unconverted residue, t / h 36.78 43.78

At fixed conversion, with the use of the extract as an aromatic diluent, 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. <u> Table 5: </ u> properties of the deasphalted oil (DAO) at the inlet, the raffinate and the extract at the outlet of the extraction unit Property 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 Nitrogen ppm wt 4000 900 6,400 Sulfur %weight 1.16 0.57 1.60 Aromatic content %weight 47 55 41 Resin content %weight 27 0 48 Hydrogen %weight 11.1 14.0 9.0

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.

Claims (14)

1. A process for deep conversion of a heavy hydrocarbon feed, comprising the following steps:

   a) ebullated bed hydroconversion of the feed, in the presence of hydrogen, in a hydroconversion section comprising at least one three-phase reactor containing at least one supported hydroconversion catalyst,

   b) atmospheric fractionation of at least a portion of the hydroconverted liquid effluent obtained from step a) in an atmospheric fractionation section in order to produce a fraction comprising a gasoline cut and a gas oil cut, and an atmospheric residue;

   c) vacuum fractionation of at least a portion of the atmospheric residue obtained from step b) in a vacuum fractionation section in order to obtain a vacuum gas oil fraction comprising light vacuum distillates (LVGO) and heavy vacuum distillates (HVGO) and an unconverted vacuum residue fraction,

   d) deasphalting at least a portion of the unconverted vacuum residue fraction obtained from step c) in a deasphalting section only by means of a paraffinic solvent under conditions for obtaining a hydrocarbon cut depleted in asphaltenes, termed deasphalted oil, and residual asphalt,

   e) liquid/liquid extraction carried out on the hydrocarbon cut depleted in asphaltenes in a section for the extraction of aromatics by means of a polar solvent under conditions for extracting aromatics in order to produce an extract enriched in aromatics and resins and a raffinate depleted in aromatics and resins, at least a portion of the extract being sent to the inlet to the hydroconversion section as an aromatic diluent.
2. The process as claimed in claim 1, comprising:

   • a step f1) for hydrocracking at least a portion of the raffinate obtained from the extraction step e) in a reactor comprising at least one fixed bed of hydrocracking catalyst in order to produce a gasoline fraction, a gas oil fraction (GO), vacuum gas oil (VGO) and an unconverted oil fraction (UCO),

   • and/or a step f2) for fluidized bed catalytic cracking of at least a portion of the raffinate obtained from the extraction e) in a fluidized bed reactor in order to produce a gaseous fraction, a gasoline fraction, a gas oil fraction and a heavy residual fraction termed slurry.
3. The process as claimed in claim 2, in which the unconverted oil fraction obtained from hydrocracking and/or the heavy residual fraction obtained from catalytic cracking are sent to the aromatics extraction section.
4. The process as claimed in one of the preceding claims, in which a portion of the extract is used as a flux oil as a mixture with residual asphalt produced by the deasphalting step d) in order to provide a liquid fuel or to form part of the bitumen composition or to be supplied to a coking unit.
5. The process as claimed in one of claims 2 to 4, in which the raffinate produced by the aromatics extraction unit is sent to the hydrocracking unit and/or to the catalytic cracking unit together with one or more other feeds selected from straight run vacuum gas oil (straight run VGO) and light (LVGO) and heavy vacuum distillates (HVGO) obtained from the outlet from the vacuum fractionation c).
6. The process as claimed in one of the preceding claims, in which at least a portion of the light vacuum distillate (LVGO) or of the heavy vacuum distillate (HVGO) is sent to the aromatics extraction section.
7. The process as claimed in one of the preceding claims, in which a portion of the atmospheric residue is sent directly to the deasphalting section.
8. The process as claimed in one of the preceding claims, in which the hydroconversion step a) is operated at an absolute pressure in the range 5 to 35 MPa, at a weighted average catalytic bed temperature of 300°C to 600°C, at an hourly space velocity of 0.1 h^-1 to 10 h^-1 and at a ratio of hydrogen to feed H₂/HC of 200 to 1000 m³/m³.
9. The process as claimed in one of claims 2 to 8, in which the hydrocracking step f1) is operated at an average catalytic bed temperature in the range 300°C to 550°C, a pressure in the range 5 to 35 MPa, and a liquid space velocity in the range 0.1 to 10 h^-1.
10. The process as claimed in one of claims 2 to 9, in which the fluidized bed catalytic cracking step f2) is operated in upflow mode with a reactor outlet temperature in the range 520°C to 600°C, a C/O ratio in the range 6 to 14, and a dwell time in the range 1 to 10 s, or in downflow mode with a reactor outlet temperature in the range 580°C to 630°C, a C/O ratio in the range 15 to 40, and with a dwell time in the range 0.1 to 1 s.
11. The process as claimed in one of claims 1 to 10, in which the deasphalting step is carried out in an extraction column, the solvent comprising at least 50% by weight of hydrocarbon compounds containing 3 to 7 carbon atoms, the extracter head temperature being in the range 50°C to 250°C, the extracter bottom temperature being in the range 30°C to 220°C, and the pressure being in the range 2 to 10 MPa.
12. The process as claimed in claim 11, in which the solvent is butane.
13. The process as claimed in one of the preceding claims, in which the liquid/liquid extraction is carried out with the aid of a solvent selected from furfural, N-methyl-2-pyrrolidone (NMP), sulfolane, dimethylformamide (DMF), dimethylsulphoxide (DMSO), phenol, or a mixture of these solvents in equal or different proportions, with a solvent/feed ratio of 0.5/1 to 3/1, at a temperature in the range between ambient temperature and 150°C, and at a pressure in the range between atmospheric pressure and 2 MPa.
14. The process as claimed in one of the preceding claims, in which the feed is selected from heavy hydrocarbon feeds of the atmospheric residue or vacuum residue type obtained, for example, by straight run distillation of an oil cut or by vacuum distillation of crude oil, distillate type feeds such as vacuum gas oil or deasphalted oils, asphaltenes obtained by solvent deasphalting oil residues, coal in suspension in a hydrocarbon fraction such as gas oil obtained from vacuum distillation of crude oil, for example, or in fact the distillate obtained from coal liquefaction, alone or as a mixture.

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