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EP0256940B1 - Process for deasphaltizing a heavy hydrocarbon feedstock - Google Patents

Process for deasphaltizing a heavy hydrocarbon feedstock Download PDF

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Publication number
EP0256940B1
EP0256940B1 EP87401848A EP87401848A EP0256940B1 EP 0256940 B1 EP0256940 B1 EP 0256940B1 EP 87401848 A EP87401848 A EP 87401848A EP 87401848 A EP87401848 A EP 87401848A EP 0256940 B1 EP0256940 B1 EP 0256940B1
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EP
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Prior art keywords
charge
shearing
solvent
phase
process according
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EP87401848A
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German (de)
French (fr)
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EP0256940A1 (en
Inventor
Roben Loutaty
Gilles Trinquet
Pierre Maroy
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TotalEnergies Marketing Services SA
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Total France SA
Compagnie de Raffinage et de Distribution Total France 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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/003—Solvent de-asphalting

Definitions

  • the present invention relates to a process for deasphalting a heavy hydrocarbon feed.
  • heavy hydrocarbon filler is meant, within the meaning of the present invention, a filler having a density at 15 ° C greater than about 930 kg / m 3 , composed essentially of hydrocarbons, but also containing other chemical compounds which, in addition to carbon and hydrogen atoms, have heteroatoms, such as oxygen, nitrogen, sulfur and metals, such as vanadium or nickel.
  • This charge can be constituted, in particular, by a crude oil or a heavy oil having the density indicated above.
  • the feedstock can also come from the fractionation or processing of crude oil, heavy oil, oil shale or even coal. It may thus be the residue from the distillation under reduced pressure or the residue from the distillation at atmospheric pressure of the starting materials mentioned above or, for example, the products obtained by the heat treatment of these starting materials or their distillation residues.
  • the heaviest part of the heavy hydrocarbon charges consists of a mixture of an oily phase and an asphaltic phase.
  • the asphaltic phase is the phase which precipitates by the addition of a low boiling point hydrocarbon (for example, propane, butane, pentane, hexane, heptane), the oily phase being soluble in said hydrocarbon.
  • a low boiling point hydrocarbon for example, propane, butane, pentane, hexane, heptane
  • the oily phase that is to say the lighter phase, which is economically more advantageous than the asphaltic phase. It can indeed serve as a catalytic cracking charge leading to the production of light products. It can also serve as a filler for obtaining bases for lubricating oils. The value of these products is higher than those of the fuels and bitumens obtained from the asphalt phase.
  • heavy hydrocarbon feedstocks contain compounds having, in addition to hydrogen and carbon atoms, heteroatoms, such as oxygen, nitrogen, sulfur and metals. Some of these compounds, especially those having metals, are contained in particular in the asphalt phase.
  • Asphaltenes like resins have polycyclic aromatic structures. Next to the aromatic rings are thiophenic and pyridine rings. But resins have less condensed structures than asphaltenes and lower molecular weights.
  • the compounds which precipitate by addition to the charge of a saturated aliphatic hydrocarbon having from 5 to 7 carbon atoms are generally designated under the name of asphaltenes: pentane, hexane, heptane.
  • pentane, hexane, heptane pentane, hexane, heptane.
  • a hydrocarbon with a lower boiling point for example propane.
  • this distinction is conventional and it is obvious that, if a given hydrocarbon is used for treating a charge at a given temperature, it will be possible, if the hydrocarbon and the temperature are suitable, to obtain the precipitation of compounds of the type asphaltenes. If the charge freed from asphaltenes is then treated with the same hydrocarbon at a higher temperature, precipitation of the resins can be obtained.
  • the oily phase and the asphaltic phase are separated in the well-known deasphalting process, as indicated above, by the operation which consists in extracting the oily phase from a hydrocarbon charge using a body called by man. solvent art.
  • the solvent is both a solvent for the oily phase and a precipitant for the asphalt phase. In the remainder of this description, it will simply be called a solvent.
  • the deasphalting can be carried out in a single step, obtaining, in this case, an oily phase and an asphaltic phase, the latter containing both the asphaltenes and the resins. It can also be carried out in two stages, with the use of two different solvents and / or different operating conditions in the two stages.
  • the oily phase, the resins and the asphaltenes are obtained separately in this two-step process (see for example French patent application No. 86 06994, filed on May 15, 1986, in the name of the applicant).
  • FR-A-716 703 describes a deasphalting process in which the precipitated asphalt passes through a screw and is therefore subjected to shearing, while the treated load is simply agitated in a tower intended to ensure the mixing of the constituents and the homogenization of this mixture.
  • FR-A-2 218 920 describes a deasphalting tower in which a rotor drives blades in different compartments which successively borrows the load to be treated. No information is given on the rotation speeds of the blades.
  • the object of the present invention is therefore, in a deasphalting process, to increase the yield in the oily phase, while retaining the latter the characteristics desired for the application which is targeted.
  • a “Conradson” residue (measured according to the AFNOR NFT 60-116 standard) of less than 10% by weight is desirable.
  • shearing is meant the application of a high stress to the load, whether diluted or not.
  • the shear can be applied to the load after and / or before the addition of at least part of the solvent.
  • the shearing can in particular be obtained by forced passage of the load, optionally containing at least part of the solvent, in an air gap limited by a fixed part and a coaxial part rotating therein.
  • the shearing can also be caused by the use of a turbine or any other means of agitation, possibly in the deasphalting tower.
  • the deasphalting operation which follows the shearing or which is carried out at the same time as this, can be carried out in one or two stages.
  • This drawing schematically represents a deasphalting unit comprising a shearing installation.
  • the heavy hydrocarbon feedstock for example an oil with a density at 15 ° C. greater than 930 kg / m 3 , is introduced via line 1 into the middle part of an extractor liquid-liquid 2.
  • the oily phase is extracted from the feedstock with a solvent, which is introduced into the extractor through line 3.
  • This solvent can in particular be an aliphatic hydrocarbon, saturated or unsaturated, having 2 to 8 atoms carbon, preferably from 3 to 5 carbon atoms, or the formula diapers of hydrocarbons, called distillates, having from 2 to 8 carbon atoms, or mixtures of all the hydrocarbons previously mentioned.
  • the solvent for starting the unit comes from a source external to the unit via line 4. Losses of solvent can be compensated by an external make-up, brought by line 4.
  • the pressure inside the extractor 2 can be between 20 ⁇ 10 5 and 1 ⁇ 10 7 absolute pascals, the temperature between 30 and 300 ° C, the mass rate being between 1 and 10.
  • the oily phase dissolved in solvent is collected at the head of extractor 2, via line 5.
  • This mixture is conducted by line 5 in a fractionation assembly 6.
  • this assembly has not been shown in detail, but it generally includes a regulator controlling a pressure drop and evaporators.
  • solvent is collected, on the one hand, by line 7, which is recycled to extractor 2 via line 3 and, on the other hand, by the line 8, the oily phase.
  • the precipitated asphalt phase and the solvent are recovered at the bottom of the extractor 2.
  • This mixture is conducted by line 10 in a fractionation assembly 11, which generally comprises an oven or an exchanger with a hot fluid, an evaporator and a water vapor drive column.
  • Part of the solvent in line 3 can optionally be brought to line 1 via line 14 to predilute the charge.
  • This restriction can also be placed after or before the intersection of lines 1 and 14, before the deasphalting tower 2.
  • This example relates to deasphalting tests carried out on a residue from the distillation under reduced pressure of the residue from the distillation at atmospheric pressure of a Safaniya crude oil, with and without prior shearing of said residue.
  • This example relates to deasphalting tests carried out on two loads C 1 and C 2 , with and without prior shearing of the loads. When it is carried out, the shearing takes place in the presence of solvent.
  • the feedstock C is identical to that used in Example 1 and is therefore constituted by a distillation residue under reduced pressure of an atmospheric distillation residue of a Safaniya crude oil. Its characteristics are given in Example 1.
  • the feed C 2 consists of a residue from the distillation under atmospheric pressure of a Maya crude oil.
  • the shearing is carried out at a temperature of 95 ° C. in a turbine having an air gap of 0.6 mm and a crenellated head (2 mm of space between the teeth) with a rotational speed of 17,000 rpm.
  • the solvent contains 78.1% by weight of normal pentane and 21.9% by weight of normal heptane.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Description

La présente invention concerne un procédé de désasphaltage d'une charge hydrocarbonée lourde.The present invention relates to a process for deasphalting a heavy hydrocarbon feed.

Par charge hydrocarbonée lourde, on entend, au sens de la présente invention, une charge ayant une masse volumique à 15° C supérieure à environ 930 kg/m3, composée essentiellement d'hydrocarbures, mais contenant également d'autres composés chimiques qui, outre des atomes de carbone et d'hydrogène, possèdent des hétéroatomes, comme l'oxygène, l'azote, le soufre et des métaux, comme le vanadium ou le nickel.By heavy hydrocarbon filler is meant, within the meaning of the present invention, a filler having a density at 15 ° C greater than about 930 kg / m 3 , composed essentially of hydrocarbons, but also containing other chemical compounds which, in addition to carbon and hydrogen atoms, have heteroatoms, such as oxygen, nitrogen, sulfur and metals, such as vanadium or nickel.

Cette charge peut être constituée, notamment, par un pétrole brut ou une huile lourde ayant la masse volumique indiquée ci-dessus.This charge can be constituted, in particular, by a crude oil or a heavy oil having the density indicated above.

La charge peut provenir également du fractionnement ou du traitement du pétrole brut, d'une huile lourde, de schistes bitumineux ou même de charbon. Il peut s'agir ainsi du résidu de la distillation sous pression réduite ou du résidu de la distillation sous pression atmosphérique des produits de départ cités ci-dessus ou, par exemple, des produits obtenus par le traitement thermique de ces produits de départ ou de leurs résidus de distillation.The feedstock can also come from the fractionation or processing of crude oil, heavy oil, oil shale or even coal. It may thus be the residue from the distillation under reduced pressure or the residue from the distillation at atmospheric pressure of the starting materials mentioned above or, for example, the products obtained by the heat treatment of these starting materials or their distillation residues.

Une tendance est apparue ces dernières années, de chercher à valoriser de plus en plus les produits hydrocarbonés ayant une masse volumique élevée, ce qui n'était pas le cas auparavant. Cette recherche de la valorisation des produits lourds est devenue plus pressante, car il est prévu que la demande de produits légers comme les carburants devrait augmenter relativement plus rapidement que celle des produits plus lourds, comme les fiouls.A trend has appeared in recent years, to seek to develop more and more hydrocarbon products with a high density, which was not the case before. This quest for the valuation of heavy products has become more pressing, since it is expected that the demand for light products such as fuels should increase relatively faster than that of heavier products, such as fuel oils.

La partie la plus lourde des charges hydrocarbonées lourdes est constituée d'un mélange d'une phase huileuse et d'une phase asphaltique.The heaviest part of the heavy hydrocarbon charges consists of a mixture of an oily phase and an asphaltic phase.

La phase asphaltique est la phase qui précipite par addition d'un hydrocarbure à bas pointd'ébullition (par exemple, propane, butane, pentane, hexane, heptane), la phase huileuse étant soluble dans ledit hydrocarbure.The asphaltic phase is the phase which precipitates by the addition of a low boiling point hydrocarbon (for example, propane, butane, pentane, hexane, heptane), the oily phase being soluble in said hydrocarbon.

C'est, en fait, la phase huileuse, c'est-à-dire la phase la plus légère, qui est économiquement plus intéressante que la phase asphaltique. Elle peut en effet servir de charge de craquage catalytique conduisant à l'obtention de produits légers. Elle peut également servir de charge pour l'obtention de bases pour huiles lubrifiantes. La valeur de ces produits est plus élevée que celles des combustibles et des bitumes obtenus à partir de la phase asphaltique.It is, in fact, the oily phase, that is to say the lighter phase, which is economically more advantageous than the asphaltic phase. It can indeed serve as a catalytic cracking charge leading to the production of light products. It can also serve as a filler for obtaining bases for lubricating oils. The value of these products is higher than those of the fuels and bitumens obtained from the asphalt phase.

Ainsi qu'il a été dit ci-dessus, les charges hydrocarbonées lourdes contiennent des composés possédant, outre des atomes d'hydrogène et de carbone, des hétéroatomes, comme l'oxygène, l'azote, le soufre et des métaux. Certains de ces composés, notamment ceux possédant des métaux, sont contenus en particulier dans la phase asphaltique.As mentioned above, heavy hydrocarbon feedstocks contain compounds having, in addition to hydrogen and carbon atoms, heteroatoms, such as oxygen, nitrogen, sulfur and metals. Some of these compounds, especially those having metals, are contained in particular in the asphalt phase.

On a l'habitude de distinguer deux familles dans les composés constituant la phase asphaltique: les résines et les asphaltènes. Les asphaltènes comme les résines ont des structures aromatiques polycycliques. A côté des cycles aromatiques se trouvent des cycles thiophéniques et pyridiniques. Mais les résines ont des structures moins condensées que les asphaltènes et des poids moléculaires plus faibles.We are used to distinguishing two families in the compounds constituting the asphalt phase: resins and asphaltenes. Asphaltenes like resins have polycyclic aromatic structures. Next to the aromatic rings are thiophenic and pyridine rings. But resins have less condensed structures than asphaltenes and lower molecular weights.

On désigne généralement sous le nom d'asphaltènes les composés qui précipitent par addition à la charge d'un hydrocarbure aliphatique saturé ayant de 5 à 7 atomes de carbone : pentane, hexane, heptane. Ainsi, selon la norme AFNOR NFT 60-115, la teneur en asphaltènes d'un produit est déterminée par une précipitation à l'aide d'un normal heptane à l'ébullition.The compounds which precipitate by addition to the charge of a saturated aliphatic hydrocarbon having from 5 to 7 carbon atoms are generally designated under the name of asphaltenes: pentane, hexane, heptane. Thus, according to AFNOR standard NFT 60-115, the asphaltene content of a product is determined by precipitation using a normal heptane at boiling point.

Les résines précipitent en même temps que les asphaltènes, quand on utilise un hydrocarbure de plus faible point d'ébullition, par exemple le propane. En fait, cette distinction est conventionnelle et il est évident que, si on emploie, pour traiter une charge, un hydrocarbure donné à une température donnée, on pourra, si l'hydrocarbure et la température sont appropriés, obtenir la précipitation de composés du type asphaltènes. Si on traite ensuite la charge débarrassée des asphaltènes par le même hydrocarbure à une température plus élevée, on pourra obtenir la précipitation des résines.Resins precipitate at the same time as asphaltenes, when using a hydrocarbon with a lower boiling point, for example propane. In fact, this distinction is conventional and it is obvious that, if a given hydrocarbon is used for treating a charge at a given temperature, it will be possible, if the hydrocarbon and the temperature are suitable, to obtain the precipitation of compounds of the type asphaltenes. If the charge freed from asphaltenes is then treated with the same hydrocarbon at a higher temperature, precipitation of the resins can be obtained.

La phase huileuse et la phase asphaltique sont séparées dans le procédé bien connu de désasphaltage, comme indiqué précédemment, par l'opération qui consiste à extraire d'une charge hydrocarbonée la phase huileuse à l'aide d'un corps appelé par l'homme de l'art solvant. Le solvant est à la fois un solvant de la phase huileuse et un précipitant de la phase asphaltique. Dans la suite de la présente description, on l'appellera simplement solvant.The oily phase and the asphaltic phase are separated in the well-known deasphalting process, as indicated above, by the operation which consists in extracting the oily phase from a hydrocarbon charge using a body called by man. solvent art. The solvent is both a solvent for the oily phase and a precipitant for the asphalt phase. In the remainder of this description, it will simply be called a solvent.

Le solvant peut être choisi dans le groupe constitué par:

  • - les hydrocarbures aliphatiques, saturés ou non saturés, ayant de 2 à 8 atomes de carbone, seuls ou en mélange,
  • - les mélanges d'hydrocarbures, appelés distillats, ayant des poids moléculaires voisins de ceux des hydrocarbures, ayant de 2 à 8 atomes de carbone,
  • - les mélanges de tous les hydrocarbures précédemment cités.
The solvent can be chosen from the group consisting of:
  • - aliphatic hydrocarbons, saturated or unsaturated, having 2 to 8 carbon atoms, alone or as a mixture,
  • - mixtures of hydrocarbons, called distillates, having molecular weights close to those of hydrocarbons, having 2 to 8 carbon atoms,
  • - mixtures of all the previously mentioned hydrocarbons.

Le désasphaltage peut être effectué en une seule étape, avec obtention, dans ce cas, d'une phase huileuse et d'une phase asphaltique, cette dernière contenant à la fois les asphaltènes et les résines. Il peut également être effectué en deux étapes, avec utilisation de deux solvants différents et/ou des conditions opératoires différentes dans les deux étapes. On obtient de façon séparée, dans ce procédé en deux étapes, la phase huileuse, les résines et les asphaltènes (voir par exemple la demande de brevet français n° 86 06994, déposée le 15 mai 1986, au nom de la demanderesse).The deasphalting can be carried out in a single step, obtaining, in this case, an oily phase and an asphaltic phase, the latter containing both the asphaltenes and the resins. It can also be carried out in two stages, with the use of two different solvents and / or different operating conditions in the two stages. The oily phase, the resins and the asphaltenes are obtained separately in this two-step process (see for example French patent application No. 86 06994, filed on May 15, 1986, in the name of the applicant).

FR-A-716 703 décrit un procédé de désasphaltage dans lequel l'asphalte précipité passe à travers une vis et est donc soumis à un cisaillement, tandis que la charge traitée est simplement agitée dans une tour destinée à assurer le mélange des constituants et l'homogénéisation de ce mélange.FR-A-716 703 describes a deasphalting process in which the precipitated asphalt passes through a screw and is therefore subjected to shearing, while the treated load is simply agitated in a tower intended to ensure the mixing of the constituents and the homogenization of this mixture.

FR-A-2 218 920 décrit une tour de désasphaltage dans laquelle un rotor entraîne des pales dans différents compartiments qu'emprunte successivement la charge à traiter. Aucune information n'est donnée sur les vitesses de rotation des pales.FR-A-2 218 920 describes a deasphalting tower in which a rotor drives blades in different compartments which successively borrows the load to be treated. No information is given on the rotation speeds of the blades.

Dans de tels procédés, comme il a été dit précédemment, c'est la phase huileuse qui, économiquement, est la plus intéressante. On a donc intérêt, dans un procédé de désasphaltage, qu'il soit à une ou deux étapes, à chercher à obtenir un rendement maximum en phase huileuse. Il est entendu que cette recherche d'un rendement maximum de phase huileuse ne doit pas nuire aux caractéristiques de celle-ci.In such processes, as has been said previously, it is the oily phase which is economically the most advantageous. It is therefore advantageous, in a deasphalting process, whether it is in one or two stages, to seek to obtain a maximum yield in the oily phase. It is understood that this search for a maximum yield of oily phase must not harm the characteristics of the latter.

Le but de la présente invention est donc, dans un procédé de désasphaltage, l'augmentation du rendement en phase huileuse, tout en conservant à celle-ci les caractéristiques désirées pour l'application qui est visée. Ainsi, par exemple, pour une application comme charge de craquage catalytique, un résidu «Conradson» (mesuré selon la norme AFNOR NFT 60-116) inférieur à 10% en poids est souhaitable.The object of the present invention is therefore, in a deasphalting process, to increase the yield in the oily phase, while retaining the latter the characteristics desired for the application which is targeted. Thus, for example, for an application as a catalytic cracking charge, a “Conradson” residue (measured according to the AFNOR NFT 60-116 standard) of less than 10% by weight is desirable.

A cet effet, l'invention a pour objet un procédé de désasphaltage d'une charge hydrocarbonée lourde constituée d'une phase huileuse et d'une phase asphaltique, ayant une masse volumique à 15° C supérieure à environ 930 kg/m3 et composée essentiellement d'hydrocarbures, mais qui contient également d'autres composés chimiques qui, outre des atomes de carbone et d'hydrogène, possèdent des hétéroatomes, ce procédé comprenant au moins:

  • - une opération en une ou deux étapes de séparation de la phase huileuse et de la phase asphaltique par addition à la charge d'un solvant de la phase huileuse précipitant de la pahse asphaltique,
  • - des opérations de récupération du solvant contenu dans les phases huileuse et asphaltique séparées, ledit solvant étant recyclé à l'opération de séparation précédente,

ce procédé étant caractérisé en ce qu'il comprend en outre une opération de cisaillement de la charge, par passage forcé de celle-ci entre deux pièces en mouvement l'une par rapport à l'autre dans des conditions telles que le cisaillement, défini par le rapport du où du est la différence de vitesse entre lesdites pièces et dx la distance séparant ces pièces, soit compris entre 103 et 106s-1 et, de préférence, entre 104 et 2 105s-1.To this end, the subject of the invention is a process for deasphalting a heavy hydrocarbon charge consisting of an oily phase and an asphaltic phase, having a density at 15 ° C greater than approximately 930 kg / m 3 and composed essentially of hydrocarbons, but which also contains other chemical compounds which, in addition to carbon and hydrogen atoms, have heteroatoms, this process comprising at least:
  • an operation in one or two stages of separation of the oily phase and the asphaltic phase by adding to the charge a solvent of the oily phase precipitating from the asphaltic pahse,
  • operations for recovering the solvent contained in the separated oily and asphaltic phases, said solvent being recycled to the previous separation operation,

this process being characterized in that it further comprises a load shearing operation, by forced passage of the latter between two moving parts relative to each other under conditions such as shearing, defined by the ratio of where du is the speed difference between said parts and dx the distance separating these parts, ie between 10 3 and 10 6 s -1 and, preferably, between 10 4 and 2 10 5 s -1 .

Au sens de la présente invention, on entend, par cisaillement, l'application d'une contrainte élevée à la charge diluée ou non.For the purposes of the present invention, by shearing is meant the application of a high stress to the load, whether diluted or not.

Le cisaillement peut être appliqué à la charge après et/ou avant addition d'au moins une partie de solvant.The shear can be applied to the load after and / or before the addition of at least part of the solvent.

Le cisaillement peut être notamment obtenu par passage forcé de la charge, contenant éventuellement au moins une partie du solvant, dans un entrefer limité par une pièce fixe et une pièce coaxiale en rotation dans celle-ci.The shearing can in particular be obtained by forced passage of the load, optionally containing at least part of the solvent, in an air gap limited by a fixed part and a coaxial part rotating therein.

Le cisaillement peut également être provoqué par l'emploi d'une turbine ou de tout autre moyen d'agitation, éventuellement dans la tour de désasphaltage.The shearing can also be caused by the use of a turbine or any other means of agitation, possibly in the deasphalting tower.

Il faut noter le caractère surprenant du résultat du cisaillement, car l'homme de l'art aurait plutôt tendance à penser que le cisaillement provoque une dispersion des asphaltènes plutôt que leur précipitation. Ainsi, il est bien connu que, pour obtenir une émulsion de fines gouttelettes d'eau dans une huile, il est recommandé d'agiter fortement le mélange eau/huile, c'est-à-dire de provoquer un fort cisaillement.It should be noted that the result of the shearing is surprising, since those skilled in the art would rather tend to think that the shearing causes dispersion of the asphaltenes rather than their precipitation. Thus, it is well known that, in order to obtain an emulsion of fine water droplets in an oil, it is recommended to vigorously stir the water / oil mixture, that is to say to cause strong shearing.

L'opération de désasphaltage, qui suit le cisaillement ou qui est effectuée en même temps que celui-ci, peut être réalisée en une ou deux étapes.The deasphalting operation, which follows the shearing or which is carried out at the same time as this, can be carried out in one or two stages.

Dans le premier cas, on obtient une phase huileuse et une phase asphaltique, dans le second cas une phase huileuse, une phase «résines» et une phase «asphaltènes».In the first case, an oily phase and an asphalt phase are obtained, in the second case an oily phase, a "resin" phase and an "asphaltenes" phase.

Le solvant utilisé dans la (ou les) étape(s) d'extraction peut être choisi dans le groupe constitué par:

  • - les hydrocarbures aliphatiques, saturés ou non saturés, ayant de 2 à 8 atomes de carbone, seuls ou en mélange,
  • - les mélanges d'hydrocarbures, appelés distillats, ayant des poids moléculaires voisins de ceux des hydrocarbures ayant de 2 à 8 atomes de carbone,
  • - les mélanges de tous les hydrocarbures précédemment cités,
  • - d'autres composés chimiques, qui, outre des atomes de carbone et d'hydrogène, possèdent des hétéroatomes comme l'oxygène, tels les alcools et les phénols, seuls ou en mélange avec les hydrocarbures précédemment cités.
The solvent used in the extraction step (s) can be chosen from the group consisting of:
  • - aliphatic hydrocarbons, saturated or unsaturated, having 2 to 8 carbon atoms, alone or as a mixture,
  • - mixtures of hydrocarbons, called distillates, having molecular weights close to those of hydrocarbons having from 2 to 8 carbon atoms,
  • - mixtures of all the previously mentioned hydrocarbons,
  • - other chemical compounds, which, in addition to carbon and hydrogen atoms, have heteroatoms such as oxygen, such as alcohols and phenols, alone or as a mixture with the previously mentioned hydrocarbons.

Les conditions opératoires, dans les étages de désasphaltage, peuvent être les suivantes:

  • - pression comprise entre 20.106 et 1.107 pascals absolus,
  • - température comprise entre 30 et 300° C,
  • - taux massique
    Figure imgb0001
     compris entre 1 et 10.
The operating conditions, in the deasphalting stages, can be as follows:
  • - pressure between 20.106 and 1.107 absolute pascals,
  • - temperature between 30 and 300 ° C,
  • - mass rate
    Figure imgb0001
     between 1 and 10.

Ces conditions varient, bien sûr, notamment selon:

  • - la nature de la charge,
  • - la nature des solvants utilisés.
These conditions vary, of course, in particular according to:
  • - the nature of the load,
  • - the nature of the solvents used.

L'invention sera mieux comprise à la lecture de la description détaillée qui va suivre, en référence au dessin annexé, qui n'a pas de caractère limitatif.The invention will be better understood on reading the detailed description which follows, with reference to the appended drawing, which is not limiting.

Ce dessin représente de façon schématique une unité de désasphaltage comportant une installation de cisaillement.This drawing schematically represents a deasphalting unit comprising a shearing installation.

Dans cette forme de mise en oeuvre de l'invention, on introduit par la ligne 1 la charge hydrocarbonée lourde, par exemple une huile de masse volumique à 15° C supérieure à 930 kg/m3, dans la partie médiane d'un extracteur liquide-liquide 2.In this embodiment of the invention, the heavy hydrocarbon feedstock, for example an oil with a density at 15 ° C. greater than 930 kg / m 3 , is introduced via line 1 into the middle part of an extractor liquid-liquid 2.

Dans l'extracteur 2, la phase huileuse est extraite de la charge par un solvant, qui est introduit dans l'extracteur par la ligne 3. Ce solvant peut être notamment un hydrocarbure aliphatique, saturé ou non saturé, ayant de 2 à 8 atomes de carbone, de préférence de 3 à 5 atomes de carbone, ou les mélanges d'hydrocarbures, appelés distillats, ayant de 2 à 8 atomes de carbone, ou les mélanges de tous les hydrocarbures précédemment cités.In extractor 2, the oily phase is extracted from the feedstock with a solvent, which is introduced into the extractor through line 3. This solvent can in particular be an aliphatic hydrocarbon, saturated or unsaturated, having 2 to 8 atoms carbon, preferably from 3 to 5 carbon atoms, or the mé diapers of hydrocarbons, called distillates, having from 2 to 8 carbon atoms, or mixtures of all the hydrocarbons previously mentioned.

Le solvant du démarrage de l'unité provient d'une source extérieure à l'unité par l'intermédiaire de la ligne 4. Les pertes de solvant peuvent être compensées par un appoint extérieur, amené par la ligne 4.The solvent for starting the unit comes from a source external to the unit via line 4. Losses of solvent can be compensated by an external make-up, brought by line 4.

La pression à l'intérieur de l'extracteur 2 peut être comprise entre 20 · 105 et 1 · 107 pascals absolus, la température entre 30 et 300° C, le taux mas- sique

Figure imgb0002
étant compris entre 1 et 10.The pressure inside the extractor 2 can be between 20 · 10 5 and 1 · 10 7 absolute pascals, the temperature between 30 and 300 ° C, the mass rate
Figure imgb0002
 being between 1 and 10.

On recueille en tête de l'extracteur 2, par la ligne 5, la phase huileuse en solution dans le solvant. Ce mélange est conduit par la ligne 5 dans un ensemble de fractionnement 6. Dans un but de simplification, cet ensemble n'a pas été représenté en détail, mais il comprend, en général, un régulateur contrôlant une chute de pression et des évaporateurs.The oily phase dissolved in solvent is collected at the head of extractor 2, via line 5. This mixture is conducted by line 5 in a fractionation assembly 6. For the purpose of simplification, this assembly has not been shown in detail, but it generally includes a regulator controlling a pressure drop and evaporators.

A la sortie de l'ensemble 6, on recueille, d'une part, par la ligne 7, du solvant, qui est recyclé vers l'extracteur 2 par l'intermédiaire de la ligne 3 et, d'autre part, par la ligne 8, la phase huileuse.At the outlet of the assembly 6, solvent is collected, on the one hand, by line 7, which is recycled to extractor 2 via line 3 and, on the other hand, by the line 8, the oily phase.

On récupère, au fond de l'extracteur 2, la phase asphaltique précipitée et du solvant. Ce mélange est conduit par la ligne 10 dans un ensemble de fractionnement 11, qui comprend en général un four ou un échangeur avec un fluide chaud, un évaporateur et une colonne d'entraînement à la vapeur d'eau.The precipitated asphalt phase and the solvent are recovered at the bottom of the extractor 2. This mixture is conducted by line 10 in a fractionation assembly 11, which generally comprises an oven or an exchanger with a hot fluid, an evaporator and a water vapor drive column.

On recueille, à la sortie de l'ensemble 11, d'une part, par la ligne 12, du solvant qui est recyclé à l'extracteur 2, par l'intermédiaire de la ligne 3, et, d'autre part, par la ligne 13, la phase asphaltique.Is collected, at the outlet of the assembly 11, on the one hand, by the line 12, of the solvent which is recycled to the extractor 2, via the line 3, and, on the other hand, by line 13, the asphalt phase.

Une partie du solvant de la ligne 3 peut éventuellement être conduite à la ligne 1 par la ligne 14 pour prédiluer la charge.Part of the solvent in line 3 can optionally be brought to line 1 via line 14 to predilute the charge.

Selon l'invention, on peut placer en 20, sur la ligne 1, au moins une restriction (on peut en envisager plusieurs en parallèle selon le débit de la charge), qui provoque un cisaillement de la charge. Cette restriction peut également être placée après ou avant l'intersection des lignes 1 et 14, avant la tour 2 de désasphaltage.According to the invention, one can place at 20, on line 1, at least one restriction (one can envisage several in parallel according to the flow rate of the load), which causes shearing of the load. This restriction can also be placed after or before the intersection of lines 1 and 14, before the deasphalting tower 2.

On peut, outre le dispositif 20, ou en remplacement, placer dans la tour 2 un moyen d'agitation comme une turbine.One can, in addition to the device 20, or as a replacement, place in the tower 2 a stirring means such as a turbine.

Les exemples ci-après illustrent la mise en oeuvre de l'invention et ses avantages.The examples below illustrate the implementation of the invention and its advantages.

Exemple 1:Example 1:

Cet exemple concerne des essais de désasphaltage effectués sur un résidu de la distillation sous pression réduite du résidu de la distillation sous pression atmosphérique d'un pétrole brut Safa- niya, avec et sans cisaillement préalable dudit résidu.This example relates to deasphalting tests carried out on a residue from the distillation under reduced pressure of the residue from the distillation at atmospheric pressure of a Safaniya crude oil, with and without prior shearing of said residue.

Les caractéristiques de cette charge sont les suivantes:

  • - masse volumique à 15° C (mesurée selon la norme AFNOR NFT 60-101): 1042 kg/m3,
  • - viscosité à 100° C (mesurée selon la norme AFNOR NFT 60-100) : 6250 mm2/s,
  • - résidu «Conradson» (mesuré selon la norme AFNOR NFT 60-116): 22,9% en poids,
  • - teneur en:
    • * asphaltènes (mesurée selon la norme AFNOR N FT 60-115): 15,1 % en poids,
    • * soufre (mesurée par fluorescence X) : 5,46% en poids,
    • * nickel (mesurée par fluorescence X): 45 p.p.m.,
    • * vanadium (mesurée par fluorescence X) : 149 p.p.m.
The characteristics of this charge are as follows:
  • - density at 15 ° C (measured according to AFNOR NFT 60-101 standard): 1042 kg / m 3 ,
  • - viscosity at 100 ° C (measured according to AFNOR NFT 60-100 standard): 6250 mm 2 / s,
  • - "Conradson" residue (measured according to AFNOR NFT 60-116): 22.9% by weight,
  • - content of:
    • * asphaltenes (measured according to AFNOR N FT 60-115 standard): 15.1% by weight,
    • * sulfur (measured by X-ray fluorescence): 5.46% by weight,
    • * nickel (measured by X-ray fluorescence): 45 ppm,
    • * vanadium (measured by X-ray fluorescence): 149 ppm

On effectue sur cette charge:

  • - des essais témoins de désasphaltage T1 et T2 sans cisaillement préalable de la charge,
  • - des essais selon le procédé de l'invention A11, A12 et A2, après cisaillement préalable de la charge, sans addition préalable de solvant.
One carries out on this load:
  • - T1 and T2 deasphalting control tests without prior shearing of the load,
  • - Tests according to the method of the invention A11, A12 and A2, after prior shearing of the load, without prior addition of solvent.

Dans tous les essais, on utilise comme solvant de désasphaltage un solvant ayant la composition suivante (en % en volume) :

  • - propane 0,82
  • - isobutane 43,99
  • - normal butane 23,01
  • - normal butène-1 8,08
  • - isobutène 9,17
  • - butène-2 cis 9,16
  • - butène-2 trans 5,70
  • - isopentane 0,07
    Figure imgb0003
    Figure imgb0004
In all the tests, a solvent having the following composition (in% by volume) is used as deasphalting solvent:
  • - propane 0.82
  • - isobutane 43.99
  • - normal butane 23.01
  • - normal butene-1 8.08
  • - isobutene 9.17
  • - butene-2 cis 9.16
  • - butene-2 trans 5.70
  • - isopentane 0.07
    Figure imgb0003
    Figure imgb0004

A l'issue de ces essais et après séparation du solvant, on obtient une phase huileuse et une phase asphaltique. On mesure les rendements obtenus et les caractéristiques de ces phases, qui figurent dans le Tableau II ci-après.

Figure imgb0005
Figure imgb0006
 At the end of these tests and after separation of the solvent, an oily phase and an asphaltic phase are obtained. The yields obtained and the characteristics of these phases are measured, which appear in Table II below.
Figure imgb0005
Figure imgb0006

Exemple 2:Example 2:

Cet exemple concerne des essais de désasphaltage effectués sur deux charges C1 et C2, avec et sans cisaillement préalable des charges. Quand il est effectué, le cisaillement a lieu en présence de solvant.This example relates to deasphalting tests carried out on two loads C 1 and C 2 , with and without prior shearing of the loads. When it is carried out, the shearing takes place in the presence of solvent.

La charge C, est identique à celle utilisée dans l'exemple 1 et est donc constituée par un résidu de distillation sous pression réduite d'un résidu de distillation atmosphérique d'un pétrole brut Safa- niya. Ses caractéristiques sont données dans l'exemple 1. La charge C2 est constituée par un résidu de distillation sous pression atmosphérique d'un pétrole brut Maya.The feedstock C, is identical to that used in Example 1 and is therefore constituted by a distillation residue under reduced pressure of an atmospheric distillation residue of a Safaniya crude oil. Its characteristics are given in Example 1. The feed C 2 consists of a residue from the distillation under atmospheric pressure of a Maya crude oil.

Les caractéristiques de cette charge sont les suivantes:

  • - masse volumique à 15° C (mesurée selon la norme AFNOR NFT 60-101): 1026 kg/m3,
  • - viscosité à 100° C (mesurée selon la norme AFNOR NFT 60-100): 876 mm2/s,
  • - résidu «Conradson» (mesuré selon la norme AFNOR NFT 60-116): 19,7% en poids,
  • ― teneur en:
    • * asphaltènes (mesurée selon la norme AFNOR N FT 60-115): 16,2% en poids,
    • * soufre (mesurée par fluorescence X) : 4,57% en poids,
    • * nickel (mesurée par fluorescence X) : 91 p.p.m.,
    • * vanadium (mesurée par fluorescence X) : 480 p.p.m..
The characteristics of this charge are as follows:
  • - density at 15 ° C (measured according to AFNOR NFT 60-101 standard): 1026 kg / m 3 ,
  • - viscosity at 100 ° C (measured according to AFNOR NFT 60-100 standard): 876 mm 2 / s,
  • - “Conradson” residue (measured according to AFNOR NFT 60-116 standard): 19.7% by weight,
  • - content of:
    • * asphaltenes (measured according to standard AFNOR N FT 60-115): 16.2% by weight,
    • * sulfur (measured by X-ray fluorescence): 4.57% by weight,
    • * nickel (measured by X-ray fluorescence): 91 ppm,
    • * vanadium (measured by X-ray fluorescence): 480 ppm.

On effectue sur ces charges:

  • - des essais témoins de désasphaltage T3 (avec C, ) et T4 (avec C2) sans cisaillement préalable de la charge,
  • - des essais selon le procédé de l'invention A3 (avec C1) et A4 (avec C2) après cisaillement préalable de la charge, avec addition de solvant avant le cisaillement.
One carries out on these loads:
  • - control tests of deasphalting T 3 (with C,) and T 4 (with C 2 ) without prior shearing of the load,
  • - Tests according to the method of the invention A 3 (with C 1 ) and A 4 (with C 2 ) after prior shearing of the load, with addition of solvent before shearing.

L'addition de solvant, du normal heptane, se fait sous agitation, à une température supérieure de 10° C à la température de ramollissement de la charge: 60° C pour C1 34° C pour C2 (mesurée selon la norme AFNOR NFT 66-008).The addition of solvent, normal heptane, is carried out with stirring, at a temperature 10 ° C higher than the softening temperature of the charge: 60 ° C for C 1 34 ° C for C 2 (measured according to AFNOR standard NFT 66-008).

Le cisaillement est effectué à une température de 95° C dans une turbine ayant un entrefer de 0,6 mm et une tête crénelée (2 mm d'espace entre les dents) avec une vitesse de rotation de 17000 tours/mn.The shearing is carried out at a temperature of 95 ° C. in a turbine having an air gap of 0.6 mm and a crenellated head (2 mm of space between the teeth) with a rotational speed of 17,000 rpm.

Pour les essais T3 et A3, on a utilisé pour le désasphaltage un solvant composé de 89% en poids de normal pentane et de 11 % en poids de normal heptane.For tests T 3 and A 3 , a solvent composed of 89% by weight of normal pentane and 11% by weight of normal heptane was used for deasphalting.

Pour les essais T4 et A4, le solvant contient 78,1 % en poids de normal pentane et 21,9% en poids de normal heptane.For tests T 4 and A 4 , the solvent contains 78.1% by weight of normal pentane and 21.9% by weight of normal heptane.

Dans ces compositions, on tient compte du normal heptane préalablement ajouté.In these compositions, the normal heptane previously added is taken into account.

Les conditions des essais figurent dans le Tableau III ci-après:

Figure imgb0007
The test conditions are shown in Table III below:
Figure imgb0007

A l'issue de ces essais et après séparation du solvant, on obtient une phase huileuse et une phase asphaltique. On mesure les rendements obtenus et les caractéristiques de ces phases, qui figurent dans le Tableau IV ci-après.

Figure imgb0008
Figure imgb0009
Figure imgb0010
 At the end of these tests and after separation of the solvent, an oily phase and an asphaltic phase are obtained. The yields obtained and the characteristics of these phases are measured, which appear in Table IV below.
Figure imgb0008
Figure imgb0009
Figure imgb0010

Claims (7)

1. A process for deasphalting a heavy hydrocar- bonic charge comprising an oily phase and an asphaltic phase, having a mass density of more than 930 kg/m3 at 15° C and composed substantially of hydrocarbons, but which also contains other chemical compounds which, in addition to carbon and hydrogen atoms, possess heteroatoms, the process comprising at least:
- one operation in one or two stages for the separation of the oily phase and the asphaltic phase by adding to the charge a solvent of the oily phase which is a precipitant of the asphaltic phase;
- operations for recovery of the solvent contained in the separate oily and asphaltic phases, said solvent being recycled to the preceding separating operation;

the process being characterised in that it additionally comprises an operation for shearing a charge, by constraining the latter to pass between two members moving relative to one another under conditions such as the shearing, defined by the ratio
Figure imgb0012
 wherein du is the difference in speed between said members and dx is the distance between these members, i.e. between 103 and 106s-1, and, preferably, between 10" and 2 · 105s-1.
2. A process according to claim 1, characterised in that the charge shearing operation is carried out before the separating operation.
3. A process according to claim 1, characterised in that the charge shearing operation is carried out during the separating operation in the deasphalting unit.
4. A process according to claim 2, characterised in that the charge shearing operation is carried out before the addition of solvent to the charge.
5. A process according to claim 2, characterised in that the shearing operation is carried out after the addition of solvent to the charge.
6. A process according to claim 1, characterised in that said shearing is effected by an agitating means, such as a turbine.
7. A process according to claim 1, characterised in that said shearing is the result of the forced passage through a clearance bounded by a stationary member and a coaxial member rotating in the stationary member.
EP87401848A 1986-08-12 1987-08-07 Process for deasphaltizing a heavy hydrocarbon feedstock Expired EP0256940B1 (en)

Applications Claiming Priority (2)

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FR8611638A FR2602783B1 (en) 1986-08-12 1986-08-12 PROCESS FOR DEASPHALTING A HEAVY HYDROCARBON LOAD
FR8611638 1986-08-12

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JP6378094B2 (en) * 2012-01-17 2018-08-22 エムイージー エナジー コーポレイション High yield conversion of heavy hydrocarbons with low complexity
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