EP0411973B1 - Process for treatment of metal containing petroleum fractions in the presence of solid particles, comprising a magnetohydrostatic separation step for these particles and recycling a part of them - Google Patents

Process for treatment of metal containing petroleum fractions in the presence of solid particles, comprising a magnetohydrostatic separation step for these particles and recycling a part of them Download PDF

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Publication number
EP0411973B1
EP0411973B1 EP90401812A EP90401812A EP0411973B1 EP 0411973 B1 EP0411973 B1 EP 0411973B1 EP 90401812 A EP90401812 A EP 90401812A EP 90401812 A EP90401812 A EP 90401812A EP 0411973 B1 EP0411973 B1 EP 0411973B1
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Prior art keywords
solid particles
fraction
density
mean density
ferrofluid
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EP90401812A
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German (de)
French (fr)
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EP0411973A1 (en
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André Buisson
Jean-Paul Euzen
Frédéric Morel
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • 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
    • C10G15/00—Cracking of hydrocarbon oils by electric means, electromagnetic or mechanical vibrations, by particle radiation or with gases superheated in electric arcs

Definitions

  • the present invention relates to a process for treating hydrocarbon cuts containing metals.
  • It relates more particularly to a multi-step process comprising at least one step for treating a cut of hydrocarbons containing metals in the presence of solid particles under conditions of at least partial elimination of the metals which it contains and of deposits of said metals on at least a fraction of said solid particles, at least one step of magnetohydrostatic separation of a portion of the solid particles and at least one step of recycling a fraction of said solid particles in the step of processing said cut.
  • solid particles preferably comprising solid particles of at least one catalyst
  • the properties of the solid particles gradually degrade over time as a result of the deposition of coke and the deposition of the metals contained in the charge. If there are very many methods of regeneration of solid particles, these are most often methods allowing the more or less complete elimination of coke and it is generally not possible without significant modification of the properties of solid particles of remove metals that have settled during processing.
  • This non-uniformity of the metal deposits on the solid particles can have several origins, it can for example in the case of a treatment carried out in a fixed bed or in a moving bed be due at least in part to a poor distribution of the charge and in the case of a treatment in a bubbling bed or in a entrained bed may be due at least in part to a more or less complete mixing of the solid particles in the reaction zone which results in the withdrawal of solid particles which have hardly been in contact with the hydrocarbon charge.
  • this method does not apply in the case where the metals which are deposited on the solid particles are in the form of metallic compounds having no significant magnetic properties.
  • a catalytic hydrotreatment of a hydrocarbon feedstock in the presence of a supported catalyst comprising at least one metal chosen from the group formed by the metals of groups VIB and VIII of the periodic table elements (Handbook of Chemistry and Physics, 55th edition, 1974-1975, inside page of the cover) the difference in magnetic properties between the particles of the new catalyst, ie having not been brought into contact with the charge of hydrocarbons under the hydrotreatment conditions, and the particles of the used catalyst, that is to say having been brought into contact with the hydrocarbon charge under the hydrotreatment conditions, is relatively low which is a handicap important for an effective separation of said particles into a still active fraction, which will be recycled, and a fraction which has become inactive or having a very low residual activity, which one will eliminate.
  • the object of the present invention is to overcome the drawbacks of the prior art and also to propose a method making it possible to avoid the rejection of solid particles still having the properties required for the envisaged treatment.
  • the process of the present invention also has the advantage of being applicable both in the case of the use of new solid particles which do not contain metals, and in that in which at least part of the new solid particles contains metals.
  • the present process makes it possible, in the two cases envisaged above, to be able to separate, after use of the solid particles by bringing them into contact with the hydrocarbon charge under the conditions of the treatment envisaged, at least a fraction of said particles. no longer having the properties required for said treatment and at least one fraction, the properties of which are still considered to be sufficient for them to be advantageously recycled in the step of treating the hydrocarbon feedstock.
  • the hydrocarbon fractions which it is envisaged to treat in step ( ⁇ ) of the present process are generally those which contain an amount of metals usually at least 1 ppm (parts per million) and for example from 1 to 3000 ppm and most often from 5 to 2000 ppm.
  • These cuts can be residues of conventional crude oils, residues from atmospheric distillation or vacuum distillation of crude oils, heavy or extra heavy oils or their residues, for example oils from Fara Petrolifera deposits. in Venezuela or Athabasca in Canada.
  • the metals which are most often found in the hydrocarbon feedstocks which are usually treated according to the process of the present invention are nickel and vanadium. Certain charges also contain significant quantities of other metals, for example iron and copper, or mercury.
  • both catalytic and non-catalytic treatment of the hydrocarbon feedstock is envisaged.
  • the present process is applicable in all cases where during the treatment of the hydrocarbon feedstock containing metals at least part of these metals is deposited on at least part of the solid particles with which the load comes into contact with the processing conditions.
  • treatments envisaged in the present invention mention may be made of catalytic cracking, hydrotreatments in particular hydrodemetallization and processes for capturing the mercury contained in liquid or gaseous hydrocarbon cuts using solid collection masses.
  • the treatments are carried out in fixed, mobile, entrained, fluidized or bubbling beds.
  • the process of the present invention is particularly applicable in the case of treatments in moving, entrained, fluidized or bubbling beds.
  • the hydrocarbon charge will be brought into contact with solid particles which comprise particles of at least one catalyst.
  • the catalyst can be an inorganic solid having a catalytic action in the envisaged treatment process and not containing metals as is for example the case of zeolites or silica-alumina used in the context of catalytic cracking or a metallic catalyst resulting from example of the deposition of metals on a solid support, for example a conventional catalyst used in the context of hydrotreatments comprising at least one metal chosen from the group formed by the metals of groups VIB and VIII of the periodic table of elements on a support, usually a mineral support and for example an alumina or a silica-alumina.
  • the new solid particles used in step ( ⁇ ) have an average initial density (d o ) which gradually increases during contact with the hydrocarbon charge under the treatment conditions as a result of the deposition on at least part of between them metals contained in the charge.
  • d o average initial density
  • at least part of the solid particles are withdrawn continuously or periodically (intermittently) which, following their contact with the hydrocarbon charge, have an average density (d1) greater than the density average (d o ) initial.
  • these particles of medium density (d1) are subjected to a combustion treatment, under conditions allowing the elimination of the majority of the coke which they contain and which is deposited during from the processing step ( ⁇ ), before being sent to the magnetohydrostatic separation step ( ⁇ ) described above.
  • the intensity of the magnetic field and its direction are chosen so that the ferrofluid has an average apparent density (d af ), different from its density in the absence of any magnetic field other than the terrestrial magnetic field, usually equal to a value of 0.5xd1 to 1.5xd1 and preferably 0.8xd1 at 1.2xd1; this average value "d af " is chosen so as to allow the separation of the solid particles of average density "d1” into at least one fraction of average density "d i " lower than the average apparent density "d af " of the ferrofluid and into at least a fraction of average density "d s " greater than said average apparent density "d af " of the ferrofluid and the average density "d1" of the solid particles withdrawn in step ( ⁇ ).
  • d af average apparent density
  • step ( ⁇ ) It is thus possible to sort or separate the solid particles from step ( ⁇ ) according to their density and / or their density and their magnetic properties in several fractions by varying the density value.
  • apparent mean "d af " of the ferrofluid one then obtains for each chosen value of this average apparent density a fraction of particles of average density greater than this density and a fraction of average density less than this density.
  • the fraction (s) whose average density is still relatively close to the value of the average density (d o ) of the new solid particles still have sufficient properties to be able to be very advantageously recycled, possibly after washing and drying in order to eliminate any trace of ferrofluid, in step ( ⁇ ) of processing the hydrocarbon cut.
  • At least a first fraction of solid particles of medium density (d i ) is separated from at least a second fraction of solid particles of medium density (d s ) whose value is at least greater 10% to the value of the average density (d i ) of said first fraction, this value (d s ) being usually at least 11% and preferably at least 15% greater than the value (d o ) of the average density of new solid particles.
  • the ferrofluid used to sort or separate the solid particles during step ( ⁇ ) of the present process is usually a stable or stabilized suspension of fine colloidal particles of at least one ferromagnetic solid, by example an oxide such as iron oxide Fe3O4 or magnetite, in the form of particles with average dimensions of 5x1O ⁇ 9 m (meter) to 2x10 ⁇ 8 m (or 50 to 200 Angstroms), in an organic or aqueous solvent and the more often in an organic solvent which is usually a hydrocarbon or a mixture of hydrocarbons liquid at normal temperature and pressure; as examples of a hydrocarbon or a mixture of hydrocarbons, mention may be made of xylene and kerosene.
  • an oxide such as iron oxide Fe3O4 or magnetite
  • suspensions are usually stabilized by means of at least one surfactant such as for example an acid or a derivative of oleic or linoleic acid.
  • concentration of ferromagnetic solid particles in the liquid is usually 1% to 10% by weight.
  • density, measured at 20 ° C relative to water at 4 ° C, of ferrofluid in the absence of any magnetic field other than the Earth's magnetic field is usually 0.8 to 1.30.
  • the average apparent density (d af ) obtained during the application of a magnetic field gradient may be greater or less than the density of the ferrofluid in the absence of an external magnetic field; it is lower if the vertical magnetic field gradient that is applied is directed upwards, that is to say in the opposite direction of the force of gravity, and it is higher if the magnetic field gradient is directed downwards. is to say in the same direction as the force of gravity.
  • the ferrofluid used usually has a saturation magnetization intensity of around 10 ⁇ 4 Tesla to 1 Tesla and most often from 10 ⁇ 2 Tesla to 5x10 ⁇ 2 Tesla.
  • the magnetic field gradient along the height of the pole pieces is usually from 105 Axm ⁇ 2 (ampere per square meter) to 108 Axm ⁇ 2 and most often from 2x105 Axm ⁇ 2 to 2x106 Axm ⁇ 2.
  • the average apparent density of the ferrofluid can thus be adjusted to values varying for example from 0.5 to 25.
  • the method of the present invention is applicable whatever the shape and size of the solid particles.
  • the size of the solid particles is usually from 10 ⁇ 6 m to 10 ⁇ 2 m and most often from 5x10 ⁇ 6 m to 5x10 ⁇ 3 m.
  • the temperature of the solid particles which is sent to the magnetohydrostatic separation step ( ⁇ ) will preferably be lower than the boiling point, under normal pressure and temperature, of the ferrofluid used; this step will be the most often performed at normal temperature and pressure (room) although it is also possible to operate under higher or lower pressure than ordinary pressure.
  • the stage of combustion of the coke which is deposited on the solid particles during the treatment is a conventional stage, the conditions of which are well known to those skilled in the art.
  • the elimination of the majority of the coke contained on the solid particles can be carried out by bringing these particles into contact with an oxygen-containing gas by gradually increasing the temperature until observes the exothermic reaction of combustion or burning of coke, usually between 300 and 500 ° C.
  • This combustion is preferably carried out with care and the operating conditions are adjusted so that preferably the temperature does not exceed 550 ° C. and preferably 500 ° C.
  • the oxygen-containing gas in the combustion step is usually a mixture of oxygen and inert gas, usually containing from 0.1 to 30% by weight of oxygen and most often from 0.2 to 10 % by weight of oxygen.
  • This gas may for example be air or air diluted with an inert gas, for example nitrogen.
  • the proportion of oxygen in the gas used for the combustion of coke can also be variable depending on the evolution of the exothermic combustion reaction: it will for example be lower at start-up and can then be gradually or incrementally increased as and as we get closer to the end of this step.
  • the apparatus used to separate solid particles according to their difference in density or their difference in density and magnetic property is a conventional apparatus such as those used for example during the separation by simple decantation of non-metallic ores ferrous.
  • the apparatus used will not be described more fully in the context of the present description and one may for example refer to the descriptions of these apparatuses and of the technique for their implementation published in AIAA Paper No. 73-959 "3rd Urban Technology Conference and Technical Display, Boston, Massachusetts, September 25-28, 1973 " by L. MIR, C. SIMARD and D.
  • the present process makes it possible, in the case of catalytic treatments, to keep the catalytic activity at a high level by replacing the particles highly charged with metals and recovered in step ( ⁇ ) of the process with particles of new catalyst which are mixed. with the fraction of solid particles sparingly loaded with metals and recycled in step ( ⁇ ) of the process.
  • Example 1 illustrates the invention without limiting its scope.
  • Example 1 is given for comparison.
  • Example 2 of implementation of the process of the present invention in the case of a hydrodemetallization of a hydrocarbon fraction, using a conventional commercial catalyst, highlights the important advantages of the present process and in particular the possibility of effecting an effective separation of catalytic particles having a low residual activity, as a result of a significant deposit of metals, without the need to use a special and expensive apparatus of the type used in the process described in French patent application FR-A-2484439 requiring an investment in material and energy essential for its operation which obeys the process of this request.
  • Example 1 is repeated until the equilibrium state is obtained, then from this equilibrium state it is withdrawn periodically, according to the same periodicity as that used in Example 1, 150 cm3 of solid catalyst particles of average density "d1" equal to 2 and they are subjected to a coke combustion treatment under atmospheric pressure.
  • the gas mixture used to carry out the combustion is a mixture containing dry air and nitrogen in proportion such that the oxygen content of this mixture is 1% by weight.
  • the temperature is gradually increased until the combustion of the coke starts and the flow rate of the gas mixture is then regulated so that the temperature at which the coke burns does not exceed approximately 450 ° C.
  • the injection of the gas mixture is continued until the temperature drops to a value below 300 ° C., then the solid particles of catalyst are then cooled to room temperature (22 ° C.).
  • the solid particles of catalyst containing practically no more coke are then suspended in a ferrofluid containing 6% by weight of magnetite in kerosene.
  • the density of the ferrofluid used in this example is, in the absence of any magnetic field other than the terrestrial magnetic field, of 0.95.
  • the apparatus used in this example is simply constituted by a plastic container, open upwards, containing the ferrofluid and placed between the poles of an electromagnet whose magnetic field intensity is adjusted so as to adjust the apparent density average "d af " of the ferrofluid at a value equal to 2; a fraction of the solid particles is thus recovered from the surface of the ferrofluid (approximately 50% by volume, ie approximately 75 cm3) of average density "d i " equal to 1.5, and at the bottom of the container a fraction of the solid particles (approximately 50% by volume) with an average density "d s " equal to 2.5.
  • the average density fraction "d i " is recycled, after washing with toluene and drying, as a mixture with an equal amount of new catalyst in the demetallization reactor. It is noted that the hydrodetallization treatment of the charge can thus be continued without significant modification of the demetallization performances which remain substantially constant over time at an average value equal to 65%.
  • the process according to the present invention allows a substantial saving (approximately 25% by volume) of new catalyst without significant modification of the demetallization performance.
  • the fractions of the solid particles of average density "d s " recovered in the process according to the present invention represent, for a given quantity of metals originating from the charge treated, a smaller volume than in the case where the catalyst is systematically replaced. with new catalyst, which is an additional advantage of the present process when it is desired to reprocess the used catalyst either with a view to possible re-use, or with a view to its destruction in order to avoid any pollution of the environment, or with a view to recover the metals deposited on the catalyst.

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Description

La présente invention concerne un procédé de traitement de coupes d'hydrocarbures contenant des métaux.The present invention relates to a process for treating hydrocarbon cuts containing metals.

Elle concerne plus particulièrement un procédé multiétapes comprenant au moins une étape de traitement d'une coupe d'hydrocarbures contenant des métaux en présence de particules solides dans des conditions d'élimination au moins partielle des métaux qu'elle contient et de dépôts desdits métaux sur au moins une fraction desdites particules solides, au moins une étape de séparation magnétohydrostatique d'une partie des particules solides et au moins une étape de recyclage d'une fraction desdites particules solides à l'étape de traitement de ladite coupe.It relates more particularly to a multi-step process comprising at least one step for treating a cut of hydrocarbons containing metals in the presence of solid particles under conditions of at least partial elimination of the metals which it contains and of deposits of said metals on at least a fraction of said solid particles, at least one step of magnetohydrostatic separation of a portion of the solid particles and at least one step of recycling a fraction of said solid particles in the step of processing said cut.

Lors des traitements thermiques ou d'hydrotraitements de coupe d'hydrocarbures contenant des métaux effectués en présence de particules solides, comprenant de préférence des particules solides d'au moins un catalyseur, il est bien connu de l'homme du métier que, aussi bien dans le cas d'un traitement catalytique que dans celui d'un traitement non catalytique, les propriétés des particules solides se dégradent peu à peu au cours du temps par suite du dépôt de coke et du dépôt des métaux contenu dans la charge. S'il existe de très nombreuses méthodes de régénération des particules solides il s'agit le plus souvent de méthodes permettant l'élimination plus ou moins complète du coke et il n'est généralement pas possible sans modification importante des propriétés des particules solides d'éliminer les métaux qui se sont déposés au cours du traitement. On est alors conduit à remplacer au moins une partie des particules solides sur lesquelles se sont déposés des métaux par des particules solides neuves, c'est à dire n'ayant pas été mises en contact avec la coupe d'hydrocarbures dans les conditions du traitement. Le dépôt des métaux sur les particules solides n'étant jamais uniforme, ni axialement, ni radialement, l'homme du métier est ainsi conduit à rejeter des particules solides dont une fraction au moins possède encore des propriétés théoriquement suffisantes pour pouvoir continuer à remplir leur rôle dans le traitement envisagé. Cette non uniformité des dépôts de métaux sur les particules solides peut avoir plusieurs origines, elle peut par exemple dans le cas d'un traitement effectué en lit fixe ou en lit mobile être due au moins en partie à une mauvaise distribution de la charge et dans le cas d'un traitement en lit bouillonnant ou en lit entraîné être due au moins en partie à un mélange plus ou moins complet des particules solides dans la zone de réaction ce qui entraîne le soutirage de particules solides n'ayant pratiquement pas été en contact avec la charge d'hydrocarbures.During heat treatments or hydrotreatments of cutting hydrocarbons containing metals carried out in the presence of solid particles, preferably comprising solid particles of at least one catalyst, it is well known to those skilled in the art that, as well in the case of a catalytic treatment than in that of a non-catalytic treatment, the properties of the solid particles gradually degrade over time as a result of the deposition of coke and the deposition of the metals contained in the charge. If there are very many methods of regeneration of solid particles, these are most often methods allowing the more or less complete elimination of coke and it is generally not possible without significant modification of the properties of solid particles of remove metals that have settled during processing. We are then led to replace at least part of the solid particles on which metals have been deposited by new solid particles, that is to say that have not been brought into contact with the hydrocarbon fraction under the treatment conditions. . Since the deposition of metals on the solid particles is never uniform, neither axially nor radially, the skilled person is thus led to reject solid particles of which at least a fraction still has theoretically sufficient properties to be able to continue to fill their role in the proposed treatment. This non-uniformity of the metal deposits on the solid particles can have several origins, it can for example in the case of a treatment carried out in a fixed bed or in a moving bed be due at least in part to a poor distribution of the charge and in the case of a treatment in a bubbling bed or in a entrained bed may be due at least in part to a more or less complete mixing of the solid particles in the reaction zone which results in the withdrawal of solid particles which have hardly been in contact with the hydrocarbon charge.

Il a été décrit dans la demande de brevet français FR-A-2484439, qui concerne spécifiquement un procédé de craquage catalytique, une méthode de séparation d'un catalyseur qui a été retiré de la circulation dans l'unité de craquage catalytique en lit fluidisé en une fraction contenant des métaux et en une fraction ne contenant pas de métaux. Selon cette demande de brevet il est possible de séparer, au moyen d'un champ magnétique à haut gradient de champ, les particules du catalyseur en particules magnétiques et en particules non magnétiques. On constate cependant que selon cette méthode il est nécessaire d'utiliser un gradient de champ très élevé (page 8, lignes 19 à 21 du texte de cette demande de brevet), ce qui implique l'utilisation d'un appareillage spécial et donc un investissement très important. De plus cette méthode ne s'applique pas dans le cas où les métaux qui se déposent sur les particules solides sont sous forme de composés métalliques n'ayant pas de propriétés magnétiques significatives. Par ailleurs, par exemple dans le cas d'un hydrotraitement catalytique d'une charge d'hydrocarbures en présence d'un catalyseur supporté comprenant au moins un métal choisi dans le groupe formé par les métaux des groupes VIB et VIII de la classification périodique des éléments (Handbook of Chemistry and Physics, 55ième édition, 1974-1975, page intérieure de la couverture), la différence de propriétés magnétiques entre les particules du catalyseur neuf, c'est à dire n'ayant pas été mises en contact avec la charge d'hydrocarbures dans les conditions de l'hydrotraitement, et les particules du catalyseur usagé, c'est à dire ayant été mises en contact avec la charge d'hydrocarbures dans les conditions de l'hydrotraitement, est relativement faible ce qui est un handicap important pour une séparation efficace desdites particules en une fraction encore active, que l'on recyclera, et une fraction devenue inactive ou ayant une très faible activité résiduelle, que l'on éliminera.It has been described in French patent application FR-A-2484439, which specifically relates to a catalytic cracking process, a method of separating a catalyst which has been removed from circulation in the catalytic cracking unit in a fluidized bed. in a fraction containing metals and in a fraction not containing metals. According to this patent application it is possible to separate, by means of a magnetic field with a high field gradient, the particles of the catalyst into magnetic particles and into non-magnetic particles. We note however that according to this method it is necessary to use a very high field gradient (page 8, lines 19 to 21 of the text of this patent application), which implies the use of special equipment and therefore a very important investment. In addition, this method does not apply in the case where the metals which are deposited on the solid particles are in the form of metallic compounds having no significant magnetic properties. Furthermore, for example in the case of a catalytic hydrotreatment of a hydrocarbon feedstock in the presence of a supported catalyst comprising at least one metal chosen from the group formed by the metals of groups VIB and VIII of the periodic table elements (Handbook of Chemistry and Physics, 55th edition, 1974-1975, inside page of the cover), the difference in magnetic properties between the particles of the new catalyst, ie having not been brought into contact with the charge of hydrocarbons under the hydrotreatment conditions, and the particles of the used catalyst, that is to say having been brought into contact with the hydrocarbon charge under the hydrotreatment conditions, is relatively low which is a handicap important for an effective separation of said particles into a still active fraction, which will be recycled, and a fraction which has become inactive or having a very low residual activity, which one will eliminate.

La présente invention a pour but de pallier les inconvénients de l'art antérieur et également de proposer un procédé permettant d'éviter le rejet de particules solides ayant encore les propriétés requises pour le traitement envisagé. Le procédé de la présente invention possède également l'avantage d'être applicable aussi bien dans le cas d'une utilisation de particules solides neuves ne renfermant pas de métaux, que dans celui où une partie au moins des particules solides neuves renferme des métaux.The object of the present invention is to overcome the drawbacks of the prior art and also to propose a method making it possible to avoid the rejection of solid particles still having the properties required for the envisaged treatment. The process of the present invention also has the advantage of being applicable both in the case of the use of new solid particles which do not contain metals, and in that in which at least part of the new solid particles contains metals.

Le présent procédé permet, dans les deux cas envisagés ci-avant, de pouvoir séparer, après utilisation des particules solides par mise en contact de celles-ci avec la charge d'hydrocarbures dans les conditions du traitement envisagé, au moins une fraction desdites particules n'ayant plus les propriétés requises pour ledit traitement et au moins une fraction dont les propriétés sont encore considérées comme suffisantes pour qu'elles puissent être avantageusement recyclées à l'étape de traitement de la charge d'hydrocarbures.The present process makes it possible, in the two cases envisaged above, to be able to separate, after use of the solid particles by bringing them into contact with the hydrocarbon charge under the conditions of the treatment envisaged, at least a fraction of said particles. no longer having the properties required for said treatment and at least one fraction, the properties of which are still considered to be sufficient for them to be advantageously recycled in the step of treating the hydrocarbon feedstock.

De façon plus précise la présente invention concerne un procédé de traitement d'une coupe d'hydrocarbures renfermant des métaux comprenant les étapes suivantes :

  • α) on traite ladite coupe d'hydrocarbures en présence de particules solides de densité moyenne (do) dans des conditions d'élimination au moins partielle des métaux qu'elle contient et de dépôts desdits métaux sur au moins une fraction desdites particules solides,
  • β) on soutire au moins une partie des particules solides provenant de l'étape (α) dont la densité moyenne est (d₁),
  • γ) on sépare magnétohydrostatiquement lesdites particules solides provenant de l'étape (β) sur la base de leur différence de densité ou de leur différence de densité et de propriété magnétique en introduisant lesdites particules solides dans un ferrofluide placé dans un champ magnétique, non uniforme et créant un gradient de champ magnétique vertical, dont l'intensité est ajustée de manière à ce que la densité apparente moyenne (daf) du ferrofluide permette la séparation desdites particules solides en au moins une fraction de densité moyenne (di) inférieure à ladite densité apparente moyenne (daf) du ferrofluide et en au moins une fraction de densité moyenne (ds) supérieure à ladite densité apparente moyenne (daf) du ferrofluide et supérieure à la densité moyenne (d₁) des particules solides soutirées à l'étape (β),
  • δ) on récupère au moins une fraction desdites particules solides de densité moyenne (ds) supérieure à la densité apparente moyenne (daf) du ferrofluide et à la densité moyenne (d₁) des particules solides soutirées à l'étape (β), et
  • ε) on recycle, à l'étape (α) de traitement de ladite coupe d'hydrocarbures, au moins une fraction desdites particules solides de densité moyenne (di) inférieure à la densité apparente moyenne (daf) du ferrofluide et inférieure à la densité moyenne (d₁).

Au cours de ce traitement dans l'étape (α) les particules se chargent en métaux ce qui fait passer la densité moyenne des particules d'une valeur initiale do à une autre valeur d₁ supérieure à do et fonction de la nature et de la quantité des métaux déposés sur lesdites particules.
Par densité apparente moyenne "daf" on désigne dans la présente description la valeur moyenne de la densité apparente en présence d'un champ magnétique mesuré en chaque point d'un axe vertical, sensiblement au centre de l'appareillage. La densité apparente en un point étant définie par la relation ρa= ρf + Mx∇Hxg⁻¹ dans laquelle ρa est la densité apparente du ferrofluide, ρf est la densité physique du ferrofluide en l'absence de tout champ magnétique autre que le champ magnétique terrestre, M est l'intensité d'aimantation du ferrofluide, ∇H est le gradient de champ magnétique vertical et g est l'accélération de la pesanteur.More specifically, the present invention relates to a process for treating a cut of hydrocarbons containing metals, comprising the following steps:
  • α) said cut of hydrocarbons is treated in the presence of solid particles of average density (d o ) under conditions of at least partial elimination of the metals which it contains and deposits of said metals on at least a fraction of said solid particles,
  • β) at least part of the solid particles from step (α) are withdrawn, the average density of which is (d₁),
  • γ) said solid particles from step (β) are magnetohydrostatically separated on the basis of their difference in density or their difference in density and magnetic property by introducing said solid particles into a ferrofluid placed in a non-uniform magnetic field and creating a vertical magnetic field gradient, the intensity of which is adjusted so that the average apparent density (d af ) of the ferrofluid allows the separation of said solid particles into at least a fraction of average density (d i ) less than said average apparent density (d af ) of the ferrofluid and in at least a fraction of average density (d s ) greater than said average apparent density (d af ) of the ferrofluid and greater than the average density (d₁) of the solid particles withdrawn at l 'step (β),
  • δ) at least a fraction of said solid particles of average density (d s ) greater than the average apparent density (d af ) of the ferrofluid and of the average density (d₁) of the solid particles withdrawn in step (β) are recovered, and
  • ε) at step (α) of processing said hydrocarbon fraction, at least a fraction of said solid particles of average density (d i ) lower than the density is recycled apparent mean (d af ) of the ferrofluid and lower than the average density (d₁).

During this treatment in step (α), the particles are charged with metals which causes the average density of the particles to pass from an initial value d o to another value d₁ greater than d o and a function of the nature and the quantity of metals deposited on said particles.
By average apparent density "d af " is meant in the present description the average value of the apparent density in the presence of a magnetic field measured at each point of a vertical axis, substantially in the center of the apparatus. The apparent density at a point being defined by the relation ρ a = ρ f + Mx∇Hxg⁻¹ in which ρ a is the apparent density of the ferrofluid, ρ f is the physical density of the ferrofluid in the absence of any other magnetic field that the earth's magnetic field, M is the magnetization intensity of the ferrofluid, ∇H is the vertical magnetic field gradient and g is the acceleration of gravity.

Les coupes d'hydrocarbures que l'on envisage de traiter dans l'étape (α) du présent procédé sont généralement celles qui renferment une quantité de métaux habituellement d'au moins 1 ppm (partie par million) et par exemple de 1 à 3000 ppm et le plus souvent de 5 à 2000 ppm. Ces coupes peuvent être des résidus de pétroles bruts conventionnels, des résidus issus de la distillation atmosphérique ou de la distillation sous vide des pétroles bruts, des huiles lourdes ou extra lourdes ou de leurs résidus par exemple les huiles en provenance des gisements de la Fara Petrolifera au Vénézuéla ou de l'Athabasca au Canada. Les métaux que l'on trouve le plus souvent dans les charges d'hydrocarbures que l'on traite habituellement selon le procédé de la présente invention sont le nickel et le vanadium. Certaines charges contiennent également des quantités non négligeables d'autres métaux, par exemple du fer et du cuivre, ou encore du mercure.The hydrocarbon fractions which it is envisaged to treat in step (α) of the present process are generally those which contain an amount of metals usually at least 1 ppm (parts per million) and for example from 1 to 3000 ppm and most often from 5 to 2000 ppm. These cuts can be residues of conventional crude oils, residues from atmospheric distillation or vacuum distillation of crude oils, heavy or extra heavy oils or their residues, for example oils from Fara Petrolifera deposits. in Venezuela or Athabasca in Canada. The metals which are most often found in the hydrocarbon feedstocks which are usually treated according to the process of the present invention are nickel and vanadium. Certain charges also contain significant quantities of other metals, for example iron and copper, or mercury.

Dans le cadre de la présente invention on envisage aussi bien un traitement catalytique que non catalytique de la charge d'hydrocarbures. Ainsi le présent procédé est applicable dans tous les cas où au cours du traitement de la charge d'hydrocarbures contenant des métaux une partie au moins de ces métaux se dépose sur une partie au moins des particules solides avec lesquelles la charge entre en contact dans les conditions du traitement. A titre d'exemples non limitatifs de traitements envisagés dans la présente invention on peut citer le craquage catalytique, les hydrotraitements en particulier l'hydrodémétallisation et les procédés de captation du mercure contenu dans des coupes d'hydrocarbures liquides ou gazeux à l'aide de masses de captation solides.In the context of the present invention, both catalytic and non-catalytic treatment of the hydrocarbon feedstock is envisaged. Thus the present process is applicable in all cases where during the treatment of the hydrocarbon feedstock containing metals at least part of these metals is deposited on at least part of the solid particles with which the load comes into contact with the processing conditions. By way of nonlimiting examples of treatments envisaged in the present invention, mention may be made of catalytic cracking, hydrotreatments in particular hydrodemetallization and processes for capturing the mercury contained in liquid or gaseous hydrocarbon cuts using solid collection masses.

Les traitements sont effectués en lits fixes, mobiles, entraînés, fluidisés ou bouillonnants. Le procédé de la présente invention s'applique particulièrement bien au cas des traitements en lits mobiles, entraînés, fluidisés ou bouillonnants. Dans le cas particulier de traitements catalytiques la charge d'hydrocarbures sera mise en contact avec des particules solides qui comprennent des particules d'au moins un catalyseur. Le catalyseur peut être un solide minéral ayant une action catalytique dans le procédé de traitement envisagé et ne contenant pas de métaux comme cela est par exemple le cas des zéolithes ou des silice-alumines utilisées dans le cadre du craquage catalytique ou un catalyseur métallique résultant par exemple du dépôt de métaux sur un support solide, par exemple un catalyseur classique utilisé dans le cadre des hydrotraitements comprenant au moins un métal choisi dans le groupe formé par les métaux des groupes VIB et VIII de la classification périodique des éléments sur un support, habituellement un support minéral et par exemple une alumine ou une silice-alumine.The treatments are carried out in fixed, mobile, entrained, fluidized or bubbling beds. The process of the present invention is particularly applicable in the case of treatments in moving, entrained, fluidized or bubbling beds. In the particular case of catalytic treatments, the hydrocarbon charge will be brought into contact with solid particles which comprise particles of at least one catalyst. The catalyst can be an inorganic solid having a catalytic action in the envisaged treatment process and not containing metals as is for example the case of zeolites or silica-alumina used in the context of catalytic cracking or a metallic catalyst resulting from example of the deposition of metals on a solid support, for example a conventional catalyst used in the context of hydrotreatments comprising at least one metal chosen from the group formed by the metals of groups VIB and VIII of the periodic table of elements on a support, usually a mineral support and for example an alumina or a silica-alumina.

Les particules solides neuves employées dans l'étape (α) ont une densité initiale moyenne (do) qui augmente progressivement au cours du contact avec la charge d'hydrocarbures dans les conditions du traitement par suite du dépôt sur au moins une partie d'entre elles des métaux contenus dans la charge. Lorsque l'on constate une diminution des performances du traitement on soutire de façon continue ou périodique (intermittente) une partie au moins des particules solides qui suite à leur contact avec la charge d'hydrocarbures ont une densité moyenne (d₁) supérieure à la densité moyenne (do) initiale. Dans une forme préférée de réalisation de l'invention ces particules de densité moyenne (d₁) sont soumises à un traitement de combustion, dans des conditions permettant l'élimination de la majorité du coke qu'elles renferment et qui s'est déposé au cours de l'étape (α) du traitement, avant d'être envoyées à l'étape (γ) de séparation magnétohydrostatique décrite ci-avant. Au cours de cette étape (γ) l'intensité du champ magnétique et sa direction sont choisies de manière à ce que le ferrofluide ait une densité apparente moyenne (daf), différente de sa densité en l'absence de tout champ magnétique autre que le champ magnétique terrestre, égale habituellement à une valeur de 0,5xd₁ à 1,5xd₁ et de préférence de 0,8xd₁ à 1,2xd₁ ; cette valeur moyenne "daf" est choisie de manière à permettre la séparation des particules solides de densité moyenne "d₁" en au moins une fraction de densité moyenne "di" inférieure à la densité apparente moyenne "daf" du ferrofluide et en au moins une fraction de densité moyenne "ds" supérieure à ladite densité apparente moyenne "daf" du ferrofluide et à la densité moyenne "d₁" des particules solides soutirées à l'étape (β). Il est possible d'effectuer ainsi un tri ou une séparation des particules solides issues de l'étape (β) en fonction de leur densité et/ou de leur densité et de leurs propriétés magnétiques en plusieurs fractions en faisant varier la valeur de la densité apparente moyenne "daf" du ferrofluide ; on obtient alors pour chaque valeur choisie de cette densité apparente moyenne une fraction de particules de densité moyenne supérieure à cette densité et une fraction de densité moyenne inférieure à cette densité. La ou les fractions dont la densité moyenne est encore relativement proche de la valeur de la densité moyenne (do) des particules solides neuves ont encore des propriétés suffisantes pour pouvoir être très avantageusement recyclées, éventuellement après lavage et séchage en vue d'éliminer toute trace de ferrofluide, à l'étape (α) de traitement de la coupe d'hydrocarbures. Dans une forme avantageuse du présent procédé on sépare au moins une première fraction de particules solides de densité moyenne (di) d'au moins une deuxième fraction de particules solides de densité moyenne (ds) dont la valeur est supérieure d'au moins 10 % à la valeur de la densité moyenne (di) de ladite première fraction, cette valeur (ds) étant habituellement supérieure d'au moins 11 % et de préférence d'au moins 15 % à la valeur (do) de la densité moyenne des particules solides neuves.The new solid particles used in step (α) have an average initial density (d o ) which gradually increases during contact with the hydrocarbon charge under the treatment conditions as a result of the deposition on at least part of between them metals contained in the charge. When a reduction in the performance of the treatment is noted, at least part of the solid particles are withdrawn continuously or periodically (intermittently) which, following their contact with the hydrocarbon charge, have an average density (d₁) greater than the density average (d o ) initial. In a preferred embodiment of the invention, these particles of medium density (d₁) are subjected to a combustion treatment, under conditions allowing the elimination of the majority of the coke which they contain and which is deposited during from the processing step (α), before being sent to the magnetohydrostatic separation step (γ) described above. During this step (γ) the intensity of the magnetic field and its direction are chosen so that the ferrofluid has an average apparent density (d af ), different from its density in the absence of any magnetic field other than the terrestrial magnetic field, usually equal to a value of 0.5xd₁ to 1.5xd₁ and preferably 0.8xd₁ at 1.2xd₁; this average value "d af " is chosen so as to allow the separation of the solid particles of average density "d₁" into at least one fraction of average density "d i " lower than the average apparent density "d af " of the ferrofluid and into at least a fraction of average density "d s " greater than said average apparent density "d af " of the ferrofluid and the average density "d₁" of the solid particles withdrawn in step (β). It is thus possible to sort or separate the solid particles from step (β) according to their density and / or their density and their magnetic properties in several fractions by varying the density value. apparent mean "d af " of the ferrofluid; one then obtains for each chosen value of this average apparent density a fraction of particles of average density greater than this density and a fraction of average density less than this density. The fraction (s) whose average density is still relatively close to the value of the average density (d o ) of the new solid particles still have sufficient properties to be able to be very advantageously recycled, possibly after washing and drying in order to eliminate any trace of ferrofluid, in step (α) of processing the hydrocarbon cut. In an advantageous form of the present process, at least a first fraction of solid particles of medium density (d i ) is separated from at least a second fraction of solid particles of medium density (d s ) whose value is at least greater 10% to the value of the average density (d i ) of said first fraction, this value (d s ) being usually at least 11% and preferably at least 15% greater than the value (d o ) of the average density of new solid particles.

Le ferrofluide utilisé pour effectuer le tri ou la séparation des particules solides au cours de l'étape (γ) du présent procédé est habituellement une suspension stable ou stabilisée de fines particules colloïdales d'au moins un solide ferromagnétique, par exemple un oxyde tel que l'oxyde de fer Fe₃O₄ ou magnétite, sous forme de particules de dimensions moyennes de 5x1O⁻⁹ m (mètre) à 2x10⁻⁸ m (soit 50 à 200 Angstroms), dans un solvant organique ou aqueux et le plus souvent dans un solvant organique qui est habituellement un hydrocarbure ou un mélange d'hydrocarbures liquide à température et pression normales ; à titre d'exemples d'hydrocarbure ou de mélange d'hydrocarbures on peut citer le xylène et le kérosène. Ces suspensions sont habituellement stabilisées au moyen d'au moins un surfactant tel que par exemple un acide ou un dérivé d'acide oléique ou linoléique. La concentration en particles solides ferromagnétiques au sein du liquide est habituellement de 1 % à 10 % en poids. La densité, mesurée à 20 °C par rapport à l'eau à 4 °C, du ferrofluide en l'absence de tout champ magnétique autre que le champ magnétique terrestre est habituellement de 0,8 à 1,30. La densité apparente moyenne (daf) obtenue lors de l'application d'un gradient de champ magnétique peut être supérieure ou inférieure à la densité du ferrofluide en l'absence de champ magnétique externe ; elle est inférieure si le gradient de champ magnétique vertical que l'on applique est dirigé vers le haut c'est à dire en sens contraire de la force de gravité et elle est supérieure si le gradient de champ magnétique est dirigé vers le bas c'est à dire dans le même sens que la force de gravité.The ferrofluid used to sort or separate the solid particles during step (γ) of the present process is usually a stable or stabilized suspension of fine colloidal particles of at least one ferromagnetic solid, by example an oxide such as iron oxide Fe₃O₄ or magnetite, in the form of particles with average dimensions of 5x1O⁻⁹ m (meter) to 2x10⁻⁸ m (or 50 to 200 Angstroms), in an organic or aqueous solvent and the more often in an organic solvent which is usually a hydrocarbon or a mixture of hydrocarbons liquid at normal temperature and pressure; as examples of a hydrocarbon or a mixture of hydrocarbons, mention may be made of xylene and kerosene. These suspensions are usually stabilized by means of at least one surfactant such as for example an acid or a derivative of oleic or linoleic acid. The concentration of ferromagnetic solid particles in the liquid is usually 1% to 10% by weight. The density, measured at 20 ° C relative to water at 4 ° C, of ferrofluid in the absence of any magnetic field other than the Earth's magnetic field is usually 0.8 to 1.30. The average apparent density (d af ) obtained during the application of a magnetic field gradient may be greater or less than the density of the ferrofluid in the absence of an external magnetic field; it is lower if the vertical magnetic field gradient that is applied is directed upwards, that is to say in the opposite direction of the force of gravity, and it is higher if the magnetic field gradient is directed downwards. is to say in the same direction as the force of gravity.

Le ferrofluide utilisé a habituellement une intensité d'aimantation à saturation d'environ 10⁻⁴ Tesla à 1 Tesla et le plus souvent de 10⁻² Tesla à 5x10⁻² Tesla. Le gradient de champ magnétique suivant la hauteur des pièces polaires est habituellement de 10⁵ Axm⁻² (ampère par mètre carré) à 10⁸ Axm⁻² et le plus souvent de 2x10⁵ Axm⁻² à 2x10⁶ Axm⁻². La densité apparente moyenne du ferrofluide peut ainsi être ajustée à des valeurs variant par exemple de 0,5 jusqu'à 25. Le procédé de la présente invention est applicable quelle que soit la forme et la taille des particules solides. La taille des particules solides est habituellement de 10⁻⁶ m à 10⁻² m et le plus souvent de 5x10⁻⁶ m à 5x10⁻³ m.The ferrofluid used usually has a saturation magnetization intensity of around 10⁻⁴ Tesla to 1 Tesla and most often from 10⁻² Tesla to 5x10⁻² Tesla. The magnetic field gradient along the height of the pole pieces is usually from 10⁵ Axm⁻² (ampere per square meter) to 10⁸ Axm⁻² and most often from 2x10⁵ Axm⁻² to 2x10⁶ Axm⁻². The average apparent density of the ferrofluid can thus be adjusted to values varying for example from 0.5 to 25. The method of the present invention is applicable whatever the shape and size of the solid particles. The size of the solid particles is usually from 10⁻⁶ m to 10⁻² m and most often from 5x10⁻⁶ m to 5x10⁻³ m.

La température des particules solides que l'on envoie à l'étape (γ) de séparation magnétohydrostatique sera de préférence inférieure au point d'ébullition, sous pression et température normales, du ferrofluide utilisé ; cette étape sera le plus souvent effectuée à température et pression normales (ambiante) bien qu'il soit possible d'opérer également sous une pression supérieure ou inférieure à la pression ordinaire.The temperature of the solid particles which is sent to the magnetohydrostatic separation step (γ) will preferably be lower than the boiling point, under normal pressure and temperature, of the ferrofluid used; this step will be the most often performed at normal temperature and pressure (room) although it is also possible to operate under higher or lower pressure than ordinary pressure.

L'étape de combustion du coke qui s'est déposé sur les particules solides au cours du traitement est une étape classique dont les conditions sont bien connues de l'homme du métier. A titre d'exemple, l'élimination de la majorité du coke contenu sur les particules solides pourra être effectuée par mise en contact de ces particules avec un gaz contenant de l'oxygène en augmentant progressivement la température jusqu'à ce que l'on observe la réaction exothermique de combustion ou brûlage du coke, habituellement entre 300 et 500 °C. Cette combustion est de préférence effectuée avec précautions et les conditions opératoires sont ajustées de manière à ce que de préférence la température ne dépasse pas 550 °C et d'une manière préférée 500 °C. Au cours de cette étape de combustion la majorité du coke est brûlé de manière à ce que la teneur pondérale en coke résiduel des particules solides après combustion soit habituellement inférieure à environ 5 % de la teneur en coke des particules solides avant combustion (c'est à dire que au moins 95 % du coke a été brûlé). Le gaz contenant de l'oxygène, dans l'étape de combustion est habituellement un mélange d'oxygène et de gaz inerte, contenant habituellement de 0,1 à 30 % en poids d'oxygène et le plus souvent de 0,2 à 10 % en poids d'oxygène. Ce gaz peut être par exemple de l'air ou de l'air dilué par un gaz inerte par exemple de l'azote. La proportion d'oxygène dans le gaz employé pour la combustion du coke peut également être variable en fonction de l'évolution de la réaction exothermique de combustion : elle sera par exemple plus faible au démarrage et pourra ensuite être augmentée progressivement ou par incrément au fur et à mesure que l'on s'approche de la fin de cette étape.The stage of combustion of the coke which is deposited on the solid particles during the treatment is a conventional stage, the conditions of which are well known to those skilled in the art. By way of example, the elimination of the majority of the coke contained on the solid particles can be carried out by bringing these particles into contact with an oxygen-containing gas by gradually increasing the temperature until observes the exothermic reaction of combustion or burning of coke, usually between 300 and 500 ° C. This combustion is preferably carried out with care and the operating conditions are adjusted so that preferably the temperature does not exceed 550 ° C. and preferably 500 ° C. During this combustion step, the majority of the coke is burnt so that the residual coke content by weight of the solid particles after combustion is usually less than about 5% of the coke content of the solid particles before combustion (this is i.e. at least 95% of the coke has been burned). The oxygen-containing gas in the combustion step is usually a mixture of oxygen and inert gas, usually containing from 0.1 to 30% by weight of oxygen and most often from 0.2 to 10 % by weight of oxygen. This gas may for example be air or air diluted with an inert gas, for example nitrogen. The proportion of oxygen in the gas used for the combustion of coke can also be variable depending on the evolution of the exothermic combustion reaction: it will for example be lower at start-up and can then be gradually or incrementally increased as and as we get closer to the end of this step.

L'appareillage utilisé pour effectuer la séparation des particules solides en fonction de leur différence de densité ou de leur différence de densité et de propriété magnétique est un appareillage classique tels que ceux employés par exemple lors de la séparation par simple décantation de minerais de métaux non ferreux. L'appareillage utilisé ne sera pas décrit plus amplement dans le cadre de la présente description et on pourra par exemple se reporter aux descriptions de ces appareillages et de la technique de leur mise en oeuvre publiées dans AIAA Paper N° 73-959 "3rd Urban Technology Conference and Technical Display, Boston, Massachusetts, September 25-28, 1973" par L. MIR, C. SIMARD et D. GRANA sous le titre "Recovery of nonferrous metals from scrap automobiles by magnetic fluid levitation" pages 1 à 7, dans les actes du 15 ième Congrès International de Minéralurgie 1985, 1, pages 307 à 316 par M.S. WALKER, A.L. DEVERNOE, R.W. STUART, W.S. URBANSKI et U. ANDRES sous le titre "A new method for the commercial separation of particles of differing densities using magnetic fluid - the MC process" et dans Physics in Technology vol. 15, 1984, pages 150 à 156, par J. POPPLEWELL sous le titre " Technological applications of Ferrofluids".The apparatus used to separate solid particles according to their difference in density or their difference in density and magnetic property is a conventional apparatus such as those used for example during the separation by simple decantation of non-metallic ores ferrous. The apparatus used will not be described more fully in the context of the present description and one may for example refer to the descriptions of these apparatuses and of the technique for their implementation published in AIAA Paper No. 73-959 "3rd Urban Technology Conference and Technical Display, Boston, Massachusetts, September 25-28, 1973 " by L. MIR, C. SIMARD and D. GRANA under the title "Recovery of nonferrous metals from scrap automobiles by magnetic fluid levitation" pages 1 to 7, in the proceedings of the 15th International Congress of Mineralurgy 1985, 1, pages 307 to 316 by MS WALKER, AL DEVERNOE, RW STUART, WS URBANSKI and U. ANDRES under the title "A new method for the commercial separation of particles of differing densities using magnetic fluid - the MC process" and in Physics in Technology vol. 15, 1984, pages 150 to 156, by J. POPPLEWELL under the title "Technological applications of Ferrofluids".

Le présent procédé permet dans le cas de traitements catalytiques de conserver l'activité catalytique à un niveau élevé en remplacant les particules très chargées en métaux et récupérées à l'étape (δ) du procédé par des particules de catalyseur neuf que l'on mélange avec la fraction de particules solides peu chargées en métaux et recyclées à l'étape (α) du procédé.The present process makes it possible, in the case of catalytic treatments, to keep the catalytic activity at a high level by replacing the particles highly charged with metals and recovered in step (δ) of the process with particles of new catalyst which are mixed. with the fraction of solid particles sparingly loaded with metals and recycled in step (α) of the process.

Les exemples suivants illustrent l'invention sans en limiter la portée. L'exemple 1 est donné à titre de comparaison.The following examples illustrate the invention without limiting its scope. Example 1 is given for comparison.

L'exemple 2 de mise en oeuvre du procédé de la présente invention, dans le cas d'une hydrodémétallisation d'une coupe d'hydrocarbures, à l'aide d'un catalyseur classique du commerce, met en relief les avantages importants du présent procédé et en particulier la possibilité d'effectuer une séparation efficace de particules catalytiques ayant une faible activité résiduelle, par suite d'un dépôt important de métaux, sans qu'il soit nécessaire d'utiliser un appareillage spécial et onéreux du type de celui employé dans le procédé décrit dans la demande de brevet français FR-A-2484439 nécessitant un investissement en matériel et en énergie indispensable pour son fonctionnement qui obére le procédé de cette demande.Example 2 of implementation of the process of the present invention, in the case of a hydrodemetallization of a hydrocarbon fraction, using a conventional commercial catalyst, highlights the important advantages of the present process and in particular the possibility of effecting an effective separation of catalytic particles having a low residual activity, as a result of a significant deposit of metals, without the need to use a special and expensive apparatus of the type used in the process described in French patent application FR-A-2484439 requiring an investment in material and energy essential for its operation which obeys the process of this request.

Exemple 1 (comparaison) Example 1 (comparison)

On effectue une hydrodémétallisation d'une charge de pétrole brut Vénézuélien Boscan, étété et dessalé, dont les caractéristiques sont indiquées dans le tableau 1 ci-après. Le test est effectué dans une unité pilote fonctionnant avec 1000 cm³ de catalyseur dans un réacteur en lit bouillonnant. Les conditions opératoires sont choisies de manière à ce que l'activité initiale en démétallisation soit de 75 %. Le catalyseur utilisé est sous forme de particules solides de dimension moyenne 1,6x10⁻³ m comprenant en poids, sur un support d'alumine, 14 % d'oxyde de molybdène MoO₃ et 3 % d'oxyde de nickel NiO ; ce catalyseur est un catalyseur commercial vendu par la socièté PROCATALYSE. La densité moyenne des particules solides de ce catalyseur neuf est de 0,85. Lorsque l'activité en démétallisation a chuté de 10 % on commence le soutirage périodique d'une fraction du catalyseur usagé et son remplacement par du catalyseur neuf de manière à maintenir l'activité démétallisante à un niveau au moins égal à 65%. Le soutirage de catalyseur usé et son remplacement par du catalyseur neuf est poursuivi dans ces conditions jusqu'à ce que la distribution des âges des particules solides de catalyseur, et donc la densité moyenne "d₁" de ces particules solides n'évolue plus au cours du temps. A partir de cet état d'équilibre on soutire périodiquement 100 cm³ de particules solides de densité moyenne "d₁" égale à 2 et on les remplace par la même quantité de catalyseur neuf ; l'activité démétallisante se maintient ainsi sensiblement constante au cours du temps à une valeur moyenne égale à environ 65 %.

Figure imgb0001
Hydrodetallization of a batch of Venezuelan Boscan crude oil, summer and desalted, the characteristics of which are indicated in table 1 below. The test is carried out in a pilot unit operating with 1000 cc of catalyst in a bubbling bed reactor. The operating conditions are chosen so as to that the initial demetallization activity is 75%. The catalyst used is in the form of solid particles of average size 1.6 × 10⁻³ m comprising by weight, on an alumina support, 14% of molybdenum oxide MoO₃ and 3% of nickel oxide NiO; this catalyst is a commercial catalyst sold by PROCATALYSE. The average density of the solid particles of this new catalyst is 0.85. When the demetallization activity has dropped by 10%, periodic withdrawal of a fraction of the used catalyst is started and its replacement with new catalyst so as to maintain the demetallizing activity at a level at least equal to 65%. The withdrawal of spent catalyst and its replacement with new catalyst is continued under these conditions until the age distribution of the solid particles of catalyst, and therefore the average density "d₁" of these solid particles no longer changes during time. From this state of equilibrium, 100 cm³ of solid particles with an average density "d₁" equal to 2 are periodically withdrawn and replaced with the same amount of new catalyst; the demetallizing activity thus remains substantially constant over time at an average value of approximately 65%.
Figure imgb0001

Exemple 2Example 2

On répète l'exemple 1 jusqu'à l'obtention de l'état d'équilibre, puis à partir de cet état d'équilibre on en soutire périodiquement, suivant la même périodicité que celle employée au cours de l'exemple 1, 150 cm³ de particules solides de catalyseur de densité moyenne "d₁" égale à 2 et on les soumet à un traitement de combustion du coke sous pression atmosphérique. Le mélange gazeux utilisé pour effectuer la combustion est un mélange contenant de l'air sec et de l'azote en proportion telle que la teneur en oxygène de ce mélange soit de 1 % en poids. La température est augmentée progressivement jusqu'au démarrage de la combustion du coke et on régule ensuite le débit de mélange gazeux de manière à ce que la température à laquelle le coke brûle ne dépasse pas environ 450 °C. L'injection du mélange gazeux est poursuivie jusqu'à ce que la température redescende à une valeur inférieure à 300 °C, puis on refroidit alors les particules solides de catalyseur jusqu'à la température ambiante (22 °C). Les particules solides de catalyseur ne contenant pratiquement plus de coke sont alors mises en suspension dans un ferrofluide contenant 6 % en poids de magnétite dans du kérosène. La densité du ferrofluide utilisé dans cet exemple est, en l'absence de tout champ magnétique autre que le champ magnétique terrestre, de 0,95. L'appareillage utilisé dans cet exemple est simplement constitué par un récipient en matière plastique, ouvert vers le haut, contenant le ferrofluide et placé entre les pôles d'un électroaimant dont on régle l'intensité de champ magnétique de manière à ajuster la densité apparente moyenne "daf"du ferrofluide à une valeur égale à 2 ; on récupère ainsi à la surface du ferrofluide une fraction des particules solides (environ 50 % en volume, soit environ 75 cm³) de densité moyenne "di" égale à 1,5, et au fond du récipient une fraction des particules solides (environ 50 % en volume) de densité moyenne "ds" égale à 2,5. La fraction de densité moyenne "di" est recyclée, après lavage au toluène et séchage, en mélange avec une quantité égale de catalyseur neuf dans le réacteur de démétallisation. On constate que le traitement d'hydrodémétallisation de la charge peut ainsi être pousuivi sans modification importante des performances en démétallisation qui se maintiennent sensiblement constantes au cours du temps à une valeur moyenne égale à 65 %.Example 1 is repeated until the equilibrium state is obtained, then from this equilibrium state it is withdrawn periodically, according to the same periodicity as that used in Example 1, 150 cm³ of solid catalyst particles of average density "d₁" equal to 2 and they are subjected to a coke combustion treatment under atmospheric pressure. The gas mixture used to carry out the combustion is a mixture containing dry air and nitrogen in proportion such that the oxygen content of this mixture is 1% by weight. The temperature is gradually increased until the combustion of the coke starts and the flow rate of the gas mixture is then regulated so that the temperature at which the coke burns does not exceed approximately 450 ° C. The injection of the gas mixture is continued until the temperature drops to a value below 300 ° C., then the solid particles of catalyst are then cooled to room temperature (22 ° C.). The solid particles of catalyst containing practically no more coke are then suspended in a ferrofluid containing 6% by weight of magnetite in kerosene. The density of the ferrofluid used in this example is, in the absence of any magnetic field other than the terrestrial magnetic field, of 0.95. The apparatus used in this example is simply constituted by a plastic container, open upwards, containing the ferrofluid and placed between the poles of an electromagnet whose magnetic field intensity is adjusted so as to adjust the apparent density average "d af " of the ferrofluid at a value equal to 2; a fraction of the solid particles is thus recovered from the surface of the ferrofluid (approximately 50% by volume, ie approximately 75 cm³) of average density "d i " equal to 1.5, and at the bottom of the container a fraction of the solid particles (approximately 50% by volume) with an average density "d s " equal to 2.5. The average density fraction "d i " is recycled, after washing with toluene and drying, as a mixture with an equal amount of new catalyst in the demetallization reactor. It is noted that the hydrodetallization treatment of the charge can thus be continued without significant modification of the demetallization performances which remain substantially constant over time at an average value equal to 65%.

On constate donc que le procédé selon la présente invention permet une économie substantielle (environ 25 % en volume) de catalyseur neuf sans modification notable des performances de démétallisation. De plus les fractions des particules solides de densité moyenne "ds" récupérées dans le procédé selon la présente invention représentent, pour une quantité donnée de métaux provenant de la charge traitée, un volume moins important que dans le cas où le catalyseur est systématiquement remplacé par du catalyeur neuf ce qui est un avantage supplémentaire du présent procédé lorsque l'on désire retraiter le catalyseur usagé soit en vue d'une réutilisation éventuelle, soit en vue de sa destruction pour éviter toute pollution de l'environnement, soit en vue de récupérer les métaux déposés sur le catalyseur.It is therefore found that the process according to the present invention allows a substantial saving (approximately 25% by volume) of new catalyst without significant modification of the demetallization performance. In addition, the fractions of the solid particles of average density "d s " recovered in the process according to the present invention represent, for a given quantity of metals originating from the charge treated, a smaller volume than in the case where the catalyst is systematically replaced. with new catalyst, which is an additional advantage of the present process when it is desired to reprocess the used catalyst either with a view to possible re-use, or with a view to its destruction in order to avoid any pollution of the environment, or with a view to recover the metals deposited on the catalyst.

Claims (10)

  1. Process for the treatment of a hydrocarbon fraction containing metals, which is characterized by the following stages :
    α) said hydrocarbon fraction is treated in the presence solid particles of a initial mean density do under conditions of at least partly eliminating the metals contained therein and deposits of said metals on at least one fraction of said solid particles ; the mean density of the particles reaching the value d₁ ;
    β) at least part of the solid particles from stage α), whose mean density is d₁ is drawn off;
    γ) said solid particles from stage β) are magnetohydrostatically separated on the basis of their density difference or their magnetic property and density difference by introducing said solid particles into a ferrofluid placed in a non-uniform magnetic field and by creating a vertical magnetic field gradient, whose intensity is adjusted in such a way that the apparent mean density daf of the ferrofluid permits the separation of said solid particles into at least one mean density fraction di below said mean apparent density daf of the ferrofluid and into at least one mean density fraction dm above said apparent mean density daf of the ferrofluid and above the mean density di of the solid particles drawn off in stage β);
    δ) at least one fraction of said mean density solid particles dm is recovered, which is above the apparent mean density daf of the ferrofluid and the mean density d₁ of the solid particles drawn off in stage β); and
    ε) recycling takes place to the hydrocarbon fraction treatment stage α) of at least one fraction of said solid particles of mean density di below the apparent mean density daf of the ferrofluid and above the mean density d₁.
  2. Process according to claim 1, wherein stage (α) is a hydrotreatment stage.
  3. Process according to claims 1 or 2, wherein the solid particles comprise particles of at least one catalyst.
  4. Process according to claim 3 wherein the catalyst is a supported catalyst comprising at least one metal chosen from the group formed by metals of groups VIB and VIII of the periodic classification of elements.
  5. Process according to one of the claims 1 to 4 wherein the treatment of the hydrocarbon fraction is performed in a fixed bed, a moving bed, an entrained bed, a fluidized bed or a boiling bed.
  6. Process according to one of the claims 1 to 5, wherein the solid particles drawn off in stage (β) undergo a combustion treatment under conditions making it possible to eliminate most of the coke contained therein before being supplied to stage (γ).
  7. Process according to one of the claims 1 to 6, wherein, during stage (γ), at least one first fraction of solid particles of mean density (di) is separated from at least one second fraction of solid particles of mean density (dm), whose value is higher by at least 10% than the density (di) of said first fraction.
  8. Process according to one of the claims 1 to 7, wherein use is made of a ferrofluid formed by a stable colloidal suspension of fine particles with average dimensions of 4x10⁻⁹ to 2x10⁻⁸ m of at least one ferromagnetic oxide in an organic or aqueous solvent.
  9. Process according to claim 8 in which the ferromagnetic oxide particle concentration is from 1 to 10% by weight.
  10. Process according to one of the claims 1 to 9, wherein the ferrofluid has a saturation magnetization intensity of approximately 10⁻⁴ to 1 Tesla and the magnetic field gradient along the height of the pole pieces is from 10⁵ to 10⁸ Axm⁻².
EP90401812A 1989-08-02 1990-06-26 Process for treatment of metal containing petroleum fractions in the presence of solid particles, comprising a magnetohydrostatic separation step for these particles and recycling a part of them Expired - Lifetime EP0411973B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8910515 1989-08-02
FR8910515A FR2650596B1 (en) 1989-08-02 1989-08-02 PROCESS FOR THE TREATMENT OF METAL-CONTAINING OIL FRACTIONS IN THE PRESENCE OF SOLID PARTICLES, INCLUDING A MAGNETOHYDROSTATIC SEPARATION OF THESE PARTICLES AND RECYCLING OF A PORTION OF THEM

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EP0411973A1 EP0411973A1 (en) 1991-02-06
EP0411973B1 true EP0411973B1 (en) 1993-05-12

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BE1007049A3 (en) * 1993-05-05 1995-02-28 Dsm Nv METHOD FOR REMOVING MERCURY
US6026966A (en) * 1996-11-05 2000-02-22 Svoboda; Jan Ferrohydrostatic separation method and apparatus
RU2747176C1 (en) * 2020-09-07 2021-04-28 Николай Иванович Спиридонов Method for demetallization of hydrocarbon products

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US2786047A (en) * 1952-02-11 1957-03-19 Phillips Petroleum Co Process for removing nickel catalyst from hydrogenated polybutadiene
US3575293A (en) * 1969-04-24 1971-04-20 Harold C Nelson Method and apparatus for separating finely divided materials of different specific gravities
US3583560A (en) * 1969-04-29 1971-06-08 Eugene Cline Apparatus and method for cleaning and concentrating fine solids
US4021367A (en) * 1973-05-08 1977-05-03 Budapesti Muszaki Egyetem Process for recovering suspended metal catalyst from their suspension
ES444739A1 (en) * 1975-10-01 1977-08-16 Anglo American Clays Corp Magnetic beneficiation of clays utilizing magnetic particulates
US4158620A (en) * 1977-12-08 1979-06-19 Atlantic Richfield Company Retorting oil shale with iron oxide impregnated porous pellets
US4359379A (en) * 1979-12-21 1982-11-16 Nippon Oil Company, Ltd. Process for fluid catalytic cracking of distillation residual oils
US4342640A (en) * 1980-11-24 1982-08-03 Chevron Research Company Magnetic separation of mineral particles from shale oil
US4819808A (en) * 1982-05-21 1989-04-11 Mag-Sep Corp. Apparatus and method employing magnetic fluids for separating particles
US4594149A (en) * 1982-05-21 1986-06-10 Mag-Sep Corp. Apparatus and method employing magnetic fluids for separating particles
US4530291A (en) * 1983-09-23 1985-07-23 Combustion Engineering, Inc. Separating spent and unreacted particles of calcium-based sulfur sorbent
US4526681A (en) * 1983-10-31 1985-07-02 Purdue Research Foundation Magnetic separation method utilizing a colloid of magnetic particles
US4643822A (en) * 1985-02-28 1987-02-17 The Secretary Of State For Trade And Industry In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Method of separation of material from material mixtures

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FR2650596B1 (en) 1991-10-31
US5169517A (en) 1992-12-08
FR2650596A1 (en) 1991-02-08
DE69001592T2 (en) 1993-08-19
DE69001592D1 (en) 1993-06-17
ES2042239T3 (en) 1993-12-01

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