EP0073690B1 - Catalytic hydroconversion process of heavy hydrocarbons in the presence of a dispersed catalyst and of carbonaceous particles - Google Patents

Catalytic hydroconversion process of heavy hydrocarbons in the presence of a dispersed catalyst and of carbonaceous particles Download PDF

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Publication number
EP0073690B1
EP0073690B1 EP82401336A EP82401336A EP0073690B1 EP 0073690 B1 EP0073690 B1 EP 0073690B1 EP 82401336 A EP82401336 A EP 82401336A EP 82401336 A EP82401336 A EP 82401336A EP 0073690 B1 EP0073690 B1 EP 0073690B1
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Prior art keywords
process according
cenospheres
charge
weight
hydrocarbon
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German (de)
French (fr)
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EP0073690A1 (en
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Pierre Giuliani
Yves Jacquin
Christian Busson
Jean-François Josserand
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/10—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 with moving solid particles
    • C10G49/12—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 with moving solid particles suspended in the oil, e.g. slurries

Definitions

  • the present invention relates to a process for the catalytic hydroconversion of heavy hydrocarbon feedstocks containing asphaltenes and metallic impurities, sulfur and nitrogen.
  • the catalytic system of the invention leads, under the conditions of hydroconversion, to the transformation of a portion of the heavy products of the feedstock into products with a lower boiling point and significantly lowers the content of impurities by hydrodemetallization, hydrodesulfurization and hydrodenitrification as well as the value of the Conradson carbon residue.
  • cenospheres Another important advantage of the presence of the cenospheres is to allow, at the end of the reaction, easy filtration of the catalyst residues (a) present in the liquid product of the reaction.
  • the fines entrained by the gas, during gasification have an average size of less than 10 ⁇ m .
  • They contain the metals from the oil, usually vanadium, iron and nickel, and, in addition, the metallic component of the oil-soluble catalytic metal compound which had been added.
  • US Patent 4204943 describes a catalytic hydroconversion process in which the catalyst consists of carbonaceous or fine particles by deriving whose diameter is less than 10 ⁇ m. These particles and fines come from the gasification of coke.
  • US Pat. No. 4,227,995 describes a catalytic hydrodemetallization process in which the catalyst consists of particles of calcined coke or of "green coke” having a porosity of less than 0.3 cm 3 / g and a specific surface smaller than 5 m 2 / g, 50 to 80% of the pores having diameters greater than 10,000 Angstroms (1 ⁇ m).
  • US Pat. No. 4,299,685 describes a process for hydrocracking heavy oil, the catalyst of which consists of fly ash; fly ash are particles with a high mineral content and low carbon content; under the electron microscope, they have a smooth appearance. Their porosity is low, of the order of 0.3 to 0.4 cm 3 / g.
  • cenospheres originating from the combustion of industrial heavy fuels, in combination with a metallic compound dissolved or finely divided in the feed, constitute an effective hydroconversion catalyst.
  • cenospheres make it a very efficient and inexpensive material for transporting insoluble materials and the metals formed during hydroconversion.
  • Their high content of metals (Fe, Ni, V) (approximately 1 to 10% by weight, in total, of at least one of these three metals) also gives them a catalytic activity of cracking, hydrogenation and demetallation. .
  • their roughly spherical shape and their relatively large size ensure their easy removal by filtration without clogging the filters.
  • the representative cenospheres used contain, by weight, from 0.1 to 2% of vanadium (preferably 0.4 to 2%), from 0.1 to 5% of iron (preferably 0.4 to 2% ) and from 0.2 to 1% of nickel (preferably 0.5 to 1%), these values not being limiting.
  • They also contain carbon, for example 60 to 90% by weight, and sulfur, for example 2 to 10% by weight, as well as common elements such as Na and Ca.
  • the specific surface of the cenospheres can be very variable, most often between 2 and 130 m 2 / g, preferably 2 to 20 m 2 / g.
  • the average diameter of the cenospheres is usually greater than 10 ⁇ m, for example between 10 and 200 ⁇ m or between 20 and 200 ⁇ m, more particularly between 20 and 60 ⁇ m.
  • Their grain density is usually from 0.3 to 0.8 g / cm 3 , preferably from 0.4 to 0.6 g / cm 3 , and their structural density usually from 1.2 to 2.5 g / cm 3 , preferably 1.3 to 2.1 g / cm 3 .
  • Their total porous volume is usually 0.8 to 2.5 cm 3 / g, preferably 1.2 to 1.7 cm 3 / g.
  • cenospheres Certain initially spherical cenospheres may have been broken and the invention also covers the use of debris from cenospheres.
  • Hydroconversion is a process in which a part of the heavy constituents of the charge is transformed under hydrogen pressure, at high temperature, into products with a lower boiling point.
  • This process is particularly well suited for the heaviest hydrocarbon feedstocks having a Conradson carbon residue of up to 50% by weight.
  • These fillers also have very high contents by weight of asphaltenes (for example up to 40%), sulfur (for example up to 8%) and metals (for example up to 3000 ppm).
  • the catalytic metal compound used in the invention is a finely divided metallic compound preferably originating from a metallic compound soluble in the charge or from an aqueous solution of a metallic salt which is dispersed in the charge or, intermediate, in a hydrocarbon solvent.
  • the metallic constituent of these soluble compounds convertible into a solid dispersed catalyst belongs to groups VB, VI B, VII B and or VIII according to the table published by EH Sargent in 1962.
  • the preferred metals are molybdenum, vanadium, chromium , tungsten, manganese, iron, nickel, cobalt.
  • the preferred compounds are molybdenum naphthenate and molybdenum blue.
  • the amount of the soluble metal compound added to the charge is for example between 10 and 1000 ppm, preferably between 50 and 500 ppm counted by weight of metal relative to the charge.
  • the metal compound can be added either alone or mixed with one or more compounds of different metals.
  • the metallic compound, dissolved in an aqueous solution optionally pre-emulsified with a hydrocarbon can be for example: ammonium or alkali metal heptamolybdate, cobalt nitrate, nickel nitrate, ferrous sulfate or sodium tungstate.
  • the preferred compound is ammonium heptamolybdate either alone or as a mixture with another metallic water-soluble compound.
  • the amount of metallic compound dissolved in the emulsified aqueous solution is between 10 and 1000 ppm, preferably between 50 and 500 ppm counted by weight of metal.
  • the cenospheres most often come from smoke dedusting installations in large thermal power plants burning heavy industrial fuels, in particular heavy No. 2 fuels.
  • cenospheres are mixed with the filler in the proportion of 0.1 to 5% by weight relative to the latter.
  • the filler containing the cenospheres, the soluble metallic compound or the metallic salt provided by an aqueous solution or emulsion may or may not be subjected to a pretreatment.
  • the purpose of this pretreatment is to transform the metal compound or the metal salt into a finely dispersed solid catalyst comprising from 10 to 1000 ppm, preferably from 50 to 300 ppm by weight of active material counted as elemental metal, based on the weight of filler .
  • the pretreatment is carried out in the presence of hydrogen sulfide alone or in admixture with hydrogen at a temperature between 200 and 450 ° C and under a pressure between 25 and 250 bars. During this pretreatment, some or all of the metals contained in the cenospheres are also transformed into metallic sulphides.
  • the charge mixed with the constituents of the catalytic system is sent to the hydroconversion reactor where the metallic compound or the metallic salt and the metals contained in the cenospheres are transformed into metallic sulfides under the action feed sulfur and / or sulfur compounds formed during the reaction, especially H 2 S.
  • FIG. 3 describes an embodiment of the method given by way of example.
  • the fresh charge, the soluble metallic compound or the emulsion of an aqueous solution of a metallic salt in a hydrocarbon are introduced respectively by lines 1, 2 and 3 into a mixing tank 4.
  • This mixture is pumped, line 5, into a pretreatment reactor 6, where it is brought into contact with hydrogen containing from 2 to 10% of hydrogen sulfide.
  • Hydrogen is a mixture of fresh hydrogen (line 7) and recycled hydrogen (line 8).
  • the hydrogen sulphide is supplied either by recycling (line 8), or by a fresh supply (line 9).
  • the temperature is between 200 and 450 ° C, preferably 350/450 ° C, the pressure between 25 and 250 bars, preferably 100/200 bars, the reaction time between 5 minutes and 4 hours, from preferably 10 minutes to 2 hours.
  • the pretreated product is introduced (line 10) into the hydroconversion reactor 11.
  • the temperature of this reactor is between 380 and 480 ° C, preferably 420 to 460 ° C, the partial pressure of hydrogen between 25 and 250 bars , preferably between 100 and 200 bars, the hydrogen flow rate between 1000 and 5000 liters TPN / liter of charge, preferably between 1000 and 2000 I / I and the space speed (VVH) defined by the charge volume per hour and per reactor volume between 0.1 and 10, preferably between 0.25 and 5.
  • the effluent which leaves the hydroconversion reactor via line 12 comprises gases and a liquid having solids in suspension. It is introduced into a high pressure separator 13. From this separator leaves a gas (line 14) which contains hydrogen, hydrogen sulfide and light hydrocarbons. Part of this gas is recycled, after treatment to remove the hydrogen sulfide, to the pretreatment reactor or the hydroconversion reactor if there is no pretreatment. The other part is eliminated (28) to maintain the partial pressures of hydrogen and hydrogen sulfide at the fixed level.
  • This fractionation unit can be a simple vacuum evaporator or a vacuum distillation column.
  • the adjustment of the separation between distillate and residue is done to obtain a flowable and pumpable residue under industrial conditions.
  • the residue drawn off through line 17 is mixed in tank 18 with an aromatic solvent with a boiling point of between 100 and 220 ° C., introduced through line 25.
  • This solvent reduces the viscosity and allows a phase to be obtained.
  • which is treated in a separation unit 20, joined at 18 by line 19. In this separation unit, the solids are separated by filtration or centrifugation or decantation.
  • the filtered or centrifuged solids are washed with the same aromatic solvent (line 26), in the separation unit 20, to remove the oily products which coat the sulfides of the metals. catalytic, the metal sulfides contained in the charge, the cenospheres more or less charged with metals and metallic sulfides and the insoluble in the aromatic solvent.
  • a fraction of these solids is eliminated via line 21. They can be burned, carbonated or treated in order to recover the metals.
  • the other fraction is recycled to the hydroconversion reactor (line 22), this via the mixing tank 4, the residual aromatic solvent can either be kept or eliminated.
  • the aromatic solvent is withdrawn, which is reinjected into the mixer 18 through line 25, and into the separation unit 20, through line 26, for washing the filtered or centrifuged solids.
  • the hydrotreated residue leaves, largely free of metals, sulfur, nitrogen and asphaltenes. This residue is either burned, or gasified, or diluted to make a heavy fuel oil No. 2.
  • a 250 ml stainless steel autoclave is used.
  • the gas-liquid contact is ensured by shaking.
  • a test is made with 30 g of filler.
  • the autoclave after loading the soluble molybdenum compound, the cenospheres and the charge, is closed and weighed at atmospheric pressure, scanned with hydrogen and subjected to a hydrogen pressure of 100 bars for one hour to check the sealing.
  • the autoclave filled with hydrogen at 100 bars at room temperature is brought to the test temperature, in 3/4 hour to 1 hour depending on the temperature.
  • the reaction time corresponds to the temperature level. Cooling is done in the open air.
  • the autoclave is first filled with hydrogen sulphide at 10 bars, then it is completed up to 100 bars with hydrogen.
  • the mixture is heated to 380 ° C., left for 1 hour, cooled to room temperature, relaxed, scanned with hydrogen and then the test is repeated as indicated above.
  • the reaction medium is diluted with toluene and filtered.
  • the solids are washed with hot toluene.
  • the two toluene solutions, for filtration and washing, are evaporated at 100 ° C. under 0.025 bar.
  • the hydrocarbons entrained with toluene are analyzed.
  • the evaporation residue constitutes the hydro-converted product.
  • the weight balance must be greater than 95% for a test to be considered valid.
  • the charge containing the soluble metallic compound and the cenospheres is mixed in line with hydrogen containing from 3 to 7% of hydrogen sulfide, then is brought to the reaction temperature through an oven, consisting of five heating elements. It then enters the bottom of a reactor, consisting of a vertical tube.
  • the reactor effluent is cooled to 150 ° C and passed through a high pressure separator. The gas from this separator is recycled after being washed with water. A purge allows the partial pressures of hydrogen and hydrogen sulfide to be adjusted.
  • the hydroconverted product is drawn off at the base of the high pressure separator.
  • the operation is carried out batchwise with 30 g of Safanya asphalt diluted with 35% by volume of diesel oil at 420 ° C. for two hours; initial hydrogen pressure: 100 bars; no pretreatment.
  • Various tests are carried out: test without catalyst, test with cenospheres alone, test with molybdenum naphthenate alone, test with molybdenum naphthenate plus cenospheres.
  • cenospheres to molybdenum naphthenate therefore improves, in a very significant way, the demetallation without appreciably increasing the amount of insoluble matter.
  • the cenospheres allow the fixation of vanadium, nickel and molybdenum.
  • Molybdenum is not found in the liquid hydroconverted product.
  • Example 2 The tests indicated in this example are carried out under the same conditions as in Example 1. A molybdenum blue in 5.8% solution in a C 7 -C 9 alcohol is used as the molybdenum compound.
  • Example 2 The procedure is as in Example 1, but adding to the hydrocarbon feedstock, in addition to cobalt naphthenate and the cenospheres, 0.5% by weight, relative to the feedstock, of cenospheres recovered at the end of the Example 1 and washed with hot toluene.
  • the addition of these recovered cenospheres makes it possible, as shown in Table IV, to reduce the supply of fresh molybdenum naphthenate to 100 ppm, without significant modification of the results.
  • the charge is mixed with molybdenum naphthenate (500 ppm by weight of molybdenum) and 1% by weight of cenospheres, identical to those used in Example 1. It is introduced into the preheating oven at the rate of 1 liter / h , where it is brought to 430 ° C, the temperature at which it enters the reaction chamber.
  • molybdenum naphthenate 500 ppm by weight of molybdenum
  • cenospheres identical to those used in Example 1. It is introduced into the preheating oven at the rate of 1 liter / h , where it is brought to 430 ° C, the temperature at which it enters the reaction chamber.
  • the total pressure is 150 bars.
  • the recycled hydrogen is introduced online just before the preheater, with an H 2 / Hydrocarbon ratio equal to 1000 liters per liter, the hydrogen being considered at normal temperature and pressure.
  • Hydrogen contains 2 to 3% hydrogen sulfide.
  • the space velocity, charge volume per hour and per reactor volume, is equal to 1.2, which corresponds to a residence time in the reactor of 54 minutes.
  • Table V shows the results obtained after 100 hours of operation under the preceding conditions.
  • Table VI provides the filtration rates for these different products as well as their viscosity at 50 "C.

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Description

La présente invention concerne un procédé d'hydroconversion catalytique de charges lourdes hydrocarbonées contenant des asphaltènes et des impuretés métalliques, soufrées et azotées.The present invention relates to a process for the catalytic hydroconversion of heavy hydrocarbon feedstocks containing asphaltenes and metallic impurities, sulfur and nitrogen.

Ce procédé utilise comme système catalytique une combinaison:

  • a) d'au moins un composé de métal catalytique en solution ou dispersion, avec
  • b) des suies constituées de particules appelées cénosphères provenant de la combustion de charges lourdes d'hydrocarbures, contenant des composés de métaux, notamment des composés de vanadium, nickel et fer. Ces suies représentent un élément catalytique bon marché.
This process uses as a catalytic system a combination:
  • a) at least one catalytic metal compound in solution or dispersion, with
  • b) soot consisting of particles called cenospheres originating from the combustion of heavy hydrocarbon charges, containing metal compounds, in particular compounds of vanadium, nickel and iron. This soot represents a cheap catalytic element.

Le système catalytique de l'invention conduit dans les conditions de l'hydroconversion à la transformation d'une partie des produits lourds de la charge en produits à plus bas point d'ébullition et abaisse notablement la teneur en impuretés par hydrodémétallation, hydrodésulfuration et hydrodénitrification ainsi que la valeur du résidu de carbone Conradson.The catalytic system of the invention leads, under the conditions of hydroconversion, to the transformation of a portion of the heavy products of the feedstock into products with a lower boiling point and significantly lowers the content of impurities by hydrodemetallization, hydrodesulfurization and hydrodenitrification as well as the value of the Conradson carbon residue.

Un autre avantage important de la présence des cénosphères est de permettre, en fin de réaction, une filtration aisée des résidus de catalyseur (a) présents dans le produit liquide de la réaction.Another important advantage of the presence of the cenospheres is to allow, at the end of the reaction, easy filtration of the catalyst residues (a) present in the liquid product of the reaction.

Un procédé d'hydroconversion de charges d'huiles lourdes hydrocarbonées utilisant comme catalyseur dispersé la combinaison de:

  • a) un composé solide de métal catalique formé in situ à partir d'un composé de ce métal soluble dans la charge d'huile lourde, avec
  • b) des particules charbonneuses ou des fines en dérivant, provenant de la gazéification de coke,

est décrit dans le brevet US 4 178 227.A process for hydroconversion of hydrocarbon heavy oil feedstocks using as a dispersed catalyst the combination of:
  • a) a solid compound of catalic metal formed in situ from a compound of this metal soluble in the charge of heavy oil, with
  • b) carbonaceous particles or fines derived therefrom from the gasification of coke,

is described in US Patent 4,178,227.

Dans ce brevet, les fines entraînées par le gaz, lors de la gazéification, ont une taille moyenne inférieure à 10 lim. Elles renferment les métaux provenant de l'huile, c'est-à-dire usuellement du vanadium, du fer et du nickel, et, en plus, le constituant métallique du composé de métal catalytique, soluble dans l'huile, qui avait été ajouté.In this patent, the fines entrained by the gas, during gasification, have an average size of less than 10 μm . They contain the metals from the oil, usually vanadium, iron and nickel, and, in addition, the metallic component of the oil-soluble catalytic metal compound which had been added.

Le brevet US 4204943 décrit un procédé d'hydroconversion catalytique dont le catalyseur est constitué de particules charbonneuses ou fines en dérivant dont le diamètre est inférieur à 10 !lm. Ces particules et ces fines proviennent de la gazéification de coke.US Patent 4204943 describes a catalytic hydroconversion process in which the catalyst consists of carbonaceous or fine particles by deriving whose diameter is less than 10 μm. These particles and fines come from the gasification of coke.

Le brevet US 4 227 995 décrit un procédé d'hydrodémétallation catalytique dont le catalyseur est constitué de particules de coke calciné ou de »green coke« ayant une porosité inférieure à 0,3 cm3/g et une surface spécifique plus petite que 5 m2/g, 50 à 80% des pores ayant des diamètres supérieurs à 10 000 Angstrôms (1 µm).US Pat. No. 4,227,995 describes a catalytic hydrodemetallization process in which the catalyst consists of particles of calcined coke or of "green coke" having a porosity of less than 0.3 cm 3 / g and a specific surface smaller than 5 m 2 / g, 50 to 80% of the pores having diameters greater than 10,000 Angstroms (1 µm).

Le brevet US 4 299 685 décrit un procédé d'hydrocracking d'huile lourde dont le catalyseur est constitué par des cendres volantes; les cendres volantes sont des particules à forte teneur en minéraux et faible teneur en carbone; au microscope électronique, elles présentent un aspect lisse. Leur porosité est faible, de l'ordre de 0,3 à 0,4 cm3/g.US Pat. No. 4,299,685 describes a process for hydrocracking heavy oil, the catalyst of which consists of fly ash; fly ash are particles with a high mineral content and low carbon content; under the electron microscope, they have a smooth appearance. Their porosity is low, of the order of 0.3 to 0.4 cm 3 / g.

On a découvert que l'utilisation de particules carbonées au moins en partie sensiblement sphériques, dites cénosphères, provenant de la combustion des fuels lourds industriels, en combinaison avec un composé métallique dissous ou finement divisé dans la charge, constituent un catalyseur efficace d'hydroconversion de charges lourdes hydrocarbonées avec de très bons rendements en conversion des produits lourds en produits plus légers, en hydrodémétallation, en hydrodésulfuration et en hydrodénitrification.It has been discovered that the use of at least partially substantially spherical carbonaceous particles, called cenospheres, originating from the combustion of industrial heavy fuels, in combination with a metallic compound dissolved or finely divided in the feed, constitute an effective hydroconversion catalyst. heavy hydrocarbon feedstocks with very good yields in conversion of heavy products into lighter products, in hydrodemetallization, in hydrodesulfurization and in hydrodenitrification.

Les caractéristiques propres de ces cénosphères en font un matériau très efficace et bon marché pour véhiculer les matières insolubles et les métaux formés au cours de l'hydroconversion. Leur teneur en métaux (Fe, Ni, V) importante (environ 1 à 10% en poids, au total, de l'un au moins de ces trois métaux) leur confère également une activité catalytique de cracking, d'hydrogénation et de démétallation. Enfin leur forme grossièrement sphérique et leur taille relativement importante assurent leur élimination facile par filtration sans colmatage des filtres.The specific characteristics of these cenospheres make it a very efficient and inexpensive material for transporting insoluble materials and the metals formed during hydroconversion. Their high content of metals (Fe, Ni, V) (approximately 1 to 10% by weight, in total, of at least one of these three metals) also gives them a catalytic activity of cracking, hydrogenation and demetallation. . Finally, their roughly spherical shape and their relatively large size ensure their easy removal by filtration without clogging the filters.

De façon préferée les cénosphères représentatives utilisées renferment, en poids, de 0,1 à 2% de vanadium (de préférence 0,4 à 2%), de 0,1 à 5% de fer (de préférence 0,4 à 2%) et de 0,2 à 1% de nickel (de préférence 0,5 à 1 %), ces valeurs n'étant pas limitatives.Preferably, the representative cenospheres used contain, by weight, from 0.1 to 2% of vanadium (preferably 0.4 to 2%), from 0.1 to 5% of iron (preferably 0.4 to 2% ) and from 0.2 to 1% of nickel (preferably 0.5 to 1%), these values not being limiting.

Elles renferment également du carbone, par exemple 60 à 90% en poids, et du soufre, par exemple 2 à 10% en poids, ainsi que des éléments courants tels que Na et Ca.They also contain carbon, for example 60 to 90% by weight, and sulfur, for example 2 to 10% by weight, as well as common elements such as Na and Ca.

La surface spécifique des cénosphères peut être très variable, le plus souvent entre 2 et 130 m2/g, de préférence 2 à 20 m2/g.The specific surface of the cenospheres can be very variable, most often between 2 and 130 m 2 / g, preferably 2 to 20 m 2 / g.

Les cénosphères, examinées au microscope électronique, présentent une structure poreuse, analogue à celle de 1, ponce ou d'une éponge.

  • La figure 1 est un agrandissement de 400 fois d'un groupe de cénosphères.
  • La figure 2 est un agrandissement do 1000 fois d'un groupe de cénosphères.
The cenospheres, examined under an electron microscope, have a porous structure, similar to that of pumice or a sponge.
  • Figure 1 is a 400-fold magnification of a group of cenospheres.
  • Figure 2 is a 1000-fold magnification of a group of cenospheres.

On admet généralement que les cénosphères résultent d'un craquage des gouttelettes de fuel. Elles se distinguent donc des particules élémentaires de suie dont la taille est de seulement quelques centaines d'Angstrôms (1 A = 10-10 mètres), bien que ces particules puissent s'agglomérer sous forme de chaînes beaucoup plus longues.It is generally accepted that the cenospheres result from cracking of the fuel droplets. They are therefore distinguished from elementary soot particles whose size is only a few hundred angstroms (1 A = 10- 10 meters), although these particles may agglomerate in the form of much longer strings.

Le diamètre moyen des cénosphères est habituellement supérieur à 10 ym, par exemple entre 10 et 200 µm ou entre 20 et 200 µm, plus particulièrement entre 20 et 60 µm.The average diameter of the cenospheres is usually greater than 10 μm, for example between 10 and 200 μm or between 20 and 200 μm, more particularly between 20 and 60 μm.

Leur densité de grain est habituellement de 0,3 à 0,8 g/cm3, de préférence de 0,4 à 0,6 g/cm3, et leur densité structurale habituellement de 1,2 à 2,5 g/cm3, de préférence 1,3 à 2,1 g/cm3.Their grain density is usually from 0.3 to 0.8 g / cm 3 , preferably from 0.4 to 0.6 g / cm 3 , and their structural density usually from 1.2 to 2.5 g / cm 3 , preferably 1.3 to 2.1 g / cm 3 .

Leurvolume poreux total est habituellement de 0,8 à 2,5 cm3/g, de préférence 1,2 à 1,7 cm3/g.Their total porous volume is usually 0.8 to 2.5 cm 3 / g, preferably 1.2 to 1.7 cm 3 / g.

Certaines cénosphères initialement sphériques peuvent avoir été brisées et l'invention couvre aussi l'utilisation des débris de cénosphères.Certain initially spherical cenospheres may have been broken and the invention also covers the use of debris from cenospheres.

On appelle hydroconversion un procédé dans lequel une partie des constituants lourds de la charge est transformée sous pression d'hydrogène, à haute température, en produits à point d'ébullition plus bas.Hydroconversion is a process in which a part of the heavy constituents of the charge is transformed under hydrogen pressure, at high temperature, into products with a lower boiling point.

Suivant l'invention, on valorise les charges lourdes hydrocarbonées suivant un procédé d'hydroconversion qui comprend:

  • 1. l'addition à la charge d'hydrocarbures de:
    • a) au moins un composé de métal catalytique, de préférence sous forme d'une solution dans un solvant, par exemple dans l'eau ou dans un solvant d'hydrocarbure, le métal du composé appartenant à l'un au moins des groupes V B, VI B, VII B et VIII, et
    • b) des cénosphères,
  • 2. le maintien du mélange résultant dans des conditions d'hydroconversion, et
  • 3. le fractionnement des produits obtenus.
According to the invention, the heavy hydrocarbon feedstocks are valued according to a hydroconversion process which comprises:
  • 1. the addition to the hydrocarbon load of:
    • a) at least one catalytic metal compound, preferably in the form of a solution in a solvent, for example in water or in a hydrocarbon solvent, the metal of the compound belonging to at least one of the VB groups , VI B, VII B and VIII, and
    • b) cenospheres,
  • 2. maintaining the resulting mixture under hydroconversion conditions, and
  • 3. the fractionation of the products obtained.

Le procédé, objet de cette invention, est applicable aux charges lourdes hyrocarbonées contenant des asphaltènes et des impuretés métalliques, soufrées et azotées. Ces charges lourdes comprennent:

  • - les pétroles bruts et les fractions dérivées de ces pétroles bruts,
  • - les fractions lourdes tirées du pétrole, telles que les résidus de distillation atmosphérique ou sous-vide,
  • - les alphates provenant des unités de désasphaltage,
  • - les goudrons, bitumes, produits venant des sables et schistes bitumineux,
  • - les fractions liquides riches en asphaltènes provenant de la liquéfaction du charbon.
The process which is the subject of this invention is applicable to hyrocarbon heavy fillers containing asphaltenes and metallic impurities, sulfur and nitrogen. These heavy loads include:
  • - crude oils and fractions derived from these crude oils,
  • - heavy fractions from petroleum, such as atmospheric or vacuum distillation residues,
  • - alphates from deasphalting units,
  • - tars, bitumens, products from tar sands and oil shales,
  • - liquid fractions rich in asphaltenes from the liquefaction of coal.

Ce procédé est particulièrement bien adapté pour les charges hydrocarbonées les plus lourdes ayant un résidu en carbone Conradson pouvant aller jusqu'à 50% en poids. Ces charges ont également des teneurs pondérales très élevées en asphaltènes (par exemple jusqu'à 40%), en soufre (par exemple jusqu'à 8%) et en métaux (par exemple jusqu'à 3000 ppm).This process is particularly well suited for the heaviest hydrocarbon feedstocks having a Conradson carbon residue of up to 50% by weight. These fillers also have very high contents by weight of asphaltenes (for example up to 40%), sulfur (for example up to 8%) and metals (for example up to 3000 ppm).

Le composé de métal catalytique, utilisé dans l'invention est un composé métallique finement divisé provenant de préférence d'un composé métallique soluble dans la charge ou d'une solution aqueuse d'un sel métallique que l'on disperse dans la charge ou, intermédiairement, dans un solvant hydrocarboné.The catalytic metal compound used in the invention is a finely divided metallic compound preferably originating from a metallic compound soluble in the charge or from an aqueous solution of a metallic salt which is dispersed in the charge or, intermediate, in a hydrocarbon solvent.

Le composé métallique soluble dans la charge peut être choisi parmi:

  • - les composés métalliques inorganiques tels que les halogénures, les oxyhalogénures, les polyhé- téroacides, par exemple: acide phosphomolybdique, bleus de molybdène, acide alkyldithiophos- phorique,
  • - les sels métalliques d'un acide organique, aliphatique, naphténique ou aromatique, d'un acide sulfonique, d'un acide sulfinique, d'un acide xanthique, d'un mercaptan, d'un phénol ou d'un composé aromatique polyhydroxylé,
  • - les chélates métalliques, tels que les complexes 8-côtoniques, les penta et hexacarbonyls, les complexes avec l'éthylènediamine, l'acide ethylènediaminetetracétique, les phtalocyanines,
  • - les sels métalliques des amines organiques et des sels d'ammonium quaternaire.
The metallic compound soluble in the filler can be chosen from:
  • - inorganic metal compounds such as halides, oxyhalides, polyheteroacids, for example: phosphomolybdic acid, molybdenum blues, alkyldithiophosphoric acid,
  • - the metal salts of an organic, aliphatic, naphthenic or aromatic acid, a sulfonic acid, a sulfinic acid, a xanthic acid, a mercaptan, a phenol or a polyhydroxy aromatic compound ,
  • - metal chelates, such as 8-ribonic complexes, penta and hexacarbonyls, complexes with ethylenediamine, ethylenediaminetetracetic acid, phthalocyanines,
  • - metal salts of organic amines and quaternary ammonium salts.

Le constituant métallique de ces composés solubles et convertibles en un catalyseur solide dispersé, appartient aux groupes V B, VI B, VII B et ou VIII suivant la table publiée par E. H. Sargent en 1962. Les métaux préférés sont le molybdène, le vanadium, le chrome, le tungstène, le manganèse, le fer, le nickel, le cobalt. Les composés préférés sont le naphténate de molybdène et le bleu de molybdène.The metallic constituent of these soluble compounds convertible into a solid dispersed catalyst belongs to groups VB, VI B, VII B and or VIII according to the table published by EH Sargent in 1962. The preferred metals are molybdenum, vanadium, chromium , tungsten, manganese, iron, nickel, cobalt. The preferred compounds are molybdenum naphthenate and molybdenum blue.

La quantité du composé métallique soluble ajouté à la charge est comprise par exemple entre 10 et 1000 ppm, de préférence entre 50 et 500 ppm comptées en poids de métal par rapport à la charge.The amount of the soluble metal compound added to the charge is for example between 10 and 1000 ppm, preferably between 50 and 500 ppm counted by weight of metal relative to the charge.

Le composé métallique peut être ajouté soit seul, soit mélangé avec un ou plusieurs composés de métaux différents.The metal compound can be added either alone or mixed with one or more compounds of different metals.

Le composé métallique, dissous dans une solution aqueuse éventuellement pré-émulsifiée avec un hydrocarbure, peut être par exemple: l'heptamolybdate d'ammonium ou d'un métal alcalin, le nitrate de cobalt, le nitrate de nickel, le sulfate ferreux ou le tungstate de sodium.The metallic compound, dissolved in an aqueous solution optionally pre-emulsified with a hydrocarbon, can be for example: ammonium or alkali metal heptamolybdate, cobalt nitrate, nickel nitrate, ferrous sulfate or sodium tungstate.

Le composé préféré est l'heptamolybdate d'ammonium soit seul, soit en mélange avec un autre composé métallique soluble dans l'eau.The preferred compound is ammonium heptamolybdate either alone or as a mixture with another metallic water-soluble compound.

La quantité de composé métallique dissous dans la solution aqueuse émulsifiée est comprise entre 10 et 1000 ppm, de préférence entre 50 et 500 ppm comptées en poids de métal.The amount of metallic compound dissolved in the emulsified aqueous solution is between 10 and 1000 ppm, preferably between 50 and 500 ppm counted by weight of metal.

Les cénosphères proviennent le plus souvent des installations de dépoussiérage des fumées dans les grandes centrales thermiques brûlant des fuels lourds industriels, en particulier des fuels lourds n" 2.The cenospheres most often come from smoke dedusting installations in large thermal power plants burning heavy industrial fuels, in particular heavy No. 2 fuels.

Ces cénosphères sont mélangées avec la charge dans la proportion de 0,1 à 5% en poids par rapport à celle-ci.These cenospheres are mixed with the filler in the proportion of 0.1 to 5% by weight relative to the latter.

La charge contenant les cénosphères, le composé métallique soluble ou le sel métallique apporté par une solution ou une émulsion aqueuse peut être soumise ou non à un prétraitement.The filler containing the cenospheres, the soluble metallic compound or the metallic salt provided by an aqueous solution or emulsion may or may not be subjected to a pretreatment.

Ce prétraitement a pour but de transformer le composé métallique ou le sel métallique en un catalyseur solide finement dispersé comprenant de 10 à 1000 ppm, de préférence de 50 à 300 ppm en poids de matière active comptée en métal élémentaire, basé sur le poids de charge. Le prétraitement se fait en présence d'hydrogène sulfuré seul ou en mélange avec de l'hydrogène à une température entre 200 et 450° C et sous une pression comprise entre 25 et 250 bars. Au cours de ce prétraitement une partie ou la totalité des métaux contenus dans les cénosphères est transformée également en sulfures métalliques.The purpose of this pretreatment is to transform the metal compound or the metal salt into a finely dispersed solid catalyst comprising from 10 to 1000 ppm, preferably from 50 to 300 ppm by weight of active material counted as elemental metal, based on the weight of filler . The pretreatment is carried out in the presence of hydrogen sulfide alone or in admixture with hydrogen at a temperature between 200 and 450 ° C and under a pressure between 25 and 250 bars. During this pretreatment, some or all of the metals contained in the cenospheres are also transformed into metallic sulphides.

Quand il n'y a pas de prétraitement, la charge mélangée avec les constituants du système catalytique est envoyée au réacteur d'hydroconversion où le composé métallique ou le sel métallique et les métaux contenus dans les cénosphères sont transformés en sulfures métalliques sous l'action du soufre de la charge et/ou des composés du soufre formés au cours de la réaction, notamment H2S.When there is no pretreatment, the charge mixed with the constituents of the catalytic system is sent to the hydroconversion reactor where the metallic compound or the metallic salt and the metals contained in the cenospheres are transformed into metallic sulfides under the action feed sulfur and / or sulfur compounds formed during the reaction, especially H 2 S.

La figure 3 décrit un mode de réalisation du procédé donné à titre d'exemple.FIG. 3 describes an embodiment of the method given by way of example.

La charge fraîche, le composé métallique soluble ou l'émulsion d'une solution aqueuse d'un sel métallique dans un hydrocarbure sont introduits respectivement par les conduites 1, 2 et 3 dans un bac de mélange 4.The fresh charge, the soluble metallic compound or the emulsion of an aqueous solution of a metallic salt in a hydrocarbon are introduced respectively by lines 1, 2 and 3 into a mixing tank 4.

Ce mélange est pompé, conduite 5, dans un réacteur de prétraitement 6, où il est mis en contact avec de l'hydrogène contenant de 2 à 10% d'hydrogène sulfuré. L'hydrogène est un mélange d'hydrogène frais (conduite 7) et d'hydrogène de recyclage (conduite 8). L'hydrogène sulfuré est apporté soit par recyclage (conduite 8), soit par un apport frais (conduite 9). Pour ce prétraitement, la température est comprise entre 200 et 450°C, de préférence 350/450°C, la pression entre 25 et 250 bars, de préférence 100/200 bars, le temps de réaction entre 5 minutes et 4 heures, de préférence 10 minutes à 2 heures.This mixture is pumped, line 5, into a pretreatment reactor 6, where it is brought into contact with hydrogen containing from 2 to 10% of hydrogen sulfide. Hydrogen is a mixture of fresh hydrogen (line 7) and recycled hydrogen (line 8). The hydrogen sulphide is supplied either by recycling (line 8), or by a fresh supply (line 9). For this pretreatment, the temperature is between 200 and 450 ° C, preferably 350/450 ° C, the pressure between 25 and 250 bars, preferably 100/200 bars, the reaction time between 5 minutes and 4 hours, from preferably 10 minutes to 2 hours.

Le produit prétraité est introduit (conduite 10) dans le réacteur d'hydroconversion 11. La température de ce réacteur est comprise entre 380 et 480°C, de préférence 420 à 460°C, la pression partielle d'hydrogène entre 25 et 250 bars, de préférence entre 100 et 200 bars, le débit d'hydrogène entre 1000 et 5000 litres TPN/litre de charge, de préférence entre 1000 et 2000 I/I et la vitesse spatiale (VVH) définie par le volume de charge par heure et par volume de réacteur entre 0,1 et 10, de préférence entre 0,25 et 5.The pretreated product is introduced (line 10) into the hydroconversion reactor 11. The temperature of this reactor is between 380 and 480 ° C, preferably 420 to 460 ° C, the partial pressure of hydrogen between 25 and 250 bars , preferably between 100 and 200 bars, the hydrogen flow rate between 1000 and 5000 liters TPN / liter of charge, preferably between 1000 and 2000 I / I and the space speed (VVH) defined by the charge volume per hour and per reactor volume between 0.1 and 10, preferably between 0.25 and 5.

L'effluent qui sort du réacteur d'hydroconversion par la conduite 12, comprend des gaz et un liquide ayant en suspension des solides. Il est introduit dans un séparateur haute pression 13. De ce séparateur part un gaz (conduite 14) qui contient de l'hydrogène, de l'hydrogène sulfuré et des hydrocarbures légers. Une partie de ce gaz est recyclée, après traitement pour éliminer le sulfure d'hydrogène, vers le réacteur de prétraitement ou le réacteur d'hydroconversion s'il n'y a pas de prétraitement. L'autre partie est éliminée (28) pour maintenir les pressions partielles d'hydrogène et d'hydrogène sulfuré au niveau fixé.The effluent which leaves the hydroconversion reactor via line 12 comprises gases and a liquid having solids in suspension. It is introduced into a high pressure separator 13. From this separator leaves a gas (line 14) which contains hydrogen, hydrogen sulfide and light hydrocarbons. Part of this gas is recycled, after treatment to remove the hydrogen sulfide, to the pretreatment reactor or the hydroconversion reactor if there is no pretreatment. The other part is eliminated (28) to maintain the partial pressures of hydrogen and hydrogen sulfide at the fixed level.

Par la conduite 15 est soutiré, à travers une vanne de détente, un produit liquide avec en suspension des solides.Via the line 15, a liquid product with suspended solids is drawn off through an expansion valve.

Pour traiter ce mélange, il est possible d'utiliser différents traitements, faisant appel à des technologies connues. Ceux-ci diffèrent suivant les caractéristiques de la charge, la sévérité de l'hydroconversion, l'utilisation des produits finis, par exemple.To treat this mixture, it is possible to use different treatments, using known technologies. These differ according to the characteristics of the charge, the severity of the hydroconversion, the use of the finished products, for example.

Atitre indicatif, est donné un mode de traitement représenté dans la figure 3 ci-jointe.Indicative title, is given a processing mode represented in figure 3 attached.

Le produit liquide, issu du séparateur 13 par la conduite 15, passe dans un séparateur basse pression (non représenté) où une purge d'eau peut être faite. Il est ensuite introduit (conduite 15) dans une unité de fractionnement 16, d'où l'on retire une ou plusieurs fractions (17 et 29).The liquid product, coming from the separator 13 through line 15, passes through a low pressure separator (not shown) where a water purge can be made. It is then introduced (line 15) into a fractionation unit 16, from which one or more fractions (17 and 29) are removed.

Cette unité de fractionnement peut être un simple vaporisateur sous vide ou une colonne de distillation sous vide. Le réglage de la séparation entre distillat et résidu est fait pour obtenir un résidu coulable et pompable dans des conditions industrielles.This fractionation unit can be a simple vacuum evaporator or a vacuum distillation column. The adjustment of the separation between distillate and residue is done to obtain a flowable and pumpable residue under industrial conditions.

Le résidu soutiré par la conduite 17 est mélangé dans le bac 18 avec un solvant aromatique de point d'ébullition compris entre 100 et 220°C, introduit par la conduite 25. Ce solvant diminue la viscosité et permet l'obtention d'une phase qui est traitée dans une unité de séparation 20, réunie à 18 par la conduite 19. Dans cette unité de séparation on sépare les solides par filtration ou centrifugation ou décantation.The residue drawn off through line 17 is mixed in tank 18 with an aromatic solvent with a boiling point of between 100 and 220 ° C., introduced through line 25. This solvent reduces the viscosity and allows a phase to be obtained. which is treated in a separation unit 20, joined at 18 by line 19. In this separation unit, the solids are separated by filtration or centrifugation or decantation.

Les solides filtrés ou centrifugés sont lavés par le même solvant aromatique (conduite 26), dans l'unité de séparation 20, pour éliminer les produits huileux qui enrobent les sulfures des métaux catalytiques, les sulfures des métaux contenus dans la charge, les cénosphères plus ou moins chargées en métaux et en sulfures métalliques et les insolubles dans le solvant aromatique.The filtered or centrifuged solids are washed with the same aromatic solvent (line 26), in the separation unit 20, to remove the oily products which coat the sulfides of the metals. catalytic, the metal sulfides contained in the charge, the cenospheres more or less charged with metals and metallic sulfides and the insoluble in the aromatic solvent.

Une fraction de ces solides est éliminée par la conduite 21. Ils peuvent être brûlés, gazéifiés ou traités en vue de récupérer les métaux. L'autre fraction est recyclée vers le réacteur d'hydroconversion (conduite 22), celà par l'intermédiaire du bac de mélange 4, le solvant aromatique résiduel pouvant être soit gardé, soit éliminé.A fraction of these solids is eliminated via line 21. They can be burned, carbonated or treated in order to recover the metals. The other fraction is recycled to the hydroconversion reactor (line 22), this via the mixing tank 4, the residual aromatic solvent can either be kept or eliminated.

La phase liquide provenant de l'unité de séparation 20, mélangée au solvant de lavage, entre par la conduite 23 dans une unité de distillation 24.The liquid phase coming from the separation unit 20, mixed with the washing solvent, enters via the line 23 into a distillation unit 24.

En tête de cette unité est soutiré le solvant aromatique qui est réinjecté dans le mélangeur 18 par la conduite 25, et dans l'unité de séparation 20, par la conduite 26, pour le lavage des solides filtrés ou centrifugés. A la base de la colonne de distillation 24, sort le résidu hydrotraité (conduit 27), en grande partie débarrassé de métaux, de soufre, d'azote et d'asphaltènes. Ce résidu est soit brûlé, soit gazéifié, soit dilué pourfaire un fuel lourd n° 2.At the head of this unit, the aromatic solvent is withdrawn, which is reinjected into the mixer 18 through line 25, and into the separation unit 20, through line 26, for washing the filtered or centrifuged solids. At the base of the distillation column 24, the hydrotreated residue (conduit 27) leaves, largely free of metals, sulfur, nitrogen and asphaltenes. This residue is either burned, or gasified, or diluted to make a heavy fuel oil No. 2.

Il convient de noter qu'avec le recyclage d'une partie des produits solides provenant de l'unité de séparation 20, il est possible soit de diminuer, soit même de suspendre par intermittence, l'introduction avec la charge de composé métallique frais. La quantité de ce composé métallique frais sera choisie en fonction du niveau d'activité désiré.It should be noted that with the recycling of part of the solid products coming from the separation unit 20, it is possible either to reduce, or even to suspend intermittently, the introduction with the charge of fresh metallic compound. The quantity of this fresh metallic compound will be chosen according to the level of activity desired.

ExempleExample Procedure experimentaleExperimental procedure a) Essai en discontinua) Batch test

On utilise un autoclave de 250 ml en acier inoxydable. Le contact gaz-liquide est assuré par une agitation par secousses.A 250 ml stainless steel autoclave is used. The gas-liquid contact is ensured by shaking.

Un essai est fait avec 30 g de charge. L'autoclave, après le chargement du composé soluble de molybdène, des cénosphères et de la charge, est fermé et pesé à pression atmosphérique, balayé à l'hydrogène et soumis à une pression d'hydrogène de 100 bars pendant une heure pour vérifier l'étanchéité.A test is made with 30 g of filler. The autoclave, after loading the soluble molybdenum compound, the cenospheres and the charge, is closed and weighed at atmospheric pressure, scanned with hydrogen and subjected to a hydrogen pressure of 100 bars for one hour to check the sealing.

L'autoclave, rempli d'hydrogène sous 100 bars à température ambiante est porté à la température de l'essai, en 3/4 heure à 1 heure suivant la température. Le temps de réaction correspond au palier de température. Le refroidissement est fait à l'air libre.The autoclave, filled with hydrogen at 100 bars at room temperature is brought to the test temperature, in 3/4 hour to 1 hour depending on the temperature. The reaction time corresponds to the temperature level. Cooling is done in the open air.

En cas de prétraitement, on remplit l'autoclave d'abord avec du sulfure d'hydrogène sous 10 bars, puis on complète jusqu'à 100 bars par de l'hydrogène. On chauffe jusqu'à 380°C, laisse 1 heure, refroidit à température ambiante, détend, balaye par de l'hydrogène puis on reprend l'essai comme indiqué plus haut.In the case of pretreatment, the autoclave is first filled with hydrogen sulphide at 10 bars, then it is completed up to 100 bars with hydrogen. The mixture is heated to 380 ° C., left for 1 hour, cooled to room temperature, relaxed, scanned with hydrogen and then the test is repeated as indicated above.

Après refroidissement l'autoclave est depressurisé. Les gaz sont lavés à la soude, mesurés dans un compteur et analysés par chromatographie en phase gazeuse.After cooling the autoclave is depressurized. The gases are washed with soda, measured in a counter and analyzed by gas chromatography.

Le milieu réactionnel est dilué par du toluène et filtré. Les solides sont lavés par du toluène chaud. Les deux solutions toluéniqùes, de filtration et de lavage, sont évaporées à 100°C sous 0,025 bar. Les hydrocarbures entraînés avec le toluène sont analysés. Le résidu d'évaporation constitue le produit hydro-converti.The reaction medium is diluted with toluene and filtered. The solids are washed with hot toluene. The two toluene solutions, for filtration and washing, are evaporated at 100 ° C. under 0.025 bar. The hydrocarbons entrained with toluene are analyzed. The evaporation residue constitutes the hydro-converted product.

Le bilan pondéral doit être supérieur à 95% pour qu'un essai soit jugé valable.The weight balance must be greater than 95% for a test to be considered valid.

b) Essai en continub) Continuous test

La charge contenant le composé métallique soluble et les cénosphères est mélangée en ligne avec de l'hydrogène contenant de 3 à 7% d'hydrogène sulfuré, puis est portée à la température de réaction à travers un four, constitué de cinq éléments chauffants. Elle entre ensuite au bas d'un réacteur, consistant en un tube vertical. L'effluent du réacteur est refroidi jusqu'à 150°C et passe dans un séparateur haute prèssion. Le gaz venant de ce séparateur est recyclé après avoir été lavé à l'eau. Une purge permet de régler les pressions partielles d'hydrogène et d'hydrogène sulfuré. Le produit hydroconverti est soutiré à la base du séparateur haute pression.The charge containing the soluble metallic compound and the cenospheres is mixed in line with hydrogen containing from 3 to 7% of hydrogen sulfide, then is brought to the reaction temperature through an oven, consisting of five heating elements. It then enters the bottom of a reactor, consisting of a vertical tube. The reactor effluent is cooled to 150 ° C and passed through a high pressure separator. The gas from this separator is recycled after being washed with water. A purge allows the partial pressures of hydrogen and hydrogen sulfide to be adjusted. The hydroconverted product is drawn off at the base of the high pressure separator.

Deux charges ont été utilisées dans les exemples (tableau I); ce sont un résidu sous vide Safanya et un asphalte, provenant d'une unité de désasphaltage au pentane du même résidu sous vide; cet asphalte est dilué avec 35% en volume de gas-oil.

Figure imgb0001
Les cénosphères présentaient les caractéristiques suivantes:
Figure imgb0002
 Two charges were used in the examples (Table I); these are a Safanya vacuum residue and an asphalt, coming from a pentane deasphalting unit of the same vacuum residue; this asphalt is diluted with 35% by volume of diesel.
Figure imgb0001
 The cenospheres had the following characteristics:
Figure imgb0002

Exemple 1Example 1

On opère en discontinu avec 30 g d'asphalte Safanya dilué avec 35% en volume de gas-oil à 420°C pendant deux heures; pression initiale d'hydrogène: 100 bars; pas de prétraitement. On effectue différents essais: essai sans catalyseur, essai avec cénosphères seules, essai avec naphténate de molybdène seul, essai avec naphténate de molybdène plus des cénosphères.The operation is carried out batchwise with 30 g of Safanya asphalt diluted with 35% by volume of diesel oil at 420 ° C. for two hours; initial hydrogen pressure: 100 bars; no pretreatment. Various tests are carried out: test without catalyst, test with cenospheres alone, test with molybdenum naphthenate alone, test with molybdenum naphthenate plus cenospheres.

Le tableau Il rassemble les résultats fournis par ces essais.

Figure imgb0003
Table II brings together the results provided by these tests.
Figure imgb0003

L'addition de cénosphères au naphténate de molybdène améliore donc, d'une façon très sensible, la démétallation sans augmenter sensiblement la quantité d'insoluble.The addition of cenospheres to molybdenum naphthenate therefore improves, in a very significant way, the demetallation without appreciably increasing the amount of insoluble matter.

Les cénosphères seules, essai 301, par rapport à l'essai 278, seulement thermique, présentent déjà une activité hydrogénante et désulfurante, ainsi que le montrent le rapport C'3/C3 et le pourcentage d'hydrodésulfuration.The cenospheres alone, test 301, compared with test 278, only thermal, already exhibit a hydrogenating and desulphurizing activity, as shown by the C ' 3 / C 3 ratio and the percentage of hydrodesulfurization.

Les cénosphères permettent la fixation du vanadium, du nickel et du molybdène.The cenospheres allow the fixation of vanadium, nickel and molybdenum.

On ne retrouve pas de molybdène dans le produit hydroconverti liquide.Molybdenum is not found in the liquid hydroconverted product.

Exemple 2Example 2

Les essais indiqués dans cet exemple sont faits dans les mêmes conditions que dans l'exemple 1. On utilise, comme composé soluble du molybdène, un bleu de molybdène en solution à 5,8% dans un alcool C7-C9.The tests indicated in this example are carried out under the same conditions as in Example 1. A molybdenum blue in 5.8% solution in a C 7 -C 9 alcohol is used as the molybdenum compound.

Le tableau III rassemble les résultats de ces essais.

Figure imgb0004
Table III collates the results of these tests.
Figure imgb0004

Ces essais confirment les résultats obtenus avec le naphténate de molybdène, à savoir la présence de cénosphères augmente l'activité d'hydrométallation et réduit le poids d'insoluble.These tests confirm the results obtained with molybdenum naphthenate, namely the presence of cenospheres increases the hydrometallation activity and reduces the weight of insoluble matter.

Exemple 3Example 3

On opère comme dans l'exemple 1, mais on ajoute à la charge d'hydrocarbures, en plus du naphténate de cobalt et des cénosphères, 0,5% en poids, par rapport à la charge, de cénosphères récupérées au terme de l'exemple 1 et lavées au toluène chaud. L'addition de ces cénosphères récupérées permet, ainsi que le montre le tableau IV, de réduire l'apport de naphténate de molybdène frais à 100 ppm, sans modification significative des résultats.

Figure imgb0005
Figure imgb0006
 The procedure is as in Example 1, but adding to the hydrocarbon feedstock, in addition to cobalt naphthenate and the cenospheres, 0.5% by weight, relative to the feedstock, of cenospheres recovered at the end of the Example 1 and washed with hot toluene. The addition of these recovered cenospheres makes it possible, as shown in Table IV, to reduce the supply of fresh molybdenum naphthenate to 100 ppm, without significant modification of the results.
Figure imgb0005
Figure imgb0006

Exemple 4Example 4

On opère selon la méthode en continu décrite plus haut aec le résidu sous vide Safanya.We operate according to the continuous method described above with the vacuum residue Safanya.

La charge est mélangée avec du naphténate de molybdène (500 ppm en poids de molybdène) et 1% en poids de cénosphères, identiques à celles utilisées dans l'exemple 1. Elle est introduite dans le four de préchauffage à raison de 1 litre/h, où elle est portée à 430° C, température à laquelle elle entre dans la chambre de réaction.The charge is mixed with molybdenum naphthenate (500 ppm by weight of molybdenum) and 1% by weight of cenospheres, identical to those used in Example 1. It is introduced into the preheating oven at the rate of 1 liter / h , where it is brought to 430 ° C, the temperature at which it enters the reaction chamber.

La pression totale est de 150 bars. L'hydrogène recyclé est introduit en ligne juste avant le préchauffeur, avec un rapport H2/Hydrocarbure égal à 1000 litres par litre, l'hydrogène étant considéré à température et pression normale. L'hydrogène contient de 2 à 3% d'hydrogène sulfuré. La vitesse spatiale, volume de charge par heure et par volume de réacteur, est égale à 1,2 ce qui correspond à un temps de séjour dans le réacteur de 54 minutes.The total pressure is 150 bars. The recycled hydrogen is introduced online just before the preheater, with an H 2 / Hydrocarbon ratio equal to 1000 liters per liter, the hydrogen being considered at normal temperature and pressure. Hydrogen contains 2 to 3% hydrogen sulfide. The space velocity, charge volume per hour and per reactor volume, is equal to 1.2, which corresponds to a residence time in the reactor of 54 minutes.

Le tableau V montre les résultats obtenus après 100 heures de fonctionnement dans les conditions précédentes.

Figure imgb0007
Table V shows the results obtained after 100 hours of operation under the preceding conditions.
Figure imgb0007

Exemple 5Example 5

On opère selon la méthode en continu décrite plus haut avec un asphalte Safanya dilué avec 50% de »Iight cycle oil«. Le mélange résultant a les caractéristiques suivantes:

Figure imgb0008
We operate according to the continuous method described above with a Safanya asphalt diluted with 50% of »Iight cycle oil«. The resulting mixture has the following characteristics:
Figure imgb0008

Deux essais sont faits dans des conditions opératoires rigoureusement identiques, indiquées dans le tableau VI.Two tests are carried out under strictly identical operating conditions, indicated in Table VI.

Dans le premier essai (111), on utilise le naphténate de molybdène seul, dans le deuxième essai (112) on additionne au naphténate de molybdène, 2% en poids, par rapport à la charge, de cénosphères.In the first test (111), molybdenum naphthenate is used alone, in the second test (112), 2% by weight, relative to the charge, of cenospheres are added to the molybdenum naphthenate.

Pour chaque essai, un bilan sur 24 heures a été réalisé à 405°C, 417°C, 430°C. Sur les produits hydroconvertis soutirés à la base du séparateur haute pression des essais de filtration ont été faits dans les conditions suivantes:

Figure imgb0009
For each test, a 24-hour review was carried out at 405 ° C, 417 ° C, 430 ° C. On the hydroconverted products drawn off at the base of the high pressure separator, filtration tests were carried out under the following conditions:
Figure imgb0009

Le tableau VI fournit les vitesses de filtration pour ces différents produits ainsi que leur viscosité à 50" C.Table VI provides the filtration rates for these different products as well as their viscosity at 50 "C.

Il apparait très nettement que pour des conditions de filtration identiques et pour des viscosités presque semblables, la présence des cénosphères, décrites ci-dessus, favorise la filtration et donc la séparation du catalyseur en vue éventuellement d'un recyclage. Tout se passe comme si ces particules charbonneuses agissaient comme un adjuvant de filtration.It appears very clearly that for identical filtration conditions and for almost similar viscosities, the presence of the cenospheres, described above, promotes filtration and therefore the separation of the catalyst with a view to possible recycling. It is as if these carbonaceous particles act as a filter aid.

A titre de comparaison, on a donnée les durées de filtration observées avec d'autres adjuvants de filtration. Seule la Célite (marque déposée) donne des résultats équivalents; l'avantage des cénosphères, après utilisation, est de pouvoir être brûlées.

Figure imgb0010
For comparison, the filtration times observed with other filtration aids were given. Only Celite (registered trademark) gives equivalent results; the advantage of the cenospheres, after use, is that they can be burned.
Figure imgb0010

Claims (9)

1. A process for converting a heavy hydrocarbon charge containing asphaltenes and metal, sulfur and nitrogen impurities, in order to obtain products of lower boiling point and lower impurities content, wherein a mixture of said charge with hydrogen is contacted with a catalyst characterized in that the catalyst comprises at least two essential elements:
a) soot of the cenosphere type, resulting from the combustion of liquid heavy hydrocarbon charges, and containing at least one metal of the iron, nickel and vanadium group, and
b) at least one catalytic metal compound distinct from the element (a) and selected from the compounds of metals of groups V B, VI B, VII B and VIII.
2. A process according to claim 1, wherein element (b) is added to the hydrocarbon charge in the form of a solution in a hydrocarbon solvent, a solution in a non-hydrocarbon solvent or an emulsion of an aqueous solution in a hydrocarbon solvent.
3. A process according to claim 1 or 2, wherein the particles of soot of the cenosphere type have an average diameter of 10 to 200 !lm and contain 60 to 90% by weight of carbon and 1 to 10% by weight of metals of the iron, nickel and vanadium group.
4. A process according to claim 3, wherein the soot of the cenosphere type contains, by weight, 0.1 to 2% of vanadium, 0.1 to 5% of iron and 0.2 to 1 % of nickel.
5. A process according to any one of claims 1 to 4, wherein the cenospheres have a specific surface of 2 to 130 m2/g, a total pore volume of 0.8 to 2.5 cm3/g, a particle density of 0.3 to 0.8 g/cm3 and a structural density of 1.2 to 2.5 g/cm3.
6. A process according to any one of claims 1 to 4, wherein the cenospheres have a specific surface of 2 to 20 m2/g, a total pore volume of 1.2 to 1.7 cm3/g, a particle density of 0.4 to 0.6 g/cm3 and a structural density of 1.3 to 2.1 g/cm3.
7. A process according to any one of claims 1 to 6, wherein the amount of cenospheres is 0.1 to 5% by weight of the hydrocarbon charge and the amount of element (b) from 10 to 1000 ppm by weight of said charge.
8. A process according to any one of claims 1 to 7, wherein the hydrocarbon charge, after introduction of the two catalyst elements, is treated with hydrogen sulfide, before being subjected or the conversion process.
9. A process according to any one of claims 1 to 8, wherein the metal of compound (b) is selected from the group consisting of molybdenum, vanadium, chromium, tungsten, manganese, iron, nickel and cobalt.
EP82401336A 1981-08-11 1982-07-16 Catalytic hydroconversion process of heavy hydrocarbons in the presence of a dispersed catalyst and of carbonaceous particles Expired EP0073690B1 (en)

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