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EP0181253B1 - Process for the catalytic hydrotreatment of heavy hydrocarbons in fixed or mobile beds with injection of a metal compound into the feed - Google Patents

Process for the catalytic hydrotreatment of heavy hydrocarbons in fixed or mobile beds with injection of a metal compound into the feed Download PDF

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Publication number
EP0181253B1
EP0181253B1 EP85402042A EP85402042A EP0181253B1 EP 0181253 B1 EP0181253 B1 EP 0181253B1 EP 85402042 A EP85402042 A EP 85402042A EP 85402042 A EP85402042 A EP 85402042A EP 0181253 B1 EP0181253 B1 EP 0181253B1
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EP
European Patent Office
Prior art keywords
charge
process according
metal
molybdenum
compound
Prior art date
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Expired
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EP85402042A
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German (de)
French (fr)
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EP0181253A1 (en
Inventor
Jean-Claude Plumail
Jean-François Le Page
Pierre Giuliani
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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
    • 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

Definitions

  • the present invention relates to a process for hydrotreating heavy hydrocarbon feedstocks containing heteroatomic impurities such as for example sulfur, nitrogenous and metallic impurities, for example those containing nickel, vanadium and / or iron.
  • heteroatomic impurities such as for example sulfur, nitrogenous and metallic impurities, for example those containing nickel, vanadium and / or iron.
  • atmospheric distillation residues vacuum distillation residues
  • heavy crude oils deasphalted oils
  • braised and asphalts diluted with an aromatic distillate. coming for example from a catalytic cracking process (light cycle oil) and carbon hydrogenates.
  • This process consists in treating with hydrogen a charge of heavy hydrocarbons in contact with at least one fixed or mobile bed of a heterogeneous catalyst containing an alumina support and at least one catalytic metal or compound of catalytic metal of l '' at least one of the metals of groups VB, VI B and VIII of the periodic table of the elements (Handbook of Chemistry and Physics 37 th edition, 1956 pages 392-393, CRC Press), said alumina support having a pore volume of 0.85 to 2 cm 3 x g- 1 and a specific surface of 80 to 250 m 2 x g- 1 , the said process being characterized in that the hydrocarbon charge to be treated is added with hydrogen added sufficient quantity to carry out the hydrotreatment reaction, continuously or periodically, at least one compound of at least one metal chosen from the group formed by halides, oxyhalides, oxides, polyacids and polyacid salts of the metals of the metals group formed by the metals of groups VI B, VII B and VIII of the periodic classification of the elements
  • the purpose of refining hydrocarbon cuts is to convert heavy molecules into lighter molecules and to eliminate the maximum of sulfur, nitrogen and metallic heteroatomic impurities.
  • the sulfur and nitrogen heteroatoms are generally eliminated respectively in the form of hydrogen sulphide and ammonia, these compounds do not deactivate the catalyst and are found in the effluents.
  • the metals of the charge and in particular nickel and vanadium are deposited on the surface of the catalyst, generally in the form of sulphides, thus causing a significant deactivation, and hardly reversible of the catalyst, which becomes progressively incapable of carrying out the reactions hydrodesulfurization and hydrodenitrogenation.
  • the processes for hydrotreating petroleum fractions, and in particular those distilling below 550 ° C., are well known to those skilled in the art.
  • the operations are generally carried out under hydrogen pressure, in the presence of catalysts such as oxides and sulfides of molybdenum, tungsten, nickel and cobalt, for example on alumina, at temperatures generally between 250 ° C and 450 ° C.
  • the object of the present invention is to overcome the above drawbacks and in particular to allow the use of catalysts supported on alumina, said alumina having a pore volume of 0.85 to 2 cm 3 x g- 1 and a surface specific from 80 to 250 m 2 x g- 1 in industrial hydrorefining units for longer treatment times than those obtained with the processes of the prior art, and making it possible in certain cases to avoid having to set up performs a second hydrotreatment step.
  • the compounds of the above metals chosen from the group formed by halides, oxyhalides, oxides, polyacids such as isopolyacids and heteropolyacids and the salts of these acids make it possible to obtain a clear improvement of the performance of the catalysts used and in particular of their lifetime.
  • halogenated compounds compounds containing chlorine, bromine or iodine are advantageously used in their formulas and more particularly compounds containing chlorine or iodine in their formulas.
  • molybdenum compounds will be used alone or in combination with nickel and / or cobalt compounds and, preferably, blues of molybdenum and / or phosphomolybdic acid or one of its salts will be used.
  • the metal compound which is injected into the charge of hydrocarbons to be treated is introduced for example in the form of a solution, or of suspension in an organic solvent having a solubility of at least 1% by weight in hydrocarbons under the conditions hydrotreatment, in the form of a solution or emulsion in a water-organic solvent mixture, or in the form of an aqueous solution of said compound if it has sufficient solubility in water.
  • metal compounds are used in solution in hydrocarbons or in solution in mixtures of alcohols, in particular CrC9 alcohols or in solution in water-CrC9 alcohol mixtures.
  • phosphomolybdic acid or its salts in aqueous solution, and / or molybdenum blues preferably chosen from those described in FR-A-1 099 953, in solution in a mixture of alcohols C 7 -C 9 or in a water-alcohol mixture C 7 -C 9 or in hydrocarbons, for example in a fraction of the feedstock from a previous treatment.
  • the catalysts which are used in the context of the present invention containing an alumina support with a pore volume of 0.85 to 2 cm3 ⁇ g- 1 and a specific surface of 80 to 250 m 2 x g- 1 .
  • the aluminas which can be used as a support are preferably chosen from aluminas of low or zero acidity, such as that having a heat of neutralization by absorption of ammonia preferably less than 10 calories and more particularly less than 7 calories per gram of alumina at 320 ° C under 0.04 megapascals (MPa).
  • the so-called neutral aluminas can also be characterized by their inertness with respect to cracking and coking reactions in the presence of hydrogen. Neutrality can be determined for example by the n-heptane cracking test which consists in measuring the quantity of n-heptane converted into lighter molecules under the following operating conditions:
  • the conversion is measured by analysis by gas chromatography of the liquid products.
  • a support is said to be neutral if its cracking activity (mole / hour and / m 2 of support) is less than 5 x 10 -6 at the temperature of 470 ° C and if it is less than 15 x 10- Q at a temperature of 500 ° C.
  • aluminas treated with alkali and / or alkaline-earth metals for example those having an Na 2 0 content of 1000 ppm by weight or higher can be used, as well as those thermally stabilized with rare earth metals and / or alkaline earth metals and / or silica, generally meet the neutrality criteria defined below.
  • autoclaved alumina denotes aluminas which have undergone a treatment with water or with steam called “autoclaving” at a temperature between approximately 80 ° C. and approximately 300 ° C. for approximately 5 minutes to 48 hours, preferably 1 to 6 hours.
  • the aqueous autoclaving medium contains at least one acid capable of dissolving part of the alumina of the agglomerates, or the mixture of such an acid with at least one compound providing an anion capable of combining with aluminum ions, for example a mixture of nitric acid and acetic or formic acid.
  • the autoclaving technique is for example described in French patent application FR-A-2 496 631.
  • an autoclaved alumina obtained according to the method described in European patent application EP-A-98 764 will be used.
  • the alumina support obtained is formed from a plurality of needle-like platelets, the platelets of each agglomerate being oriented generally radially with respect to each other and relative to the center of the agglomeration.
  • the aforementioned structure includes macropores and mesopores (we call mesopores, the pores of size between that of the micropores and that of the macropores: the mesopores are therefore, roughly between 10 and 100 nanometers) and practically no micropores.
  • the preferred supports are those which contain a preponderant proportion of wedge-shaped mesopores.
  • the catalytic metal or metals or compounds of catalytic metals is deposited by any known method of at least one of the metals of groups VB, VI B, and VIII of the periodic table of the elements and preferably at least one of the metals from the group formed by molybdenum, tungsten, iron, cobalt, nickel, chromium and vanadium. Preferred combinations are molybdenum + cobalt, molybdenum + nickel, tungsten + nickel, vanadium + nickel.
  • the metal content of the final catalyst used in the present invention is generally from 0.5 to 40% by weight of metals (expressed as oxide) relative to the weight of the finished catalyst. In a preferred embodiment of the invention, one of the combinations of metals mentioned above is used, the metal content then preferably being from 1 to 30% by weight of metals (expressed as oxide) relative to the weight. of the finished catalyst.
  • the catalysts described in European patent application EP-A-98 764 including the support formed from autoclaved alumina with the structure mentioned above, which have a structure identical to that of the support, and have improved resistance to clogging of mouths of pores compared for example to bimodal (macroporous and microporous) or monomodal (microporous) catalysts are preferred within the framework of the invention.
  • the support of these catalysts is inert to the n-heptane cracking test. Yielded specific activities of 0,610- 6 mol / (h. M 2) at 470 ° C and 8 x 10- 6 mole / (h. M 2) at 500 ° C.
  • the continuous or periodic injection of metal compounds, and in particular of molybdenum compounds is carried out after adding hydrogen in an amount sufficient to carry out the hydrorefining reaction of the feed.
  • the metal compound is introduced before the said charge, previously added with hydrogen, passes through the heterogeneous catalyst bed.
  • the metal compound is introduced into the charge previously added with hydrogen and previously brought to a temperature of at least 330 ° C, advantageously from 330 ° C to about 450 ° C and preferably, previously brought to a temperature of about 350 ° C to about 450 ° C.
  • the amount of the metal compound added to the charge is such that the concentration of metal added relative to the total weight of the charge is from 10 to 1500 ppm and preferably from 30 to 600 ppm.
  • this metallic compound in particular of the molybdenum compounds makes it possible, in addition to the increase in the cycle time, to keep the demetallizing activity of the catalyst constant, to improve the hydrodenitrogenation activities, d hydrodesulfurization and conversion of heavy molecules.
  • the metal compounds in particular the molybdenum compounds, decompose on the catalyst and the metal atoms (molybdenum) then attach to the surface of the catalyst, thus making it possible to avoid deactivation thereof, by continuous or periodic regeneration of the active phase.
  • the injection of the metal compounds, preferably molybdenum compounds, is in an advantageous form of the present invention carried out periodically.
  • a quantity of compound is thus introduced during a determined period into the charge, at variable intervals, for a more or less long time; for example, this compound is introduced for 1 to 30 hours every 100, 200 or 300 hours and advantageously for 10 to 20 hours every 200 hours.
  • the usual conditions for the hydrotreatment reaction are a temperature of approximately 250 to approximately 500 ° C and preferably approximately 350 to approximately 450 ° C, a pressure of approximately 5 to approximately 30 megapascals (MPa) and preferably approximately 8 to approximately 20 MPa and a flow rate of hydrocarbon feedstock per volume of catalyst and per hour (VVH) of approximately 0.1 to approximately 10 and preferably approximately 0.2 to approximately 2.
  • the flow rate of hydrogen is for example from about 50 to about 5000 liters per liter of filler and preferably from about 200 to about 3000 x 1- 1 .
  • the support for these catalysts is alumina, it is prepared according to the method described in Example 1 of patent application EP-A-98 764 and has all the characteristics described in this example. Then deposited on this support molybdenum and nickel using the method described in Example 1 of application EP-A-98 764.
  • the metal contents expressed by weight of oxide relative to the weight of the finished catalyst of the catalysts A and B obtained are the following:
  • Test 1 1 1 of catalyst A is placed in a hydrotreating pilot unit operating in a fixed bed.
  • the operating conditions for using this catalyst are as follows:
  • the petroleum cut used to carry out the test is atmospheric petroleum residue from Safaniya (Saudi Arabia), the characteristics of which are as follows:
  • the pilot unit consists of a preheating oven, allowing the charge to be brought to the desired temperature for the catalytic hydrotreatment reaction, in series with a catalytic hydrotreatment reactor comprising a fixed catalyst bed.
  • the above charge and the hydrogen are introduced into the preheating furnace so as to raise the temperature of this mixture to 400 ° C., this charge plus hydrogen mixture then passes into the catalytic hydrotreatment reactor.
  • Test 2 Under the same operating conditions, with the same apparatus and the same catalyst as that used in test 1, another test is carried out by continuously adding, in the charge-hydrogen mixture leaving the preheating oven, molybdenum, in the form of an emulsion at 5.8% by weight of molybdenum blue in a water-organic solvent mixture containing 2% by weight of water, the organic solvent consisting of a mixture of CrCg alcohols.
  • the quantity of this aquo-organic emulsion introduced into the charge is such that the molybdenum content, counted by weight of metal relative to the weight of the charge, is 100 ppm.
  • Test 1 1 I of catalyst B is placed in a pilot hydrotreatment unit operating in a fixed bed.
  • the apparatus, the operating conditions and the test load used are identical to those of test 1 of Example 1.
  • Test 2 1 I of the same catalyst B is placed in the same pilot unit, under the same operating conditions. However, in the feed, phosphomolybdic acid in aqueous solution is added at the outlet of the preheating oven before its injection into the catalytic hydrotreatment reactor. The amount of acid added is such that the molybdenum content in the feed is 50 ppm.
  • the test load is an asphalt diluted with 35% by weight of light cycle oil (LCO).
  • LCO light cycle oil
  • the charge-hydrogen mixture is brought to 410 ° C. in the preheating oven and then introduced into the catalytic hydrotreatment reactor.
  • Test 2 1 I of catalyst A is loaded into the same pilot unit and is put under the same operating conditions as those of test 1. In the same test load as that used in test 1, the output is added the molybdenum blue preheating oven in solution at 5.8% by weight in a mixture of C 7 -C 9 alcohols. The amount of solution added is such that the molybdenum content in the feed is 150 ppm by weight.
  • Test 3 This test is identical to test 2 except that the blue of molybdenum is replaced by molybdenum trioxide in a water-alcohol mixture C 7 -C 9 at 10% by weight of water and a sufficient amount of this composition is introduced to have 150 ppm by weight of molybdenum in the feed.
  • Test 4 This test is identical to test 2 with the exception that the molybdenum blue prepared using the method described in FR-A-1 099 953 is used. A sufficient amount of this compound is introduced to have 150 ppm by weight of molybdenum in the feed.
  • the hydrocarbon charge used to carry out the test is Boscan crude deasphalted with pentane (Venezuelan crude from the Orinoco belt), the characteristics of which are:
  • the charged hydrogen mixture is brought to 380 ° C. in the preheating oven and then introduced into the catalytic hydrotreatment reactor.
  • Test 2 1 1 of catalyst A is placed under the same conditions as those of test 1.
  • the test charge used is also that of test 1. But during the test, every 200 hours, for 12 hours phosphomolybdic acid in aqueous solution is added to the charge at the outlet of the preheating oven, in an amount such that the molybdenum concentration in the charge which is introduced during these 12 hours is 600 ppm by weight.
  • Test 1 1 liter of catalyst A is placed in a pilot hydrotreatment unit operating in a fixed bed.
  • the apparatus, the operating conditions and the test load used are identical to those of test 1 of Example 4.
  • Test 2 1 liter of the same catalyst A is placed in the same pilot unit, under the same operating conditions. However, in the charge-hydrogen mixture, molybdenum naphthenate is added at the outlet of the preheating oven, before its injection into the catalytic hydrotreatment reactor, in the form of a 6% by weight solution in a mixture of alcohols. C 7 -C 9 . The amount of solution added is such that the molybdenum content in the feed is 600 ppm.

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

Abstract

The invention relates to a process for catalytic treatment of heavy hydrocarbons, in a fixed or moving bed, over a catalyst containing an alumina carrier and at least one catalytic metal or compound of metal from groups VB, VI B and VIII of the periodic classification of elements, characterized by the direct injection into the charge, continuously or periodically, of at least one metal compound selected from the group consisting of halides, oxyhalides, oxides, polyacids and polyacid salts of metals from groups VI B, VII B and VIII, before introducing the charge into the hydrotreatment zone.

Description

La présente invention concerne un procédé d'hydrotraitement de charges lourdes hydrocarbonées contenant des impuretés hétéroatomiques telles que par exemple des impuretés soufrées, azotées et métalliques, par exemple celles contenant du nickel, du vanadium et/ou du fer. Parmi les charges envisagées on peut citer, sans que cette liste ne soit considérée comme restrictive, les résidus de distillation atmosphérique, les résidus de distillation sous vide, les pétroles bruts lourds, les huiles désasphaltées, les brais et les asphaltes dilués par un distillat aromatique provenant par exemple d'un procédé de craquage catalytique (huile de cycle légère) et les hydrogénats de charbon.The present invention relates to a process for hydrotreating heavy hydrocarbon feedstocks containing heteroatomic impurities such as for example sulfur, nitrogenous and metallic impurities, for example those containing nickel, vanadium and / or iron. Among the charges envisaged, there may be mentioned, without this list being considered restrictive, atmospheric distillation residues, vacuum distillation residues, heavy crude oils, deasphalted oils, braised and asphalts diluted with an aromatic distillate. coming for example from a catalytic cracking process (light cycle oil) and carbon hydrogenates.

Ce procédé consiste à traiter par l'hydrogène une charge d'hydrocarbures lourds au contact d'au moins un lit fixe ou mobile d'un catalyseur hétérogène renfermant un support d'alumine et au moins un métal catalytique ou composé de métal catalytique de l'un au moins des métaux des groupes V B, VI B et VIII de la classification périodique des éléments (Handbook of Chemistry and Physics 37ème édition, 1956 pages 392-393, CRC Press), ledit support d'alumine ayant un volume poreux de 0,85 à 2 cm3 x g-1 et une surface spécifique de 80 à 250 m2 x g-1, ledit procédé étant caractérisé en ce que l'on ajoute à la charge d'hydrocarbures à traiter additionnée d'hydrogène en quantité suffisante pour effectuer la réaction d'hydrotraitement, de manière continue ou périodique au moins un composé d'au moins un métal choisi dans le groupe formé par les halogénures, les oxyhalogénures, les oxydes, les polyacides et les sels de polyacides des métaux du groupe formé par les métaux des groupes VI B, VII B et VIII de la classification périodique des éléments avant passage de ladite charge à travers le lit de catalyseur hétérogène.This process consists in treating with hydrogen a charge of heavy hydrocarbons in contact with at least one fixed or mobile bed of a heterogeneous catalyst containing an alumina support and at least one catalytic metal or compound of catalytic metal of l '' at least one of the metals of groups VB, VI B and VIII of the periodic table of the elements (Handbook of Chemistry and Physics 37 th edition, 1956 pages 392-393, CRC Press), said alumina support having a pore volume of 0.85 to 2 cm 3 x g- 1 and a specific surface of 80 to 250 m 2 x g- 1 , the said process being characterized in that the hydrocarbon charge to be treated is added with hydrogen added sufficient quantity to carry out the hydrotreatment reaction, continuously or periodically, at least one compound of at least one metal chosen from the group formed by halides, oxyhalides, oxides, polyacids and polyacid salts of the metals of the metals group formed by the metals of groups VI B, VII B and VIII of the periodic classification of the elements before passage of said charge through the heterogeneous catalyst bed.

Le raffinage des coupes d'hydrocarbures a pour but de convertir les molécules lourdes en molécules plus légères et d'éliminer le maximum d'impuretés hétéroatomiques soufrées, azotées et métalliques.The purpose of refining hydrocarbon cuts is to convert heavy molecules into lighter molecules and to eliminate the maximum of sulfur, nitrogen and metallic heteroatomic impurities.

Les hétéroatomes de soufre et d'azote sont en général respectivement éliminés sous forme d'hydrogène sulfuré et d'ammoniac, ces composés ne désactivent pas le catalyseur et se retrouvent dans les effluents.The sulfur and nitrogen heteroatoms are generally eliminated respectively in the form of hydrogen sulphide and ammonia, these compounds do not deactivate the catalyst and are found in the effluents.

Par contre les métaux de la charge et en particulier le nickel et le vanadium se déposent à la surface du catalyseur, en général sous forme de sulfures, provoquant ainsi une désactivation importante, et difficilement réversible du catalyseur, qui devient progressivement inapte à effectuer les réactions d'hydrodésulfuration et d'hydrodéazotation.On the other hand, the metals of the charge and in particular nickel and vanadium are deposited on the surface of the catalyst, generally in the form of sulphides, thus causing a significant deactivation, and hardly reversible of the catalyst, which becomes progressively incapable of carrying out the reactions hydrodesulfurization and hydrodenitrogenation.

Les procédés d'hydrotraitement des fractions pétrolières, et en particulier de celles distillant en dessous de 550 °C, sont bien connus de l'Homme de l'Art. Les opérations sont en général conduites sous pression d'hydrogène, en présence de catalyseurs tels que les oxydes et sulfures de molybdène, tungstène, nickel et cobalt, par exemple sur alumine, à des températures généralement comprises entre 250 °C et 450 °C.The processes for hydrotreating petroleum fractions, and in particular those distilling below 550 ° C., are well known to those skilled in the art. The operations are generally carried out under hydrogen pressure, in the presence of catalysts such as oxides and sulfides of molybdenum, tungsten, nickel and cobalt, for example on alumina, at temperatures generally between 250 ° C and 450 ° C.

Les nombreuses recherches effectuées ont rapidement montré qu'en particulier une adaptation de la texture poreuse des catalyseurs conventionnels d'hydroraffinage permet d'accroître nettement le niveau d'activité en hydrodémétallation et en conversion des molécules lourdes. Cette modification du catalyseur permet d'autre part d'accroître notablement la durée de vie des catalyseurs (période de temps pendant laquelle le catalyseur mis en oeuvre est suffisamment actif pour que l'on ne soit pas obligé de le remplacer par une nouvelle charge de catalyseur frais). De très nombreux brevets ou demandes de brevets parmi lesquels on peut citer US-A-4 395 329, US-A-4 225 421, US-A-4 166 026, US-A-4 134 856 et EP-A-98 764 revendiquent une telle amélioration. Les catalyseurs décrits dans la demande de brevet EP-A-98 764 ayant une texture poreuse particulière et une structure ressemblant à l'image d'un tas de bogues épineuses de châtaignes ou encore à un tas d'oursins de mer, sont particulièrement efficaces dans des réactions de démétallisation de fraction lourde de pétrole et peuvent être employés au niveau industriel.The numerous researches carried out quickly showed that in particular an adaptation of the porous texture of the conventional hydrorefining catalysts makes it possible to clearly increase the level of activity in hydrodemetallization and in conversion of heavy molecules. This modification of the catalyst also makes it possible to appreciably increase the lifetime of the catalysts (period of time during which the catalyst used is sufficiently active so that it is not necessary to replace it with a new charge of fresh catalyst). Numerous patents or patent applications, including US-A-4,395,329, US-A-4,225,421, US-A-4,166,026, US-A-4,134,856 and EP-A-98 764 claim such an improvement. The catalysts described in patent application EP-A-98 764 having a particular porous texture and a structure resembling the image of a bunch of spiny chestnut bugs or even a bunch of sea urchins, are particularly effective. in heavy metal demetallization reactions and can be used on an industrial level.

Cependant de tels catalyseurs, utilisés seuls, ne permettent pas d'avoir, d'une part des activités d'hydrodésulfuration (HDS) et d'hydrodéazotation (HDN) suffisantes et d'autre part les activités d'HDS, d'HDN, d'hydrodémétallisation (HDM) et de conversion des molécules lourdes décroissent au cours du temps, en raison de l'empoisonnement de la phase active par dépôt de vanadium et de nickel. Cette insuffisance dans la stabilité de l'activité d'hydroraffinage de ces catalyseurs, oblige en général à mettre en ceuvre une seconde étape d'hydrotraitement pour obtenir des produits utilisables comme produits finis ou comme charge dans les unités de craquage catalytique d'hydrocraquage ou vapocraquage. La mise en oeuvre de cette deuxième étape est très coûteuse car elle nécessite des investissements en matériels, notamment, très importants.However, such catalysts, used alone, do not allow, on the one hand sufficient hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) activities and on the other hand the activities of HDS, HDN, hydrodemetallization (HDM) and conversion of heavy molecules decrease over time, due to poisoning of the active phase by deposition of vanadium and nickel. This insufficiency in the stability of the hydrorefining activity of these catalysts generally forces a second hydrotreatment step to be implemented in order to obtain products which can be used as finished products or as feedstock in the catalytic cracking units of hydrocracking or steam cracking. The implementation of this second step is very costly because it requires investments in equipment, in particular, very large.

L'objet de la présente invention est de pallier aux inconvénients ci-dessus et en particulier de permettre d'utiliser des catalyseurs supportés sur alumine, ladite alumine ayant un volume poreux de 0,85 à 2 cm3 x g-1 et une surface spécifique de 80 à 250 m2 x g-1 dans des unités industrielles d'hydroraffinage pendant des durées de traitements plus importantes que celles obtenues avec les procédés de l'art antérieur, et permettant dans certains cas d'éviter à avoir à mettre en oeuvre une seconde étape d'hydrotraitement.The object of the present invention is to overcome the above drawbacks and in particular to allow the use of catalysts supported on alumina, said alumina having a pore volume of 0.85 to 2 cm 3 x g- 1 and a surface specific from 80 to 250 m 2 x g- 1 in industrial hydrorefining units for longer treatment times than those obtained with the processes of the prior art, and making it possible in certain cases to avoid having to set up performs a second hydrotreatment step.

D'une façon surprenante on a découvert que l'addition à la charge d'hydrocarbures à traiter de manière continue ou périodique (par bouffée) d'au moins un composé d'au moins un métal choisi parmi les métaux des groupes VI B, VII B et VIII de la classification périodique des éléments et d'une manière avantageuse d'au moins un composé d'au moins un métal du groupe formé par le molybdène. le tungstène, le nickel, le cobalt et le chrome, dans la mise en oeuvre en lit fixe ou mobile de catalyseurs supportés sur alumine, dans des conditions classiques d'hydrotraitement de produits lourds, permet en particulier d'augmenter de façon importante la durée de vie de ces catalyseurs.Surprisingly, it has been discovered that the addition to the feedstock of hydrocarbons to be treated continuously or periodically (by puffing) of at least one compound of at least one metal chosen from the metals of groups VI B, VII B and VIII of the Periodic Table of the Elements and in a way advantageous of at least one compound of at least one metal from the group formed by molybdenum. tungsten, nickel, cobalt and chromium, in the implementation in a fixed or mobile bed of catalysts supported on alumina, under conventional conditions for hydrotreating heavy products, in particular makes it possible to significantly increase the duration life of these catalysts.

Tous les composés de métaux ne sont pas utilisables dans le présent procédé. Avec les catalyseurs que nous utilisons dans la présente invention et qui sont définis de façon plus précise ci-dessous certains composés et en particulier les composés organiques tels que par exemple le naphténate de molybdène, semblent se décomposer très rapidement au contact du catalyseur, en tête de lit, provoquant un croûtage et ne permettent pas d'améliorer les performances des catalyseurs utilisés.Not all metal compounds can be used in the present process. With the catalysts which we use in the present invention and which are defined more precisely below certain compounds and in particular organic compounds such as for example molybdenum naphthenate, seem to decompose very quickly on contact with the catalyst, at the head bed, causing crusting and do not improve the performance of the catalysts used.

D'une manière surprenante on a découvert que les composés des métaux ci-dessus choisis dans le groupe formé par les halogénures, les oxyhalogénures, les oxydes, les polyacides tels que isopolyacides et hétéropolyacides et les sels de ces acides permettent d'obtenir une nette amélioration des performances des catalyseurs utilisés et en particulier de leur durée de vie. Parmi les composés halogénés on emploie avantageusement des composés contenant du chlore, du brome ou de l'iode dans leurs formules et plus particulièrement des composés contenant du chlore ou de l'iode dans leurs formules. D'une façon très avantageuse on emploiera des composés de molybdène seuls ou associés à des composés de nickel et/ou de cobalt et de façon préférée on utilisera les bleus de molybdène et/ou l'acide phosphomolybdique ou l'un de ses sels.Surprisingly, it has been discovered that the compounds of the above metals chosen from the group formed by halides, oxyhalides, oxides, polyacids such as isopolyacids and heteropolyacids and the salts of these acids make it possible to obtain a clear improvement of the performance of the catalysts used and in particular of their lifetime. Among the halogenated compounds, compounds containing chlorine, bromine or iodine are advantageously used in their formulas and more particularly compounds containing chlorine or iodine in their formulas. In a very advantageous manner, molybdenum compounds will be used alone or in combination with nickel and / or cobalt compounds and, preferably, blues of molybdenum and / or phosphomolybdic acid or one of its salts will be used.

Le composé de métal que l'on injecte dans la charge d'hydrocarbures à traiter est introduit par exemple sous forme de solution, ou de suspension dans un solvant organique présentant une solubilité d'au moins 1 % en poids dans les hydrocarbures dans les conditions de l'hydrotraitement, sous forme de solution ou d'émulsion dans un mélange eau-solvant organique, ou sous forme d'une solution aqueuse dudit composé s'il présente une solubilité suffisante dans l'eau.The metal compound which is injected into the charge of hydrocarbons to be treated is introduced for example in the form of a solution, or of suspension in an organic solvent having a solubility of at least 1% by weight in hydrocarbons under the conditions hydrotreatment, in the form of a solution or emulsion in a water-organic solvent mixture, or in the form of an aqueous solution of said compound if it has sufficient solubility in water.

Parmi les solvants organiques que l'on peut utiliser on peut citer les hydrocarbures, les alcools, les éthers, les cétones, les esters, les amides et les nitriles. On utilise de préférence les alcools et en particulier des mélanges d'alcools ayant de 6 à 18 atomes de carbone ou les hydrocarbures.Among the organic solvents which can be used, mention may be made of hydrocarbons, alcohols, ethers, ketones, esters, amides and nitriles. Alcohols and in particular mixtures of alcohols having from 6 to 18 carbon atoms or hydrocarbons are preferably used.

Lorsque l'on utilise des mélanges eau-solvant organique pour introduire le composé de métal, on emploie avantageusement des mélanges contenant de 50 à 99 % en poids et d'une manière préférée de 70 à 99 % en poids de solvant organique par rapport au poids total du mélange eau-solvant organique. Dans une forme préférée de l'invention on utilise des composés de métaux en solution dans les hydrocarbures ou en solution dans des mélanges d'alcools en particulier des alcools en CrC9 ou en solution dans des mélanges eau-alcools CrC9. Il est particulièrement avantageux d'employer par exemple l'acide phosphomolybdique ou ses sels en solution aqueuse, et/ou des bleus de molybdène choisis de préférence parmi ceux décrits dans FR-A-1 099 953, en solution dans un mélange d'alcools en c7-C9 ou dans un mélange eau-alcools en C7-C9 ou dans des hydrocarbures, par exemple dans une fraction de la charge issue d'un précédent traitement.When water-organic solvent mixtures are used to introduce the metal compound, mixtures containing from 50 to 99% by weight and preferably from 70 to 99% by weight of organic solvent are preferably used relative to the total weight of the water-organic solvent mixture. In a preferred form of the invention, metal compounds are used in solution in hydrocarbons or in solution in mixtures of alcohols, in particular CrC9 alcohols or in solution in water-CrC9 alcohol mixtures. It is particularly advantageous to use for example phosphomolybdic acid or its salts in aqueous solution, and / or molybdenum blues preferably chosen from those described in FR-A-1 099 953, in solution in a mixture of alcohols C 7 -C 9 or in a water-alcohol mixture C 7 -C 9 or in hydrocarbons, for example in a fraction of the feedstock from a previous treatment.

Les catalyseurs que l'on emploie dans le cadre de la présente invention, renfermant un support d'alumine de volume poreux de 0,85 à 2 cm3 · g-1 et de surface spécifique de 80 à 250 m2 x g-1.The catalysts which are used in the context of the present invention, containing an alumina support with a pore volume of 0.85 to 2 cm3 · g- 1 and a specific surface of 80 to 250 m 2 x g- 1 .

Les alumines utilisables comme support sont de préférence choisies parmi les alumines d'acidité faible ou nulle, telle que celle ayant une chaleur de neutralisation par absorption d'ammoniac de préférence inférieure à 10 calories et plus particulièrement inférieure à 7 calories par gramme d'alumine à 320 °C sous 0,04 mégapascals (MPa). Les alumines dites neutres peuvent aussi être caractérisées par leur inertie vis-à-vis des réactions de craquage et de cokage en présence d'hydrogène. La neutralité peut être déterminée par exemple par le test de craquage du n-heptane qui consiste à mesurer la quantité de n-heptane converti en molécules plus légères dans les conditions opératoires suivantes :

Figure imgb0001
The aluminas which can be used as a support are preferably chosen from aluminas of low or zero acidity, such as that having a heat of neutralization by absorption of ammonia preferably less than 10 calories and more particularly less than 7 calories per gram of alumina at 320 ° C under 0.04 megapascals (MPa). The so-called neutral aluminas can also be characterized by their inertness with respect to cracking and coking reactions in the presence of hydrogen. Neutrality can be determined for example by the n-heptane cracking test which consists in measuring the quantity of n-heptane converted into lighter molecules under the following operating conditions:
Figure imgb0001

La conversion est mesurée par analyse par chromatographie en phase gazeuse des produits liquides.The conversion is measured by analysis by gas chromatography of the liquid products.

Dans ce test un support est dit neutre si son activité de craquage (mole/heure et /m2 de support) est inférieure à 5 x 10-6 à la température de 470 °C et si elle est inférieure à 15 x 10-Q à la température de 500 °C.In this test, a support is said to be neutral if its cracking activity (mole / hour and / m 2 of support) is less than 5 x 10 -6 at the temperature of 470 ° C and if it is less than 15 x 10- Q at a temperature of 500 ° C.

Les alumines traitées par les métaux alcalins et/ou alcalino-terreux, par exemple celles ayant une teneur en Na20 de 1000 ppm en poids ou supérieure sont utilisables, de même que celles thermiquement stabilisées par des métaux de terres rares et/ou des métaux alcalino-terreux et/ou de la silice, répondent en général aux critères de neutralité définis ci-dessous.The aluminas treated with alkali and / or alkaline-earth metals, for example those having an Na 2 0 content of 1000 ppm by weight or higher can be used, as well as those thermally stabilized with rare earth metals and / or alkaline earth metals and / or silica, generally meet the neutrality criteria defined below.

D'une manière avantageuse on peut aussi utiliser les alumines autoclavées. Par alumine autoclavée, on désigne les alumines qui ont subi un traitement à l'eau ou à la vapeur d'eau appelé « autoclavage » à une température comprise entre environ 80 °C et environ 300 °C pendant environ 5 minutes à 48 heures, de préférence de 1 à 6 heures.Advantageously, it is also possible to use autoclaved aluminas. The term “autoclaved alumina” denotes aluminas which have undergone a treatment with water or with steam called “autoclaving” at a temperature between approximately 80 ° C. and approximately 300 ° C. for approximately 5 minutes to 48 hours, preferably 1 to 6 hours.

De préférence le milieu aqueux d'autoclavage renferme au moins un acide capable de dissoudre une partie de l'alumine des agglomérés, ou le mélange d'un tel acide avec au moins un composé apportant un anion capable de se combiner avec les ions aluminium, par exemple un mélange d'acide nitrique et d'acide acétique ou formique. La technique d'autoclavage est par exemple décrite dans la demande de brevet français FR-A-2 496 631.Preferably, the aqueous autoclaving medium contains at least one acid capable of dissolving part of the alumina of the agglomerates, or the mixture of such an acid with at least one compound providing an anion capable of combining with aluminum ions, for example a mixture of nitric acid and acetic or formic acid. The autoclaving technique is for example described in French patent application FR-A-2 496 631.

Dans une forme particulièrement préférée de l'invention on emploiera une alumine autoclavée obtenue suivant la méthode décrite dans la demande de brevet européen EP-A-98 764. Le support d'alumine obtenu est formé d'une pluralité de plaquettes aciculaires, les plaquettes de chaque agglomérat étant orientées généralement radialement les unes vis-à-vis des autres et par rapport au centre de l'agglomérat. La structure précitée comprend des macropores et des mésopores (on appelle mésopores, les pores de taille comprise entre celle des micropores et celle des macropores : les mésopores se situent donc, en gros entre 10 et 100 nanomètres) et pratiquement pas de micropores.In a particularly preferred form of the invention, an autoclaved alumina obtained according to the method described in European patent application EP-A-98 764 will be used. The alumina support obtained is formed from a plurality of needle-like platelets, the platelets of each agglomerate being oriented generally radially with respect to each other and relative to the center of the agglomeration. The aforementioned structure includes macropores and mesopores (we call mesopores, the pores of size between that of the micropores and that of the macropores: the mesopores are therefore, roughly between 10 and 100 nanometers) and practically no micropores.

Les supports préférés sont ceux qui contiennent une proportion prépondérante de mésopores en forme de coins.The preferred supports are those which contain a preponderant proportion of wedge-shaped mesopores.

Sur les supports d'alumines, décrits ci-dessus on dépose par toutes méthodes connues le ou les métaux catalytiques ou composés de métaux catalytiques de l'un au moins des métaux des groupes V B, VI B, et VIII de la classification périodique des éléments et de préférence l'un au moins des métaux du groupe formé par le molybdène, le tungstène, le fer, le cobalt, le nickel, le chrome et le vanadium. Des associations préférées sont molybdène + cobalt, molybdène + nickel, tungstène + nickel, vanadium + nickel. La teneur en métaux du catalyseur final employé dans la présente invention est en général de 0,5 à 40 % en poids de métaux (exprimé en oxyde) par rapport au poids du catalyseur fini. Dans une forme préférée de réalisation de l'invention on emploie l'une des associations de métaux mentionnées ci-dessus, la teneur en métaux étant alors de préférence de 1 à 30 % en poids de métaux (exprimé en oxyde) par rapport au poids du catalyseur fini.On the alumina supports, described above, the catalytic metal or metals or compounds of catalytic metals is deposited by any known method of at least one of the metals of groups VB, VI B, and VIII of the periodic table of the elements and preferably at least one of the metals from the group formed by molybdenum, tungsten, iron, cobalt, nickel, chromium and vanadium. Preferred combinations are molybdenum + cobalt, molybdenum + nickel, tungsten + nickel, vanadium + nickel. The metal content of the final catalyst used in the present invention is generally from 0.5 to 40% by weight of metals (expressed as oxide) relative to the weight of the finished catalyst. In a preferred embodiment of the invention, one of the combinations of metals mentioned above is used, the metal content then preferably being from 1 to 30% by weight of metals (expressed as oxide) relative to the weight. of the finished catalyst.

Les catalyseurs décrits dans la demande de brevet européen EP-A-98 764, dont le support formé d'alumine autoclavée à la structure rappelée ci-dessus, qui possèdent une structure identique à celle du support, et ont une résistance améliorée en colmatage des bouches de pores par rapport par exemple aux catalyseurs bimodaux (macroporeux et microporeux) ou monomodaux (microporeux) sont préférés dans le cadre de l'invention. Le support de ces catalyseurs sont inertes au test de craquage du n-heptane. On a obtenu des activités spécifiques de 0,610-6 mole/(h . m2) à 470 °C et 8 x 10-6 mole/(h . m2) à 500 °C.The catalysts described in European patent application EP-A-98 764, including the support formed from autoclaved alumina with the structure mentioned above, which have a structure identical to that of the support, and have improved resistance to clogging of mouths of pores compared for example to bimodal (macroporous and microporous) or monomodal (microporous) catalysts are preferred within the framework of the invention. The support of these catalysts is inert to the n-heptane cracking test. Yielded specific activities of 0,610- 6 mol / (h. M 2) at 470 ° C and 8 x 10- 6 mole / (h. M 2) at 500 ° C.

L'injection en continu ou de manière périodique de composés de métal, et en particulier de composés de molybdène est effectuée après avoir ajouté l'hydrogène en quantité suffisante pour effectuer la réaction d'hydroraffinage de la charge. L'introduction de composé de métal a lieu avant le passage de ladite charge, préalablement additionnée d'hydrogène, à travers le lit de catalyseur hétérogène. Le composé de métal est introduit dans la charge préalablement additionnée d'hydrogène et préalablement portée à une température d'au moins 330 °C, avantageusement de 330 °C à 450 °C environ et de préférence, préalablement portée à une température d'environ 350 °C à environ 450 °C. La quantité du composé métalique ajouté à la charge est telle que la concentration en métal ajouté par rapport au poids total de la charge soit de 10 à 1500 ppm et de préférence de 30 à 600 ppm.The continuous or periodic injection of metal compounds, and in particular of molybdenum compounds is carried out after adding hydrogen in an amount sufficient to carry out the hydrorefining reaction of the feed. The metal compound is introduced before the said charge, previously added with hydrogen, passes through the heterogeneous catalyst bed. The metal compound is introduced into the charge previously added with hydrogen and previously brought to a temperature of at least 330 ° C, advantageously from 330 ° C to about 450 ° C and preferably, previously brought to a temperature of about 350 ° C to about 450 ° C. The amount of the metal compound added to the charge is such that the concentration of metal added relative to the total weight of the charge is from 10 to 1500 ppm and preferably from 30 to 600 ppm.

L'injection en continu ou par bouffée de ce composé métallique en particulier des composés de molybdène permet, outre l'augmentation de la durée de cycle, de maintenir constante l'activité démétallisante du catalyseur, d'améliorer les activités d'hydrodéazotation, d'hydrodésulfuration et de conversion des molécules lourdes.The continuous or puff injection of this metallic compound, in particular of the molybdenum compounds makes it possible, in addition to the increase in the cycle time, to keep the demetallizing activity of the catalyst constant, to improve the hydrodenitrogenation activities, d hydrodesulfurization and conversion of heavy molecules.

Sans vouloir être lié par une quelconque théorie, il semble que les composés métalliques, en particulier les composés de molybdène, se décomposent sur le catalyseur et les atomes de métaux (molybdène) se fixent alors à la surface du catalyseur, permettant ainsi d'éviter la désactivation de celui- ci, par régénération en continu ou périodique de la phase active.Without wishing to be bound by any theory, it seems that the metal compounds, in particular the molybdenum compounds, decompose on the catalyst and the metal atoms (molybdenum) then attach to the surface of the catalyst, thus making it possible to avoid deactivation thereof, by continuous or periodic regeneration of the active phase.

L'injection des composés de métaux, de préférence des composés de molybdène, est dans une forme avantageuse de la présente invention faite de manière périodique. On introduit ainsi une quantité de composé pendant une durée déterminée dans la charge, à intervalle variable, durant un temps plus ou moins long ; par exemple on introduit ce composé pendant 1 à 30 heures toutes les 100, 200 ou 300 heures et avantageusement pendant 10 à 20 heures toutes les 200 heures.The injection of the metal compounds, preferably molybdenum compounds, is in an advantageous form of the present invention carried out periodically. A quantity of compound is thus introduced during a determined period into the charge, at variable intervals, for a more or less long time; for example, this compound is introduced for 1 to 30 hours every 100, 200 or 300 hours and advantageously for 10 to 20 hours every 200 hours.

Les conditions usuelles de la réaction d'hydrotraitement sont une température d'environ 250 à environ 500 °C et de préférence environ 350 à environ 450 °C, une pression d'environ 5 à environ 30 mégapascals (MPa) et de préférence d'environ 8 à environ 20 MPa et un débit de charge hydrocarbonée par volume de catalyseur et par heure (VVH) d'environ 0,1 à environ 10 et de préférence d'environ 0,2 à environ 2. Le débit d'hydrogène est par exemple d'environ 50 à environ 5000 litres par litre de charge et de préférence d'environ 200 à environ 3000 x 1-1.The usual conditions for the hydrotreatment reaction are a temperature of approximately 250 to approximately 500 ° C and preferably approximately 350 to approximately 450 ° C, a pressure of approximately 5 to approximately 30 megapascals (MPa) and preferably approximately 8 to approximately 20 MPa and a flow rate of hydrocarbon feedstock per volume of catalyst and per hour (VVH) of approximately 0.1 to approximately 10 and preferably approximately 0.2 to approximately 2. The flow rate of hydrogen is for example from about 50 to about 5000 liters per liter of filler and preferably from about 200 to about 3000 x 1- 1 .

Dans les exemples suivants qui illustrent l'invention sans en limiter la portée on utilise deux catalyseurs A et B préparés suivant la méthode décrite dans la demande de brevet européen EP-A-98 764.In the following examples which illustrate the invention without limiting its scope, two catalysts A and B are used, prepared according to the method described in European patent application EP-A-98 764.

Les caractéristiques de ces deux catalyseurs sont celles qui sont décrites dans la demande de brevet EP-A-98 764 pour ce qui est de leurs structures, de leurs répartitions poreuses et de leurs compositions.The characteristics of these two catalysts are those which are described in patent application EP-A-98 764 with regard to their structures, their porous distributions and their compositions.

Le support de ces catalyseurs est de l'alumine, il est préparé suivant la méthode décrite dans l'exemple 1 de la demande de brevet EP-A-98 764 et possède toutes les caractéristiques décrites dans cet exemple. On dépose ensuite sur ce support du molybdène et du nickel en employant la méthode décrite dans l'exemple 1 de la demande EP-A-98 764. Les teneurs en métaux exprimées en poids d'oxyde par rapport au poids du catalyseur fini des catalyseurs A et B obtenus sont les suivantes :

Figure imgb0002
The support for these catalysts is alumina, it is prepared according to the method described in Example 1 of patent application EP-A-98 764 and has all the characteristics described in this example. Then deposited on this support molybdenum and nickel using the method described in Example 1 of application EP-A-98 764. The metal contents expressed by weight of oxide relative to the weight of the finished catalyst of the catalysts A and B obtained are the following:
Figure imgb0002

Exemple 1Example 1

Essai 1 : On met 1 1 de catalyseur A dans une unité pilote d'hydrotraitement fonctionnant en lit fixe. Les conditions opératoires de la mise en oeuvre de ce catalyseur sont les suivantes :

Figure imgb0003
Test 1: 1 1 of catalyst A is placed in a hydrotreating pilot unit operating in a fixed bed. The operating conditions for using this catalyst are as follows:
Figure imgb0003

Présulfuration du catalyseur par un mélange gazeux H2 + 3 % en volume d'hydrogène sulfuré (H2S), à 350 °C et à 0,1 MPa pendant 6 heures.Presulfurization of the catalyst with a gas mixture H 2 + 3% by volume of hydrogen sulfide (H 2 S), at 350 ° C and 0.1 MPa for 6 hours.

La coupe pétrolière utilisée pour effectuer le test est du résidu atmosphérique de pétrole de Safaniya (Arabie Saoudite) dont les caractéristiques sont les suivantes :

Figure imgb0004
The petroleum cut used to carry out the test is atmospheric petroleum residue from Safaniya (Saudi Arabia), the characteristics of which are as follows:
Figure imgb0004

L'unité pilote est constituée d'un four de préchauffage, permettant de porter la charge à la température désirée pour la réaction d'hydrotraitement catalytique, en série avec un réacteur d'hydrotraitement catalytique comportant un lit fixe de catalyseur.The pilot unit consists of a preheating oven, allowing the charge to be brought to the desired temperature for the catalytic hydrotreatment reaction, in series with a catalytic hydrotreatment reactor comprising a fixed catalyst bed.

On introduit la charge ci-dessus et l'hydrogène dans le four de préchauffage de manière à élever la température de ce mélange à 400 °C, ce mélange charge plus hydrogène passe ensuite dans le réacteur d'hydrotraitement catalytique.The above charge and the hydrogen are introduced into the preheating furnace so as to raise the temperature of this mixture to 400 ° C., this charge plus hydrogen mixture then passes into the catalytic hydrotreatment reactor.

Essai 2 : Dans les mêmes conditions opératoires, avec le même appareillage et le même catalyseur que celui employé dans l'essai 1, on effectue un autre test en ajoutant en continu dans le mélange charge-hydrogène sortant du four de préchauffage, du bleu de molybdène, sous forme d'une émulsion à 5,8 % en poids de bleu de molybdène dans un mélange eau-solvant organique contenant 2 % en poids d'eau, le solvant organique étant constitué par un mélange d'alcools en CrCg. La quantité de cette émulsion aquo-organique introduite dans la charge est telle que la teneur en molybdène, comptée en poids de métal par rapport au poids de la charge soit de 100 ppm.Test 2: Under the same operating conditions, with the same apparatus and the same catalyst as that used in test 1, another test is carried out by continuously adding, in the charge-hydrogen mixture leaving the preheating oven, molybdenum, in the form of an emulsion at 5.8% by weight of molybdenum blue in a water-organic solvent mixture containing 2% by weight of water, the organic solvent consisting of a mixture of CrCg alcohols. The quantity of this aquo-organic emulsion introduced into the charge is such that the molybdenum content, counted by weight of metal relative to the weight of the charge, is 100 ppm.

Au cours de ces deux essais les analyses de la teneur en soufre, nickel, vanadium et asphaltènes des effluents à la sortie du réacteur d'hydrotraitement catalytique sont effectuées, afin de comparer au cours du temps l'évolution des performances avec chacun des deux systèmes.During these two tests, the analyzes of the sulfur, nickel, vanadium and asphaltenes content of the effluents at the outlet of the catalytic hydrotreatment reactor are carried out, in order to compare over time the performance evolution with each of the two systems. .

Les résultats sont donnés dans le tableau I ci-dessous :

Figure imgb0005
Figure imgb0006
 The results are given in Table I below:
Figure imgb0005
Figure imgb0006

Les résultats montrent donc très nettement que les activités d'HDS, d'HDM et d'HDA (hydroconver- sion des asphaltènes) sont toujours supérieures lorsqu'on ajoute du bleu de molybdène à la charge. II est clair que la désactivation après 500 heures est beaucoup moins importante lorsqu'on ajoute du bleu de molybdène ce qui permet bien d'avoir une durée de cycle plus longue.The results therefore very clearly show that the activities of HDS, HDM and HDA (asphaltene hydroconversion) are always higher when molybdenum blue is added to the charge. It is clear that the deactivation after 500 hours is much less important when adding molybdenum blue, which makes it possible to have a longer cycle time.

Exemple 2Example 2

Essai 1 : 1 I de catalyseur B est placé dans une unité pilote d'hydrotraitement fonctionnant en lit fixe. L'appareillage, les conditions opératoires et la charge de test utilisée, sont identiques à celles de l'essai 1 de l'exemple 1.Test 1: 1 I of catalyst B is placed in a pilot hydrotreatment unit operating in a fixed bed. The apparatus, the operating conditions and the test load used are identical to those of test 1 of Example 1.

Essai 2 : 1 I du même catalyseur B est placé dans la même unité pilote, dans les mêmes conditions opératoires. Mais dans la charge on ajoute à la sortie du four de préchauffage avant son injection dans le réacteur d'hydrotraitement catalytique, de l'acide phosphomolybdique en solution aqueuse. La quantité d'acide ajoutée est telle que la teneur en molybdène dans la charge est de 50 ppm.Test 2: 1 I of the same catalyst B is placed in the same pilot unit, under the same operating conditions. However, in the feed, phosphomolybdic acid in aqueous solution is added at the outlet of the preheating oven before its injection into the catalytic hydrotreatment reactor. The amount of acid added is such that the molybdenum content in the feed is 50 ppm.

Les résultats obtenus au cours de chacun de ces deux essais sont portés tableau Il.

Figure imgb0007
The results obtained during each of these two tests are shown in Table II.
Figure imgb0007

Il apparaît donc que même avec un catalyseur plus actif, une injection, en quantité modérée, de molybdène dans la charge permet d'améliorer l'activité du système catalytique et d'avoir une meilleure stabilité au cours du temps.It therefore appears that even with a more active catalyst, an injection, in moderate quantity, of molybdenum into the feed makes it possible to improve the activity of the catalytic system and to have better stability over time.

Exemple 3Example 3

Essai 1 : 1 I de catalyseur A est chargé dans une unité pilote d'hydrotraitement en lit fixe identique à celle de l'exemple 1. Les conditions opératoires sont les suivantes :

  • - température 410°C
  • - pression totale 14 MPa
  • - VVH 0,3
  • - Rapport H2/charge 1 000 I/I
  • - Présulfuration par un mélange gazeux H2 + 3 % H2S en volume, à 350 °C et à 0,1 MPa pendant 6 heures.
Test 1: 1 I of catalyst A is loaded into a pilot hydrotreating unit in a fixed bed identical to that of Example 1. The operating conditions are as follows:
  • - temperature 410 ° C
  • - total pressure 14 MPa
  • - VVH 0.3
  • - Ratio H 2 / load 1000 I / I
  • - Presulfurization with a gas mixture H 2 + 3% H 2 S by volume, at 350 ° C and 0.1 MPa for 6 hours.

La charge de test est un asphalte dilué par 35 % poids d'huile de cycle légère (LCO).The test load is an asphalt diluted with 35% by weight of light cycle oil (LCO).

Les caractéristiques de cette charge sont les suivantes :

  • - Densité à 20 °C d4 20 1,065 g/cm3
  • - Viscosité à 100 °C 1 000 cSt (mm2/s)
  • - Carbone Conradson 27,5 % poids
  • - Asphaltène (nC7) 22,5 % poids
    Figure imgb0008
The characteristics of this charge are as follows:
  • - Density at 20 ° C d 4 20 1,065 g / cm 3
  • - Viscosity at 100 ° C 1000 cSt (mm 2 / s)
  • - Conradson carbon 27.5% by weight
  • - Asphaltene (nC 7 ) 22.5% by weight
    Figure imgb0008

Le mélange charge-hydrogène est porté à 410 °C dans le four de préchauffage puis introduit dans le réacteur d'hydrotraitement catalytique.The charge-hydrogen mixture is brought to 410 ° C. in the preheating oven and then introduced into the catalytic hydrotreatment reactor.

Essai 2: 1 I de catalyseur A est chargé dans la même unité pilote et est mis dans les mêmes conditions opératoires que celles de l'essai 1. Dans la même charge de test que celle utilisée dans l'essai 1 on ajoute à la sortie du four de préchauffage du bleu de molybdène en solution à 5,8 % en poids dans un mélange d'alcools en C7-C9. La quantité de solution ajoutée est telle que la teneur en molybdène dans la charge est de 150 ppm en poids.Test 2: 1 I of catalyst A is loaded into the same pilot unit and is put under the same operating conditions as those of test 1. In the same test load as that used in test 1, the output is added the molybdenum blue preheating oven in solution at 5.8% by weight in a mixture of C 7 -C 9 alcohols. The amount of solution added is such that the molybdenum content in the feed is 150 ppm by weight.

Essai 3 : Cet essai est identique à l'essai 2 à l'exception du fait que l'on remplace le bleu de molybdène par le trioxyde de molybdène dans un mélange eau-alcools C7-C9 à 10 % en poids d'eau et on introduit une quantité suffisante de cette composition pour avoir 150 ppm en poids de molybdène dans la charge.Test 3: This test is identical to test 2 except that the blue of molybdenum is replaced by molybdenum trioxide in a water-alcohol mixture C 7 -C 9 at 10% by weight of water and a sufficient amount of this composition is introduced to have 150 ppm by weight of molybdenum in the feed.

Essai 4 : Cet essai est identique à l'essai 2 à l'exception du fait que l'on utilise le bleu de molybdène préparé suivant la méthode décrite dans FR-A-1 099 953. On introduit une quantité suffisante de ce composé pour avoir 150 ppm en poids de molybdène dans la charge. Ces quatre essais sont résumés dans le tableau III ci-dessous :

Figure imgb0009
Test 4: This test is identical to test 2 with the exception that the molybdenum blue prepared using the method described in FR-A-1 099 953 is used. A sufficient amount of this compound is introduced to have 150 ppm by weight of molybdenum in the feed. These four tests are summarized in Table III below:
Figure imgb0009

Ces résultats montrent que l'addition dans la charge de bleu de molybdène, ou de trioxyde de molybdène permet d'augmenter les activités d'HDS, d'HDM et d'HDA, et également d'avoir une activité catalytique plus stable au cours du temps.These results show that the addition of molybdenum blue, or molybdenum trioxide, to the charge makes it possible to increase the activities of HDS, HDM and HDA, and also to have a more stable catalytic activity during time.

Exemple 4Example 4

Essai 1 : 1 1 de catalyseur A est placé dans une unité pilote d'hydrotraitement identique à celle décrite dans l'exemple 1. Les conditions opératoires sont les suivantes :

Figure imgb0010

  • - présulfuration du catalyseur par un mélange gazeux H2 + 3 % en volume d'H2S, pendant 6 heures à 350 °C et à pression atmosphérique.
Test 1: 1 1 of catalyst A is placed in a hydrotreating pilot unit identical to that described in Example 1. The operating conditions are as follows:
Figure imgb0010
  • - Presulfurization of the catalyst with a gas mixture H 2 + 3% by volume of H 2 S, for 6 hours at 350 ° C and at atmospheric pressure.

La charge d'hydrocarbures utilisée pour effectuer le test est du brut de Boscan désasphalté au pentane (brut Vénézuélien de la ceinture de l'Orénoque), dont les caractéristiques sont :

Figure imgb0011
The hydrocarbon charge used to carry out the test is Boscan crude deasphalted with pentane (Venezuelan crude from the Orinoco belt), the characteristics of which are:
Figure imgb0011

Le mélange chargé hydrogène est porté à 380 °C dans le four de préchauffage puis introduit dans le réacteur d'hydrotraitement catalytique.The charged hydrogen mixture is brought to 380 ° C. in the preheating oven and then introduced into the catalytic hydrotreatment reactor.

Essai 2 : 1 1 de catalyseur A est placé dans les mêmes conditions que celles de l'essai 1. La charge de test utilisée est également celle de l'essai 1. Mais au cours du test, toutes les 200 heures, pendant 12 heures on ajoute à la charge à la sortie du four de préchauffage de l'acide phosphomolybdique en solution aqueuse, en quantité telle que la concentration en molybdène dans la charge que l'on introduit pendant ces 12 heures soit de 600 ppm en poids.Test 2: 1 1 of catalyst A is placed under the same conditions as those of test 1. The test charge used is also that of test 1. But during the test, every 200 hours, for 12 hours phosphomolybdic acid in aqueous solution is added to the charge at the outlet of the preheating oven, in an amount such that the molybdenum concentration in the charge which is introduced during these 12 hours is 600 ppm by weight.

Les résultats obtenus au cours de chacun de ces deux essais sont regroupés tableau IV.

Figure imgb0012
The results obtained during each of these two tests are collated in Table IV.
Figure imgb0012

Ces résultats montrent bien que l'addition à la charge, à intervalle régulier, d'un composé de molybdène, permet d'augmenter l'activité catalytique et de la garder plus stable au cours du fonctionnement du système catalytique.These results clearly show that the addition, at regular intervals, of a molybdenum compound makes it possible to increase the catalytic activity and to keep it more stable during the operation of the catalytic system.

Exemple 5 (comparatif)Example 5 (comparative)

Essai 1 : 1 litre de catalyseur A est placé dans une unité pilote d'hydrotraitement fonctionnant en lit fixe. L'appareillage, les conditions opératoires et la charge de test utilisée, sont identiques à celles de l'essai 1 de l'exemple 4.Test 1: 1 liter of catalyst A is placed in a pilot hydrotreatment unit operating in a fixed bed. The apparatus, the operating conditions and the test load used are identical to those of test 1 of Example 4.

Essai 2 : 1 litre du même catalyseur A est placé dans la même unité pilote, dans les mêmes conditions opératoires. Mais dans le mélange charge-hydrogène on ajoute à la sortie du four de préchauffage, avant son injection dans le réacteur d'hydrotraitement catalytique, du naphténate de molybdène sous forme d'une solution à 6 % en poids dans un mélange d'alcools en C7-C9. La quantité de solution ajoutée est telle que la teneur en molybdène dans la charge est de 600 ppm.Test 2: 1 liter of the same catalyst A is placed in the same pilot unit, under the same operating conditions. However, in the charge-hydrogen mixture, molybdenum naphthenate is added at the outlet of the preheating oven, before its injection into the catalytic hydrotreatment reactor, in the form of a 6% by weight solution in a mixture of alcohols. C 7 -C 9 . The amount of solution added is such that the molybdenum content in the feed is 600 ppm.

Les résultats obtenus au cours de chacun de ces deux essais sont donnés dans le tableau V ci-après.

Figure imgb0013
The results obtained during each of these two tests are given in Table V below.
Figure imgb0013

D'autre part au cours de l'essai 2, à partir de la 400ième heure, d'importantes pertes de charge ont été observées.On the other hand, during test 2, from the 400th hour, significant pressure drops were observed.

Claims (11)

1. A process for the hydrotreatment of a heavy hydrocarbons charge by contact with at least one fixed or moving bed of heterogeneous catalyst, containing an alumina carrier, at least one catalytic metal or compound of catalytic metal from groups V B, VI B and VIII of the periodic classification of elements, said alumina carrier having a pore volume from 0.85 to 2 cm3. g-1, and a specific surface from 80 to 250 - g-1 characterized by the continuous or periodical introduction into said hydrocarbon charge with hydrogen previously added thereto in a sufficient amount for the hydrotreatment reaction, and previously heated to a temperature of at least 330 °C, of at least one compound of at least one metal selected from the group formed of halides, oxyhalides, oxides, polyacids and poiyacid salts of metals from groups VI B, VII B and VIII of the periodic classification of elements, before passing said charge through the bed of heterogeneous catalyst said compound being introduced in such amount that the content of metal added to the charge be from 10 to 1,500 ppm by weight.
2. A process according to claim 1, wherein the alumina carrier is selected from aluminas of nil or low acidity, thermally stabilized aluminas and autoclaved aluminas inert in the n-heptane cracking test.
3. A process according to claim 2, wherein the alumina carrier is an autoclaved alumina formed of a plurality of acicular small plates, the plates of each conglomerate being generally oriented radially with respect to one another and with respect to the center of the conglomerate.
4. A process according to one of claims 1 to 3, wherein the metal compound is introduced into the charge as a solution or emulsion in a water-organic solvent mixture containing 70 à 99 % by weight of organic solvent, as a solution in an organic solvent or as a solution in water.
5. A process according to claim 4, wherein the metal compound is introduced into the charge as a solution or emulsion in a water-organic solvent mixture, said organic solvent containing at least one alcohol of 6-18 carbon atoms.
6. A process according to one of claims 1 to 5, wherein the metal compound is introduced into the charge in such amount that the metal content added to the charge be from 30 to 600 ppm by weight.
7. A process according to one of claims 1 to 6, wherein the metal compound introduced into the charge is a molybdenum compound selected from the group consisting of molybdenum blues, phosphomolybdic acid and salts of phosphomolybdic acid.
8. A process according to one of claims 1 to 7, wherein the heterogeneous catalyst comprises from 1 to 30 % by weight (expressed as oxide) of a nickel and molybdenum, or cobalt and molybdenum, or nickel and tungsten associations.
9. A process according to one of claims 1 to 8, wherein the metal compound is introduced periodically into the charge.
10. A process according to one of claims 1 to 8, wherein the metal compound is introduced continuously into the charge.
11. A process according to one of claims 1 to 10, wherein the charge of hydrocarbons to be treated is selected from the group consisting of straight-run residues, vacuum residues, heavy crude oils, deasphalted oils, pitches and asphalts diluted with an aromatic distillate and coal hydrogenates and wherein the hydrotreatment is performed at a temperature from about 250 to about 500 °C under a pressure from about 5 to about 30 MPa, at a hourly space velocity (VVH) from about 0.1 to about 10 liters per liter of catalyst and per hour and with a hydrogen feed rate from about 50 to about 5 000 liters per liter of charge.
EP85402042A 1984-10-24 1985-10-22 Process for the catalytic hydrotreatment of heavy hydrocarbons in fixed or mobile beds with injection of a metal compound into the feed Expired EP0181253B1 (en)

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