EP0181253A1 - 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 PDFInfo
- Publication number
- EP0181253A1 EP0181253A1 EP85402042A EP85402042A EP0181253A1 EP 0181253 A1 EP0181253 A1 EP 0181253A1 EP 85402042 A EP85402042 A EP 85402042A EP 85402042 A EP85402042 A EP 85402042A EP 0181253 A1 EP0181253 A1 EP 0181253A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- charge
- metal
- molybdenum
- metal compound
- feed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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), said alumina support having a pore volume of 0.85 a 2 cm 3 x g-1 and a specific surface of 80 to 250 m 2 x g- 1 , said process being characterized in that one adds to the charge of hydrocarbons to be treated added with hydrogen in 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 group formed by the metals of groups VI B, VII B and VIII of the periodic table of elements before passage of said
- 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 filler 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 xg -1 and a specific surface from 80 to 250 m 2 xg -1 in industrial hydrorefining units for longer treatment times than those obtained with the methods of the prior art, and in certain cases making it possible to avoid having to carry out a second hydrotreatment step.
- 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 peri classification contains elements and advantageously 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 fixed bed or mobile catalyst supported on alumina, under conventional conditions for hydrotreating heavy products, in particular allows to significantly increase the life of these catalysts.
- 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 C 7 -C 9 alcohols or in solution in water-alcohol mixtures C 7 - C 9 .
- phosphomolybdic acid or its salts in aqueous solution, and / or blues of molybdenum preferably chosen from those described in FR-A-1 099 953, in solution in a mixture of alcoholen C 7 -C 9 or in a mixture water-alcohol C 7 -C 9 or hydrocarbons, for example in a fraction of the load after a previous treatment.
- the catalysts that are used in the context of the present invention containing an alumina support with a pore volume of 0.85 to 2 cm 3 g -1 and a specific surface of 80 to 250 m 2 ⁇ 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 / 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 -6 at the temperature of 500 ° C.
- Aluminas treated with alkali metal and / or alkaline - earth metal for example those having a content of Na 2 0 to 1000 ppm by weight or more are usable, as well as the 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 of a plurality of needle-shaped plates, the plates of each agglomerate being oriented generally radially with respect to each other and relative to the center of the agglomerate.
- the aforementioned structure includes macropores and mesopores (we call mesopores, pores of size between that of micropores and that of 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 are deposited by any 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 of which the support formed from autoclaved alumina has the structure recalled above, which have a structure identical to that of the support, and have improved resistance in 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. Were obtained spec i fi c activities q ues of 0.610 -6 mol / h / m 2 at 470 ° C and 8 ⁇ 10 -6 mol / 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 enough hydrogen to perform. the feed hydrorefining reaction.
- the introduction of metal compound takes place before the passage of said charge added with hydrogen through the heterogeneous catalyst bed, in a preferred form of the invention the metal compound is introduced into the charge added with hydrogen previously carried at a temperature of at least 330 ° C, advantageously from 330 ° C to 450 ° C approximately and preferably, previously brought to a temperature of approximately 350 ° C to approximately 450 ° C.
- this metallic compound in particular of the molybdenum compounds, makes it possible, in addition to increasing the cycle time, to keep the demetallizing activity of the catalyst constant, to improve the hydrodenitrogenation activities, 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 duration into the charge, at variable intervals, for a more or less long time; for example, this compound is introduced for 1 to 30 h every 100,200 or 300 hours and advantageously for 10 to 20 h every 200 hours.
- the amount of the metal compound added to the charge is advantageously 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.
- the usual conditions for the hydrotreatment reaction are a temperature of about 250 to about 500 ° C and preferably about 350 to about 450 ° C, a pressure of about 5 to about 30 megapascals (MPa) and preferably from 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 d 'Hydrogen is for example from about 50 to about 5000 liters per liter of feed 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 EP-A-98 764.
- the metal contents expressed by weight of oxide relative to the weight of the finished catalyst A and B obtained are the following:
- 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 bed of catalyst.
- 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 being constituted killed by a mixture of C 7 -C 9 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 1 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:
- 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 1 of catalyst A is loaded into the same pilot unit and is placed under the same operating conditions as those of test 1. In the same test load as that used in test 1, the following is added to the out of the preheating oven of molybdenum blue 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 d 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 quantity 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 feed 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.
Landscapes
- 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
Description
La présente invention concerne un procédé d'hydrotraitement de charges lourdes hydrocarbonées contenant des impuretés hétéroatomiques telle 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), ledit support d'alumine ayant un volume poreux de 0,85 a 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), said alumina support having a pore volume of 0.85 a 2 cm 3 x g-1 and a specific surface of 80 to 250 m 2 x g- 1 , said process being characterized in that one adds to the charge of hydrocarbons to be treated added with hydrogen in 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 group formed by the metals of groups VI B, VII B and VIII of the periodic table of elements before passage of said charge through the catalyst bed heterogeneous.
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'hydrodéazo- tation.On the other hand, the metals of the filler 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 chataignes ou encore à un tas d'oursins de mer, sont particulièrement efficaces dans des réactions de démétallation 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 among which we can cite 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 demetallation 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'hydrodémétallation (HDtl) 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 oeuvre 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 (HDtl) 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 used in order to obtain products which can be used as finished products or as feedstock in catalytic hydrocracking cracking units 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 xg -1 and a specific surface from 80 to 250 m 2 xg -1 in industrial hydrorefining units for longer treatment times than those obtained with the methods of the prior art, and in certain cases making it possible to avoid having to carry out a second hydrotreatment step.
D'une façon surprenante on a découvert que l'addition à la charge d'hydrocarbures à traiter de manière continu 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 peri classification contains elements and advantageously 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 fixed bed or mobile catalyst supported on alumina, under conventional conditions for hydrotreating heavy products, in particular allows to significantly increase the 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 lenaphténatede 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 lenaphthénatee molybdenum, seem to decompose very quickly in contact with the catalyst, at the head of the 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 composes contenant du chlore, du brome ou de l'iode dans leurs formules et plus particulièremenc 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 are preferably used and especially mixtures of alcohols having 6 to 18 carbon atoms or hydrocarbons.
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 C7-C9 ou en solution dans des mélanges eau-alcools C7-C9. 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'alcoolsen 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 C 7 -C 9 alcohols or in solution in water-alcohol mixtures C 7 - C 9 . It is particularly advantageous to use, for example phosphomolybdic acid or its salts in aqueous solution, and / or blues of molybdenum preferably chosen from those described in FR-A-1 099 953, in solution in a mixture of alcoholen C 7 -C 9 or in a mixture water-alcohol C 7 -C 9 or hydrocarbons, for example in a fraction of the load after 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×g-1.The catalysts that are used in the context of the present invention, containing an alumina support with a pore volume of 0.85 to 2 cm 3 g -1 and a specific surface of 80 to 250 m 2 × 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 megapascals (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 :
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/m2 de support) est inférieure à 5 x 10-6 à la température de 470°C et si elle est inférieure à 15 x 10-6 à la température de 500°C.In this test, a support is said to be neutral if its cracking activity (mole / hour / 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 -6 at the 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 celle 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.Aluminas treated with alkali metal and / or alkaline - earth metal, for example those having a content of Na 2 0 to 1000 ppm by weight or more are usable, as well as the 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 précitéecomprend 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 of a plurality of needle-shaped plates, the plates of each agglomerate being oriented generally radially with respect to each other and relative to the center of the agglomerate. The aforementioned structure includes macropores and mesopores (we call mesopores, pores of size between that of micropores and that of 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, décrit ci-dessus on dépose par toutes méthodes connues le ou les métaux catalytiques ou composés de métaux catalytiquesde 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 préférés 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 a 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 are deposited by any 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 a 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 spéci-fiques 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, of which the support formed from autoclaved alumina has the structure recalled above, which have a structure identical to that of the support, and have improved resistance in 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. Were obtained spec i fi c activities q ues of 0.610 -6 mol / h / m 2 at 470 ° C and 8 × 10 -6 mol / 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 ajouter 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 additionnée d'hydrogène à travers le lit de catalyseur hétérogène, dans une forme préférée de l'invention le composé de métal est introduit dans la charge additionnée d'hydrogène 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.The continuous or periodic injection of metal compounds, and in particular of molybdenum compounds is carried out after adding enough hydrogen to perform. the feed hydrorefining reaction. The introduction of metal compound takes place before the passage of said charge added with hydrogen through the heterogeneous catalyst bed, in a preferred form of the invention the metal compound is introduced into the charge added with hydrogen previously carried at a temperature of at least 330 ° C, advantageously from 330 ° C to 450 ° C approximately and preferably, previously brought to a temperature of approximately 350 ° C to approximately 450 ° C.
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 increasing the cycle time, to keep the demetallizing activity of the catalyst constant, to improve the hydrodenitrogenation activities, 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 h toutes les 100,200 ou 300 heures et avantageusement pendant 10 à 20 h 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 duration into the charge, at variable intervals, for a more or less long time; for example, this compound is introduced for 1 to 30 h every 100,200 or 300 hours and advantageously for 10 to 20 h every 200 hours.
La quantité du composé métallique ajouté à la charge est avantageusement 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 amount of the metal compound added to the charge is advantageously 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.
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 about 250 to about 500 ° C and preferably about 350 to about 450 ° C, a pressure of about 5 to about 30 megapascals (MPa) and preferably from 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 d 'Hydrogen is for example from about 50 to about 5000 liters per liter of feed 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 : 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 EP-A-98 764. The metal contents expressed by weight of oxide relative to the weight of the finished catalyst A and B obtained are the following:
- • 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 : • 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:
La coupe pétrolière utilisée pour effectuer le test est du résidu atmosphérique de pétrole de Safaniya (Arabie Saoudite) dont les caractéristiques sont les suivantes :
L'unité pilote est constituée d'un four de préchauffage, permettant de porter la charge à la température disirée 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 bed of catalyst.
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 C7-C9. 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 being constituted killed by a mixture of C 7 -C 9 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 :
Les résultats montrent donc très nettement que les activités d'HDS, d'HDM et d'HDA (hydroconversion des asphaltènes) sont toujours supérieures lorsqu'on ajoute du bleu de molybdène à la charge. Il 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 deactivation after 500 hours is much less important when molybdenum blue is added, which makes it possible to have a longer cycle time.
- • Essai 1 : 1 1 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 1 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 1 du même catalyseur Best 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 1 of the same Best catalyst 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 II.
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 charge makes it possible to improve the activity of the catalytic system and to have better stability over time.
• Essai 1 : 1 1 de catalyseur A est charge dans une unité pilote d'hydrotraitement en lit fixe identique a celle de l'exemple 1. Les conditions opératoires sont les suivantes :
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 :
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 1 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 1 of catalyst A is loaded into the same pilot unit and is placed under the same operating conditions as those of test 1. In the same test load as that used in test 1, the following is added to the out of the preheating oven of molybdenum blue 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 d 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 :
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.
0 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 : 0 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:
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 :
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 feed 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.
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.
. 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.
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)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT85402042T ATE36555T1 (en) | 1984-10-24 | 1985-10-22 | PROCESS FOR THE CATALYTIC HYDROTREATMENT OF HEAVY CARBON FUEL IN FIXED OR MOVING BED WITH INJECTION OF A METAL COMPOUND INTO THE CARGO. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8416255 | 1984-10-24 | ||
FR8416255A FR2572088B1 (en) | 1984-10-24 | 1984-10-24 | PROCESS FOR CATALYTIC HYDROTREATMENT OF HEAVY HYDROCARBONS, IN FIXED OR MOBILE BED, WITH INJECTION OF A METAL COMPOUND INTO THE LOAD |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0181253A1 true EP0181253A1 (en) | 1986-05-14 |
EP0181253B1 EP0181253B1 (en) | 1988-08-17 |
Family
ID=9308953
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP85402042A Expired EP0181253B1 (en) | 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 |
Country Status (7)
Country | Link |
---|---|
US (1) | US4655905A (en) |
EP (1) | EP0181253B1 (en) |
JP (1) | JPS61111394A (en) |
AT (1) | ATE36555T1 (en) |
CA (1) | CA1243975A (en) |
DE (1) | DE3564447D1 (en) |
FR (1) | FR2572088B1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0256528A2 (en) * | 1986-08-15 | 1988-02-24 | Phillips Petroleum Company | Hydrofining process for hydrocarbon containing feed streams |
EP0280917A1 (en) * | 1987-02-06 | 1988-09-07 | Phillips Petroleum Company | Support material for fixed hydrofining beds |
EP0349358A1 (en) * | 1988-07-01 | 1990-01-03 | Eurecat Europeenne De Retraitement De Catalyseurs | Process for presulfiding and controlling the activity of a hydrocarbon treatment catalyst |
FR2633528A1 (en) * | 1988-07-01 | 1990-01-05 | Europ Retraitement Catalyse | Process for presulphurising and controlling the activity of catalyst for treating hydrocarbons |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8926555D0 (en) * | 1989-11-24 | 1990-01-17 | Shell Int Research | Process for upgrading a sulphur-containing feedstock |
JPH03167292A (en) * | 1989-11-27 | 1991-07-19 | Kawasaki Steel Corp | Method for reclaiming hydrodesulfurization catalyst |
US5336654A (en) * | 1990-12-24 | 1994-08-09 | Exxon Research And Engineering Company | Method for the preparation of supported hydrogenation and hydrotreating catalysts |
US5338717A (en) * | 1990-12-24 | 1994-08-16 | Exxon Research And Engineering Company | Method for the preparation of supported hydrogenation and hydrotreating catalysts |
US5198100A (en) * | 1990-12-24 | 1993-03-30 | Exxon Research And Engineering Company | Hydrotreating using novel hydrotreating catalyst |
US5897768A (en) * | 1997-02-28 | 1999-04-27 | Exxon Research And Engineering Co. | Desulfurization process for removal of refractory organosulfur heterocycles from petroleum streams |
EP1473082B1 (en) * | 2002-02-06 | 2013-10-09 | JX Nippon Oil & Energy Corporation | Method for preparing a hydroraffination catalyst |
MX2011009116A (en) | 2011-08-31 | 2013-02-28 | Mexicano Inst Petrol | Process of hydroconversion-distillation of heavy and/or extra-heavy crude oils. |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3169919A (en) * | 1962-07-02 | 1965-02-16 | Universal Oil Prod Co | Hydrorefining of petroleum crude oil and catalyst therefor |
US3331769A (en) * | 1965-03-22 | 1967-07-18 | Universal Oil Prod Co | Hydrorefining petroleum crude oil |
FR91785E (en) * | 1966-01-27 | 1968-08-09 | Shell Int Research | Hydrocracking process of hydrocarbon oils |
EP0098764A1 (en) * | 1982-06-17 | 1984-01-18 | Société Française des Produits pour Catalyse "PRO-CATALYSE" | Supported catalyst with resistance against metal poisoning, and its use in the hydrotreatment of petroleum fractions containing metal |
US4430207A (en) * | 1983-05-17 | 1984-02-07 | Phillips Petroleum Company | Demetallization of hydrocarbon containing feed streams |
EP0111912A1 (en) * | 1982-12-20 | 1984-06-27 | Phillips Petroleum Company | Demetallization of hydrocarbon containing feed streams |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2988501A (en) * | 1958-08-18 | 1961-06-13 | Union Oil Co | Hydrorefining of crude oils |
US3161585A (en) * | 1962-07-02 | 1964-12-15 | Universal Oil Prod Co | Hydrorefining crude oils with colloidally dispersed catalyst |
US3249530A (en) * | 1963-08-19 | 1966-05-03 | Universal Oil Prod Co | Hydrorefining of petroleum crude oil |
US3252894A (en) * | 1963-10-14 | 1966-05-24 | Universal Oil Prod Co | Crude oil hydrorefining process |
US3231488A (en) * | 1963-10-28 | 1966-01-25 | Universal Oil Prod Co | Process for hydrorefining heavy hydrocarbon charge stocks and catalyst therefor |
US3317421A (en) * | 1964-09-25 | 1967-05-02 | Universal Oil Prod Co | Hydrorefining of petroleum crude oil |
NL6601027A (en) * | 1966-01-27 | 1967-07-28 | ||
US3553106A (en) * | 1968-06-28 | 1971-01-05 | Gulf Research Development Co | Catalytic removal of vanadium and nickel from oils |
US3622499A (en) * | 1970-01-22 | 1971-11-23 | Universal Oil Prod Co | Catalytic slurry process for black oil conversion with hydrogen and ammonia |
US4148717A (en) * | 1977-08-19 | 1979-04-10 | Union Oil Company Of California | Demetallization of petroleum feedstocks with zinc chloride and titanium tetrachloride catalysts |
US4191635A (en) * | 1977-12-21 | 1980-03-04 | Standard Oil Company (Indiana) | Process for the cracking of heavy hydrocarbon streams |
US4255253A (en) * | 1979-01-03 | 1981-03-10 | The Standard Oil Company | Hydrogen processing of hydrocarbon feeds using coated catalysts |
US4306965A (en) * | 1979-03-19 | 1981-12-22 | Standard Oil Company (Indiana) | Hydrotreating process |
DE2967599D1 (en) * | 1979-11-13 | 1986-07-03 | Exxon Research Engineering Co | High surface area catalysts, their preparation, and hydrocarbon processes using them |
FR2473056A1 (en) * | 1980-01-04 | 1981-07-10 | Inst Francais Du Petrole | METHOD FOR HYDROPROCESSING HEAVY HYDROCARBONS IN THE PRESENCE OF A MOLYBDENATED CATALYST |
US4549957A (en) * | 1981-06-17 | 1985-10-29 | Amoco Corporation | Hydrotreating catalyst and process |
-
1984
- 1984-10-24 FR FR8416255A patent/FR2572088B1/en not_active Expired
-
1985
- 1985-10-22 AT AT85402042T patent/ATE36555T1/en not_active IP Right Cessation
- 1985-10-22 DE DE8585402042T patent/DE3564447D1/en not_active Expired
- 1985-10-22 EP EP85402042A patent/EP0181253B1/en not_active Expired
- 1985-10-24 CA CA000493710A patent/CA1243975A/en not_active Expired
- 1985-10-24 US US06/791,002 patent/US4655905A/en not_active Expired - Fee Related
- 1985-10-24 JP JP60238532A patent/JPS61111394A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3169919A (en) * | 1962-07-02 | 1965-02-16 | Universal Oil Prod Co | Hydrorefining of petroleum crude oil and catalyst therefor |
US3331769A (en) * | 1965-03-22 | 1967-07-18 | Universal Oil Prod Co | Hydrorefining petroleum crude oil |
FR91785E (en) * | 1966-01-27 | 1968-08-09 | Shell Int Research | Hydrocracking process of hydrocarbon oils |
EP0098764A1 (en) * | 1982-06-17 | 1984-01-18 | Société Française des Produits pour Catalyse "PRO-CATALYSE" | Supported catalyst with resistance against metal poisoning, and its use in the hydrotreatment of petroleum fractions containing metal |
EP0111912A1 (en) * | 1982-12-20 | 1984-06-27 | Phillips Petroleum Company | Demetallization of hydrocarbon containing feed streams |
US4430207A (en) * | 1983-05-17 | 1984-02-07 | Phillips Petroleum Company | Demetallization of hydrocarbon containing feed streams |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0256528A2 (en) * | 1986-08-15 | 1988-02-24 | Phillips Petroleum Company | Hydrofining process for hydrocarbon containing feed streams |
EP0256528A3 (en) * | 1986-08-15 | 1988-11-09 | Phillips Petroleum Company | Hydrofining process for hydrocarbon containing feed streams |
EP0280917A1 (en) * | 1987-02-06 | 1988-09-07 | Phillips Petroleum Company | Support material for fixed hydrofining beds |
EP0349358A1 (en) * | 1988-07-01 | 1990-01-03 | Eurecat Europeenne De Retraitement De Catalyseurs | Process for presulfiding and controlling the activity of a hydrocarbon treatment catalyst |
FR2633528A1 (en) * | 1988-07-01 | 1990-01-05 | Europ Retraitement Catalyse | Process for presulphurising and controlling the activity of catalyst for treating hydrocarbons |
Also Published As
Publication number | Publication date |
---|---|
EP0181253B1 (en) | 1988-08-17 |
ATE36555T1 (en) | 1988-09-15 |
FR2572088A1 (en) | 1986-04-25 |
DE3564447D1 (en) | 1988-09-22 |
JPS61111394A (en) | 1986-05-29 |
CA1243975A (en) | 1988-11-01 |
US4655905A (en) | 1987-04-07 |
FR2572088B1 (en) | 1987-07-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2169032B1 (en) | Catalyst capable of at least partially decomposing or hydrogenating unsaturated sulfur compounds | |
EP1800748B1 (en) | Method of selective hydrogenation using a sulphided catalyst | |
EP1002853B1 (en) | Process for the production of low sulfur gasolines | |
CA2688843C (en) | Hydrocracking process including switchable reactors with feedstock containing 220 ppm weight -2% asphaltene weight | |
EP1174485B1 (en) | Process comprising two gasoline hydrodesulphurisation steps with intermediary elimination of H2S | |
EP0343045B1 (en) | Catalytic composition comprising a metal sulfide suspended in an asphaltene containing liquid and hydrocarbon feed hydroviscoreduction process | |
EP2161076B1 (en) | Selective hydrogenation method using a sulphurated catalyst with a specific composition | |
EP1612255B1 (en) | Hydrodesulfurization process for naphtha fractions using a catalyst with controled porosity. | |
EP0181253B1 (en) | Process for the catalytic hydrotreatment of heavy hydrocarbons in fixed or mobile beds with injection of a metal compound into the feed | |
EP0785022B2 (en) | Process for incorporating sulphur in the porosity of a catalyst for the treatment of hydrocarbons | |
EP2962753A1 (en) | Hydrotreating catalyst with high molybdenum density and its method of preparation | |
EP0329499A1 (en) | Process for the presulfurization of hydrocarbon treatment catalysts | |
EP2255873A2 (en) | hydrodemetallation catalysts and hydrodesulfurization catalysts and a process using said catalysts | |
FR2950072A1 (en) | Pre-refining and hydroconversion of heavy crude oil containing e.g. asphaltene for producing pre-refined synthetic crude, by subjecting feedstock to treatment in hydrodemetallization section, and hydrocracking effluent of demetallized part | |
EP1369468B1 (en) | Process of production of hydrocarbons with low content of sulfur and of nitrogen | |
EP2745931A1 (en) | Device for hydrotreating of hyrocarbon residues comprising vanadium and use thereof in a method for hydrocoversion of waste | |
EP0153233B1 (en) | Process for the presulfurisation of a hydrocarbon treatment catalyst | |
EP3338887A1 (en) | Process for sulphurising a catalyst using a previously hydrotreated hydrocarbon fraction and a sulphur compound | |
WO2002066161A1 (en) | Method for sulphurizing hydrotreating catalysts | |
EP1715026B1 (en) | New desulphurising process of gasolines by rendering sulphur compounds heavier | |
CA2672615C (en) | Sulphidation agent for hydroprocessing catalyst and use thereof for in-situ and ex-situ presulphidation | |
FR2631631A1 (en) | Process for hydrovisbreaking of a hydrocarbon feedstock in the presence of a catalyst composition comprising a metal sulphide in suspension in a liquid containing asphaltenes | |
EP0955090A1 (en) | Catalyst for the hydrogenation of aromatic compounds in a hydrocarbon feedstock containing sulfur | |
EP4251712A1 (en) | Method for hydrodesulfurisation of a petroleum fraction using a catalyst containing a graphitic material characterised by the h/c ratio thereof | |
EP3870680A1 (en) | Deep desulphurization of low sulphur content feedstock |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE DE GB IT NL SE |
|
17P | Request for examination filed |
Effective date: 19860605 |
|
17Q | First examination report despatched |
Effective date: 19870526 |
|
ITF | It: translation for a ep patent filed |
Owner name: DE DOMINICIS & MAYER S.R.L. |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE DE GB IT NL SE |
|
REF | Corresponds to: |
Ref document number: 36555 Country of ref document: AT Date of ref document: 19880915 Kind code of ref document: T |
|
REF | Corresponds to: |
Ref document number: 3564447 Country of ref document: DE Date of ref document: 19880922 |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
ITTA | It: last paid annual fee | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19920917 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19920924 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 19921002 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19921016 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19921031 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19921121 Year of fee payment: 8 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19931022 Ref country code: AT Effective date: 19931022 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19931023 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Effective date: 19931031 |
|
BERE | Be: lapsed |
Owner name: INSTITUT FRANCAIS DU PETROLE Effective date: 19931031 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19940501 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee | ||
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19931022 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19940701 |
|
EUG | Se: european patent has lapsed |
Ref document number: 85402042.7 Effective date: 19940510 |