EP0263522B1 - Procédé d'hydroconversion d'huiles lourdes et résiduelles - Google Patents

Procédé d'hydroconversion d'huiles lourdes et résiduelles Download PDF

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Publication number
EP0263522B1
EP0263522B1 EP87114725A EP87114725A EP0263522B1 EP 0263522 B1 EP0263522 B1 EP 0263522B1 EP 87114725 A EP87114725 A EP 87114725A EP 87114725 A EP87114725 A EP 87114725A EP 0263522 B1 EP0263522 B1 EP 0263522B1
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EP
European Patent Office
Prior art keywords
particle size
weight
oils
fraction
process according
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.)
Expired - Lifetime
Application number
EP87114725A
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German (de)
English (en)
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EP0263522A2 (fr
EP0263522A3 (en
Inventor
Klaus Kretschmar
Ludwig Dr. Merz
Klaus Dr. Niemann
José Guitian
Julio Dr. Krasuk
Franzo Dr. Marruffo
Klaus Kurzeja
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Veba Oel Technologie und Automatisierung GmbH
Intevep SA
Original Assignee
Veba Oel Technologie und Automatisierung GmbH
Intevep SA
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Publication date
Application filed by Veba Oel Technologie und Automatisierung GmbH, Intevep SA filed Critical Veba Oel Technologie und Automatisierung GmbH
Priority to EP92112758A priority Critical patent/EP0516187B1/fr
Priority to AT87114725T priority patent/ATE94583T1/de
Publication of EP0263522A2 publication Critical patent/EP0263522A2/fr
Publication of EP0263522A3 publication Critical patent/EP0263522A3/de
Application granted granted Critical
Publication of EP0263522B1 publication Critical patent/EP0263522B1/fr
Priority to GR950402920T priority patent/GR3017825T3/el
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
    • C10M175/0025—Working-up used lubricants to recover useful products ; Cleaning by thermal processes
    • C10M175/0041—Working-up used lubricants to recover useful products ; Cleaning by thermal processes by hydrogenation processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C1/00—Working-up tar
    • C10C1/20—Refining by chemical means inorganic or organic compounds
    • C10C1/205—Refining by chemical means inorganic or organic compounds refining in the presence of hydrogen
    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/086—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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
    • C10G47/26—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles suspended in the oil, e.g. slurries

Definitions

  • the invention relates to a process for the hydrogenative conversion of heavy and residual oils, waste and waste oils in the sump or combined sump and gas phase with hydrogen-containing gases at a hydrogen partial pressure of 50 to 300 bar, preferably 150 to 200 bar, one Temperature of 250 to 500 ° C, preferably 400 to 490 ° C, a gas-oil ratio of 100 to 10,000 Nm3 / t, preferably 1,000 to 5,000 Nm3 / t liquid and solid feed products with the addition of at least one component from the Group of activated coke from hard coal or lignite, soot, red mud, ferric oxide, blast furnace dust, ash from the gasification process of crude oils, natural inorganic ferrous minerals, laterites and limonites in an amount of 0.5 to 15% by weight based on the total amount liquid and solid feed products.
  • the feedstocks are characterized by a high metal, sulfur and asphalt content as well as a high tendency to form coke.
  • the invention particularly relates to a catalytic process for converting hydrocarbon-containing feedstocks such as Orinoco Belt Crudes, Maracaibo Lake Crudes, tar sands from Athabasca and Canada crude oils such as Gold Lake in the sump phase in the presence of hydrogen.
  • feedstocks have a sulfur content between 2 and 6%, a metal content (vanadium and nickel) of 200 to 1400 ppm and more, a density of less than 20 ° API, a coking residue of more than 2% and a residue content of more than 40 % By weight (500 ° C +).
  • hydrocracking conditions pressure, temperature, gas / oil ratio, etc.
  • a component such as activated coke made from hard coal or lignite, soot, red mud, iron III oxide, blast furnace dust, ash from gasification processes of the aforementioned crude oils , natural, inorganic ferrous minerals such as laterite and limonite, in an amount of 0.5 to 15 wt .-% based on the liquid or liquid and solid use added to the hydrogenation process.
  • Document CA-A-1,117,887 describes a hydrocracking process for converting heavy oil into lighter hydrocarbons under high pressure and high temperature.
  • the heavy oil is mixed with a finely divided brown coal additive with a grain size of less than 149 ⁇ m, which is loaded with at least one metal from element group IVa or VIII of the periodic table.
  • Document US-A-4,591,426 also describes a hydroconversion process for heavy feedstocks with a metal content of at least 200 ppm at temperatures above 400 ° C. and a total hydrogen pressure of 1022 bar using a natural inorganic material such as laterite or limonite.
  • a natural inorganic material such as laterite or limonite.
  • 1 to 15% by weight of particles with particle sizes between 1270 and 12700 ⁇ m, based on the feed are supplied, these making up 20 to 80% by weight of the content of the reaction zone.
  • Document GB-A-2 135 691 describes a process for hydrocracking heavy oils in the presence of an additive made from finely ground coal or another carbon-containing material with the addition of a compound of a catalytically active metal such as iron, cobalt or molybdenum. Particle sizes of the additive of less than 74 ⁇ m are disclosed.
  • the invention has for its object to avoid excessive foam formation in a method of the type mentioned.
  • Another object of the invention is the improved utilization of the reaction zone of the hydrogenation reactor or reactors.
  • the component is added in two different grain size distributions from separate grindings, such that a fine grain fraction with a grain size of 90 ⁇ m or less and a coarse grain fraction with a grain size of 90 to 1,000 ⁇ m, preferably 100 Up to 500 microns is present and the latter makes up a share of 5 - 80 wt .-% of the added component.
  • One embodiment of the method according to the invention is that the proportion of the coarse grain fraction is between 10 and 30 and in particular between 20 and 30% by weight of the added component.
  • a preferred embodiment for the start-up phase of the present method is that the coarse grain fraction is more than 20% by weight of the amount of the component added.
  • the invention can also be used for the hydrogenation of mixtures of heavy or residual oils or waste oils with ground brown coal and / or hard coal, the oil / coal weight ratio being between 5: 1 and 1: 1.5.
  • the coal can be used as a coarse grain fraction with a corresponding proportion of a grain size of 100 ⁇ m and more.
  • the amount of liquid in the hydrocracking zone of the reactor initially increases for a given gas velocity when larger particles are used.
  • the present invention enables improved utilization of the reaction zone by using two metering streams of the catalyst with two different particle size distributions.
  • An embodiment of the present invention discloses a conversion process for heavy crude oils with a density of less than 20 ° API, more than 200 ppm metal content and more than 5% by weight Conradson coal in the presence of hydrogen and a catalyst in a bottom phase reactor in which an upward three-phase flow is formed.
  • the catalyst can comprise metals from element group Va, VIa or VIIIa of the periodic table, with or without a porous support, on which metals also contained in the crude oil are deposited.
  • the present invention discloses that for very high conversion rates (90% and more) of fractions boiling above 500 ° C. at moderately high flow rates (0.5 t / m3h or more), a considerable proportion of small particles (below 50 ⁇ m) are required because this brings significant advantages for the hydrogenation capacity of the catalyst system.
  • thermodynamic, fluid dynamic and kinetic relationships in the bottom phase hydrogenation with the addition of additives or catalysts in a bottom-flow tube reactor have not yet been completely clarified, it is assumed that the coarse grain fraction limits the foam formation or the gas residence time and that the amount of liquid is limited to Cost of the gas portion within the reactor, which is reflected by the differential pressure across the reactor height as well expresses the conversion rate and the preheating temperature. This phenomenon is noticeable at gas velocities in the reactor of more than 3 cm / s, temperatures of more than 250 ° C and pressures between 50 and 300 bar.
  • the highly active fine grain fraction preferably having a grain size of less than 50 ⁇ m by means of a metering system and the coarse grain fraction of a less active catalyst by means of a second metering system or inert material with a grain size of 100 to 1000 microns, preferably 150 to 1000 microns is fed, which serves to adapt the system to the fluid dynamic requirements, the amount of liquid in the bottom phase reactor is maximized.
  • the corresponding catalyst mixture which is formed from components of two different particle size distributions, can also be prepared beforehand in another separate apparatus, in order then to be brought into contact with the oil insert via a single metering system.
  • a remarkable aspect of the present invention is that two separate particle size distributions of the catalyst are used, where both fractions can consist of the same or different materials.
  • FIG. 1 shows the hydroconversion process according to the invention with subsequent distillation and hydrodesulfurization in a flow diagram.
  • the fine-grain fraction is introduced via line 1, from the storage vessel 2 discontinuously via valve 3 into a weighing container 4, from which the desired amount of the added component is fed via line 6 to the mixing container 13 via a continuous screw conveyor 5.
  • the coarse grain fraction of the single-use catalyst or additive fed.
  • the coarse grain fraction is provided via line 7 in the storage vessel 8 and fed discontinuously to the weighing container 10 via valve 9.
  • the desired amount of coarse grain fraction is introduced into the mixing container 13 via a continuous screw conveyor 11 and mixed with the heavy oil and the fine grain fraction supplied via line 16.
  • the invention is not limited to the illustrated embodiment with the two dosing systems described.
  • the different grain fractions of the catalyst can also be supplied in other ways.
  • the heavy oil and the two grain fractions of the catalyst are fed from the mixing tank 13 via line 14 to a high-pressure pump 15 and via line 15 'to the heat exchangers 49 and 50, in which this material flow is preheated using the heat of reaction of the reaction products.
  • the fresh hydrogen is fed via line 61, the hydrogen-containing cycle gas via line 59 to the cycle gas preheater 63, where the gas is heated to 200 to 500 ° C. and is fed to the heater 18 together with the preheated feed stream from line 50 ′.
  • the reactor system consists of one or at least two reactors connected in series. To be favoured three reactors connected in series.
  • the reactors 20, 24 and 27 are vertical tubular reactors with or without internals, which are operated with the flow direction from bottom to top. Here the conversion takes place at temperatures between 400 and 490 ° C, preferably 430 and 480 ° C, a hydrogen partial pressure between 50 and 300 bar and a circulating gas volume of 100 Nm3 / t to 10000 Nm3 / t.
  • a quasi-isothermal mode of operation of the reactors is possible by supplying cold gas via lines 21, 23 and 26.
  • downstream hot separators which are operated at approximately the same temperature level as the reactors, the unconverted portion of the heavy and residual oils used as well as the solids is separated from the gaseous reaction products under process conditions.
  • the bottom product of the hot separator is expanded in a multi-stage flash unit.
  • the top product of the hot separators, the flash stills and any crude oil distillate fractions to be processed are combined and fed to the downstream gas phase reactors. Hydrotreating or mild hydrocracking is carried out on a fixed catalytic bed under trickle-flow conditions under the same total pressure as in the sump phase.
  • the gaseous reaction products (C1 to C4 gases, H2S, NH3) are largely separated from the process gas, the remaining hydrogen is recycled as recycle gas.
  • the amount of liquid in the reactor can be optimized so that the conversion of the heavy crude oil in the reaction system increases while the preheating temperature is reduced, thereby reducing the investment and operating costs of the preheater system.
  • the process according to the invention has particular advantages in the event that the gas velocity in the Reactor under reaction conditions is greater than 3 cm / s based on the reactor cross section, which is normally true for gas velocities in industrial reactors.
  • the same material is added as a fine grain and a coarse grain fraction.
  • material of different compositions for the fine and coarse grain fraction e.g. B. Fe2O3 as a fine grain fraction with a particle size with an upper limit of 30 microns and for the coarse grain fraction activated coke from lignite with a lower grain size of 100 microns.
  • the two catalyst fractions do not necessarily have to be fed to the catalyst-oil mixing container 13 (FIG. 1) via two separate metering systems. but can also be mixed beforehand and added directly as a catalyst mixture.
  • the only decisive factor is the use of two different particle size distributions of the catalyst or additive from the same or different chemical species. The use of these two catalyst fractions leads to the unexpected result described in the invention.
  • the hydrocracking product is fed via line 28 into the first hot separator 29 in order to separate the gas / vapor phase from the heavier liquid products which contain unconverted residues (catalyst).
  • the temperature of the hot separators 29 and 33 is regulated in a range from 300 to 450 ° C. by supplying quench gas via lines 32 and 34, which is fed in at the bottom.
  • the second hot separator 33 mainly serves as a scraper for the gas phase reactors 40 and 46.
  • the top product of the second hot separator 33 is combined via line 36, the flash distillate 77 as well as the crude oil distillate 36 ', which is produced elsewhere, and the gas phase reactors 40 and 46 at the same total pressure and approximately the same or fed to a somewhat reduced temperature as in the bottom phase reactor.
  • the operating conditions of these reactors are according to the invention for the pressure between 50 and 300 bar, for the temperature between 300 and 450 ° C and for the gas / liquid ratio between 50 and 10000 Nm3 / t.
  • Hydrotreating or mild is carried out in this conventional reactor Hydrocracking at fixed bed reaction zones under trickle flow conditions using a conventional hydrodesulfurization catalyst or a mild hydrocracking catalyst from groups VIa or VIIIa of the periodic table on an alumina support.
  • the product is fed via line 47 to intensive cooling and condensation (49, 50).
  • the heat of reaction is used to preheat the fresh insert.
  • the gas / liquid mixture is fed to the high-pressure cold separator 52 via line 51.
  • the liquid product is relaxed and can then be fed to the standard refinery technology.
  • the gaseous reaction product After passing through the cold separator 52, the gaseous reaction product is separated as much as possible from the process gas which is discharged via line 56. The remaining hydrogen is fed to the compressor 58 via line 57 and returned to the process via line 59.
  • the bottom product of the hot separators 29 and 33 is fed via lines 32 and 34 to a multi-stage flash unit 65 and 72, decompressed and the residue of the used catalysts or additives is removed for workup, for example by carbonization, gasification or solids separation, via line 73 in order to be used again later can.
  • a vertical bubble column reactor without internals the temperature of which is controlled via the outlet temperature of a preheater system and via a cold gas quench system, is charged with a specific throughput of 1.5 t / m3h with vacuum residue from a conventional residual oil of Venezuelan origin at a hydrogen partial pressure of 190 bar, whereby 2000 Nm3 of hydrogen can be used per ton of residue.
  • the gas velocity is 6 cm / s. 2% by weight of lignite coke with a sharp upper grain limit at 90 ⁇ m are added to the feed product.
  • a temperature in the reactor of 455 ° C. is reached at a preheater outlet temperature of 447 ° C.
  • the differential pressure across the reactor height is about 100 mbar. A residue conversion of approximately 45% is achieved under these conditions.
  • the system was then operated with two different dosing systems.
  • the total amount of catalyst was again 2% by weight.
  • the differential pressure increased from 100 mbar to approximately 300 mbar, while the preheater outlet temperature decreased from 447 ° C to 438 ° C.
  • the conversion rate (RU) of the residue rose from 45 to 62%.
  • H middle Temperature ° C Conversion% A 100% by weight 30 ⁇ m 0.5 461 90 B 75% by weight 30 ⁇ m 0.5 455 90 25% by weight 90-130 ⁇ m C. like B 0.75 455 78 D like B 0.75 461 90

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
  • Lubricants (AREA)

Claims (7)

  1. Procédé d'hydroconversion d'huiles lourdes et résiduelles, d'huiles usées et de déchets d'huile en phase liquide ou en phase combinée liquide et gazeuse avec des gaz contenant de l'hydrogène à une pression partielle d'hydrogène de 50 à 300 bars de préférence de 150 à 200 bars, une température de 250 à 500°C, de préférence de 400 à 490°C, une proportion gaz/huile de 100 à 10 000 Nm3/t, de préférence de 1 000 à 5 000 Nm3/t de produits mis en oeuvre liquides et solides en ajoutant au moins un composant du groupe coke actif de houille ou de lignite, noir de carbone, boue rouge, oxyde de fer III, poussière de haut fourneau, cendres de procédés de gazéification d'huiles brutes, minéraux naturels contenant du fer, latérite et limonite, à une concentration de 0,5 à 15 % en poids par rapport à la quantité totale de produits liquides et solides mis en oeuvre, caractérisé en ce qu'on ajoute les composants en deux répartitions granulométriques différentes provenant de deux broyages différents, de sorte qu'il existe une fraction granulométrique fine avec une taille de grain de 90 µm ou inférieure et une fraction granulométrique grossière avec une taille de grain de 90 à 1 000 µm et que, celle-ci représente une proportion de 5 à 80 % en poids du composant ajouté.
  2. Procédé selon la revendication 1, caractérisé en ce que la fraction à grain grossier a une granulométrie comprise entre 100 et 500 µm
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que la proportion de la fraction grossière est comprise entre 10 et 30, notamment entre 20 et 30 % en poids du composant ajouté.
  4. Procédé selon la revendication 1 ou 2, caractérisé en ce que la fraction grossière représente, dans la phase de démarrage plus de 20 % en poids de la quantité des composants ajoutés.
  5. Procédé selon au moins l'une des revendications précédentes, caractérisé en ce qu'on utilise deux répartitions granulométriques séparées du composant ajouté, les deux fractions pouvant être constituées du même matériau ou de matériaux différents.
  6. Procédé selon la revendication 1, caractérisé en ce qu'on utilise des mélanges d'huiles lourdes ou résiduelles, des huiles usagées ou des déchets d'huile avec de la houille ou du lignite, la proportion pondérale de l'huile au charbon étant comprise entre 5 : 1 et 1 : 1,5.
  7. Procédé selon la revendication 6, caractérisé en ce qu'on utilise une partie du lignite ou du charbon correspondant à la fraction grossière du composant à une granulométrie de 100 µm ou supérieure.
EP87114725A 1986-10-08 1987-10-08 Procédé d'hydroconversion d'huiles lourdes et résiduelles Expired - Lifetime EP0263522B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP92112758A EP0516187B1 (fr) 1986-10-08 1987-10-08 Procédé d'hydroconversion d'huiles lourdes et résiduelles
AT87114725T ATE94583T1 (de) 1986-10-08 1987-10-08 Verfahren zur hydrierenden konversion von schwer- und rueckstandsoelen.
GR950402920T GR3017825T3 (en) 1986-10-08 1995-10-20 Process for the hydroconversion of heavy and residual oils.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3634275 1986-10-08
DE19863634275 DE3634275A1 (de) 1986-10-08 1986-10-08 Verfahren zur hydrierenden konversion von schwer- und rueckstandsoelen

Related Child Applications (2)

Application Number Title Priority Date Filing Date
EP92112758A Division-Into EP0516187B1 (fr) 1986-10-08 1987-10-08 Procédé d'hydroconversion d'huiles lourdes et résiduelles
EP92112758.5 Division-Into 1987-10-08

Publications (3)

Publication Number Publication Date
EP0263522A2 EP0263522A2 (fr) 1988-04-13
EP0263522A3 EP0263522A3 (en) 1989-04-12
EP0263522B1 true EP0263522B1 (fr) 1993-09-15

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EP87114725A Expired - Lifetime EP0263522B1 (fr) 1986-10-08 1987-10-08 Procédé d'hydroconversion d'huiles lourdes et résiduelles
EP92112758A Expired - Lifetime EP0516187B1 (fr) 1986-10-08 1987-10-08 Procédé d'hydroconversion d'huiles lourdes et résiduelles

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EP92112758A Expired - Lifetime EP0516187B1 (fr) 1986-10-08 1987-10-08 Procédé d'hydroconversion d'huiles lourdes et résiduelles

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US (1) US4851107A (fr)
EP (2) EP0263522B1 (fr)
JP (1) JPH0696710B2 (fr)
AT (1) ATE128174T1 (fr)
CA (1) CA1302332C (fr)
DE (3) DE3634275A1 (fr)
ES (2) ES2043629T3 (fr)
NO (1) NO171219C (fr)

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DE3912807A1 (de) * 1989-04-19 1990-11-08 Gfk Kohleverfluessigung Gmbh Katalysator bzw. additiv zur hydrierenden behandlung von schweren erdoelen bzw. schweren erdoelfraktionen sowie verfahren zur gewinnung des katalysators
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US4851107A (en) 1989-07-25
NO874205L (no) 1988-04-11
CA1302332C (fr) 1992-06-02
DE3751534D1 (de) 1995-10-26
EP0516187A2 (fr) 1992-12-02
ES2043629T3 (es) 1994-01-01
EP0263522A2 (fr) 1988-04-13
JPH0696710B2 (ja) 1994-11-30
ES2078610T3 (es) 1995-12-16
EP0263522A3 (en) 1989-04-12
EP0516187A3 (en) 1992-12-09
NO171219C (no) 1993-02-10
DE3787434D1 (de) 1993-10-21
EP0516187B1 (fr) 1995-09-20
NO171219B (no) 1992-11-02
ATE128174T1 (de) 1995-10-15
JPS63146989A (ja) 1988-06-18
NO874205D0 (no) 1987-10-07
DE3634275A1 (de) 1988-04-28

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