EP0113283A1 - Behandlung von Schwerölen oder Schwerölfraktionen zur Umwandlung in leichtere Fraktionen - Google Patents

Behandlung von Schwerölen oder Schwerölfraktionen zur Umwandlung in leichtere Fraktionen Download PDF

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Publication number
EP0113283A1
EP0113283A1 EP83402494A EP83402494A EP0113283A1 EP 0113283 A1 EP0113283 A1 EP 0113283A1 EP 83402494 A EP83402494 A EP 83402494A EP 83402494 A EP83402494 A EP 83402494A EP 0113283 A1 EP0113283 A1 EP 0113283A1
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EP
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Prior art keywords
catalyst
pores
pore volume
nanometers
alumina
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Granted
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EP83402494A
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English (en)
French (fr)
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EP0113283B1 (de
Inventor
Alain Billon
Yves Jacquin
Jean-Pierre Peries
Hervé Toulhoat
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C

Definitions

  • the invention relates to the treatment of heavy oils or heavy petroleum fractions, with a high asphaltene content, with the aim of converting them into lighter fractions, more easily transportable or treatable by the usual refining processes.
  • Coal hydrogenation oils can also be processed.
  • the invention solves the problem of the transformation of a viscous crude oil, non-transportable, rich in metals, sulfur and asphaltenes, and containing more than 50% of constituents with normal boiling point greater than 520 ° C., into a stable, easily transportable hydrocarbon product, of low content of metals, sulfur and asphaltenes and having only a reduced content, for example less than 20% by weight, of constituents with normal boiling point greater than 520 ° C. .
  • the problem solved by the invention has long been the subject of work; the main difficulty to be overcome is that of deactivation of the catalysts by impurities, in particular metallic impurities, of the treated charges.
  • impurities in particular metallic impurities
  • crude oil from Boscan or Cerro Negro can contain 200 to 1,000 ppm by weight, or more, of metals; these metals are mainly vanadium and nickel, with varying proportions of iron and other metals.
  • step (c) is implemented in two successive steps:
  • a catalyst (C 1 ) containing alumina, at least one molybdenum and / or tungsten compound and at least one nickel and / or cobalt compound the weight ratio of the metals being fixed between 0.8: 1 and 3: 1 and preferably between 1: 1 and 2: 1;
  • One of the metals in the numerator or denominator may be absent;
  • One of the metals in the numerator or denominator may be absent.
  • the weight ratio of catalyst C2 to catalyst C1 is preferably from 1: 1 to 9: 1.
  • FIG. 1 makes it possible to compare the porous distribution curve of a catalyst (A) as used in step (a) of the invention and those corresponding to monomodal (C) or bimodal (B) catalysts produced according to prior art.
  • the specific surface of this catalyst is between 50 and 250 m 2 / g and particularly preferably between 120 and 180 m 2 / g.
  • FIGS. 2 to 5 show four micrographs at 300 times, 3000 times, 10,000 times and 20,000 times respectively of a catalyst used according to the invention (catalyst A) which illustrate the particular structure in juxtaposed sea urchins just to describe.
  • FIG. 6 presents a photomicrograph at nominal magnification 110,000 times of a bundle of needle-like plates of catalyst A, which clearly illustrates the typical appearance of these plates.
  • the intervals between the opposite arrows marked 1 mark the trace of platelets on the field and are an approximate measure of the thickness of these platelets.
  • the interval between the opposite arrows marked 2 marks a plate parallel to the plane of the photograph and is a measure of the average width of this plate.
  • the scale is 9 nanometers per millimeter and the dark parts correspond to the catalytic material.
  • Figures 7 to 10 show four micrographs taken at the same respective magnifications as Figures 2 to 5 and with the same apparatus, on a sample of catalyst (catalyst B) prepared using bimodal alumina beads obtained by the process patented in France under number 2 449 474: these photographs illustrate the description given in this latter patent , namely that the macroporosity results from the interparticle voids existing between spheroidal microporous particles, whose particle size distribution and the compactness of the stack determine the macroporous volume and the size of the macropores.
  • the dark areas correspond to the empty spaces of the structures of the catalysts, that is to say to the macroporosity, while the light parts correspond to the catalytic material.
  • the distribution of the diameters of the macropores of catalyst B can be measured in the photographs and it corresponds well to that which is obtained by porosimetry with mercury and which is represented in FIG. 1.
  • the comparison of the microphotographs clearly shows that the spheroidal particles microporous catalyst B do not have the sea urchin structure obtained for catalyst A used in step (a) of the invention.
  • a catalyst which can be used for stage (a) of the invention can be prepared according to the following method, without limiting the invention to this particular method of preparation:
  • Alumina agglomerates in particles of the order of 0.1 to 10 millimeters or in powdered particles in the order of 20 to 100 micrometers are themselves used as support, themselves having the above-mentioned sea urchin structure and responding substantially to the same characteristics than those of the catalyst of the invention, in particular as regards the shapes and dimensions of the wafers and agglomerates, the specific surface and the porosity.
  • the catalytic metal or metals namely at least one metal or metal compound belonging to at least one of groups V, VI and VIII (iron group) of the classification periodic, more particularly at least one of the following metals: molybdenum, tungsten, iron, vanadium, cobalt and nickel.
  • molybdenum + cobalt molybdenum + nickel, vanadium + nickel, tungsten + nickel.
  • the aforementioned metals are most often introduced in the form of precursors such as oxides, acids, salts, organic complexes, and in amounts such that the catalyst contains from 0.5 to 40% and preferably from 1 to 20% by weight of these metals expressed as oxides. These precursors are well known and: it is therefore useless to list them here. We end with optional drying and heat treatment at a temperature between 400 and 800 degrees centigrade.
  • the active alumina agglomerates used according to the present invention can be prepared from an active alumina powder having a poorly crystallized and / or amorphous structure, for example obtained according to the process described in French patent n ° 1 438,497.
  • the active alumina used is generally obtained by rapid dehydration of aluminum hydroxides such as bayerite, hydrargillite or gibbsite, nordstrandite or aluminum oxyhydroxides such as boehmite and diaspore.
  • the agglomeration of active alumina is carried out according to methods well known to those skilled in the art and, in particular, by pelleting, extrusion, bead shaping with a rotating bezel, etc.
  • this agglomeration is carried out, as is well known to those skilled in the art, by adding blowing agents to the mixture to be agglomerated.
  • blowing agents which can be used are in particular wood flour, charcoal, cellulose, starches, naphthalene and, in general, all the organic compounds capable of being eliminated by calcination.
  • the active alumina agglomerates obtained generally have the following characteristics: their loss on ignition measured by calcination at 1000 ° C. is between approximately 1 and approximately 15%, their surface specific is between about 100 and about 350 m 2 / g, their total pore volume is between about 0.45 and about 1.5 cm3 / g
  • the active alumina agglomerates are then treated in an aqueous medium consisting of a mixture of at least one acid making it possible to dissolve at least part of the alumina of the agglomerates and at least one compound providing an anion capable of forming combine with aluminum ions in solution.
  • the acid must dissolve at least 0.5% and at most 15% by weight of alumina in the agglomerates. Its concentration in the aqueous treatment medium must be less than 20% by weight and preferably between 1% and 15 % .
  • Use will preferably be made of strong acids such as nitric acid, hydrochloric acid, perchloric acid, sulfuric acid or weak acids used at a concentration such that their aqueous solution has a pH of less than about 4 .
  • the term “compound providing an anion capable of combining with aluminum ions in solution” means any compound capable of liberating in an anion A (-n) capable of forming with the cations Al (3+) products in which the atomic ratio n (A / Al) is less than or equal to 3.
  • a particular case of these compounds can be illustrated by the basic salts of general formula A12 (OH) xAy in which 0 ⁇ x ⁇ 6; ny ⁇ 6; n represents the number of charges of anion A.
  • the concentration of this compound in the aqueous treatment medium must be less than 50% by weight and preferably between 3% and 30 % .
  • the compounds capable of releasing in solution the anions chosen from the group consisting of the nitrate, chloride, sulphate, perchlorate, chloroacetate, dichloracetate, trichloroacetate, brichoacetate, bromoacetate, dibromacetate anions are preferably used, and the anions of general formula: in which R represents a radical taken from the group comprising H, CH 3 , C 2 H 5 , CH 3 CH 2 CH 2 , (CH 3 ) 2 CH.
  • the compounds capable of liberating the anion A (-n) in solution can effect this liberation, either directly for example by dissociation, or indirectly for example by hydrolysis.
  • the compounds can in particular be chosen from the group comprising: mineral or organic acids, anhydrides, organic or mineral salts, esters.
  • mineral salts there may be mentioned the alkaline or alkaline-earth salts soluble in an aqueous medium, such as those of sodium, potassium, magnesium or calcium, ammonium salts, aluminum salts, earth salts rare.
  • This treatment can be carried out either by dry impregnation of the agglomerates, or by immersion of the agglomerates in the aqueous solution consisting of the above-mentioned mixture of acid and of compound providing the desired anion.
  • dry impregnation is intended to bring the alumina agglomerates into contact with a volume of solution less than or equal to the total pore volume of the agglomerates treated.
  • mixtures of nitric and acetic acid or nitric and formic acid will be used as the aqueous medium.
  • the agglomerates thus treated are subjected simultaneously or subsequently to a treatment at a temperature between approximately 80 and approximately 250 ° C. for a period of time between approximately 5 minutes and approximately 36 hours.
  • This hydrothermal treatment does not cause any loss of alumina.
  • the operation is preferably carried out at a temperature between 120 and 220 ° C. for a period of time between 15 minutes and 18 hours.
  • This treatment constitutes a hydrothermal treatment of the active alumina agglomerates which realizes the transformation of at least part of these into boehmite.
  • This hydrothermal treatment can be carried out either under saturated vapor pressure, or under a partial vapor pressure of water at least equal to 70% of the saturated vapor pressure corresponding to the treatment temperature.
  • the concentration of the acid and of the compound in the treatment mixture and the hydrothermal treatment conditions used are such that there is no loss of alumina.
  • the increase in porosity following the treatment is therefore due to an expansion of the agglomerates during the treatment and not to a loss of alumina.
  • the agglomerates thus treated are then optionally dried at a temperature generally between approximately 100 and 200 ° C. for a period of time sufficient to remove the water which is not chemically bound.
  • the agglomerates are then subjected to thermal activation at a temperature between about 500 ° C and about 1100 ° C for a period between about 15 minutes and 24 hours.
  • Activation operations can be done in several stages. An activation will preferably be carried out at a temperature between about 550 ° C and 950 ° C.
  • the aforementioned process for the preparation of alumina agglomerates makes it possible in particular and completely unexpectedly to modify the distribution of the pore volumes according to the pore size of the untreated agglomerates. It makes it possible in particular to increase the proportion of pores between 10 and 100 nanometers, to reduce the proportion of pores less than 10 nanometers and to decrease the proportion of pores greater than 500 nanometers by modifying little the proportion of pores between 100 and 500 nanometers.
  • the alumina agglomerates thus obtained may have been thermally stabilized by rare earths, silica or alkaline earth metals.
  • step (c) of the process it has been specified above that the operation is preferably carried out using two successive beds catalysts, named above (CI) and (C 2 ).
  • the catalyst support (C 1 ) preferably consists of an alumina of low acidity, that is to say having a heat of neutralization by adsorption of ammonia at 320 ° C. of less than 40 joules (and preferably less than 30 joules) per gram of alumina, under an ammonia pressure of 0.4 bars.
  • This alumina support has an area of 50 to 300 m 2 / g and preferably 40 to 150 m 2 / g, as well as a pore volume generally between 0.4 and 1.3 cm 3 / g .
  • the aluminas which have undergone autoclaving under steam pressure can be cited.
  • the catalyst (C 2 ) used in the second catalytic bed will preferably be incorporated on a support having a more acidic character than the support of the catalyst (C l ): its acidity, determined as above by adsorption of ammonia, will preferably be greater than 30 joules / g. Its surface is preferably between 150 and 350 m 2 / g, and its pore volume preferably between 0.4 and 1 cm3 / g. Mention may be made, as supports meeting these characteristics of alumina y ex boehmite or n ex bayerite, or else supports of the alumina / magnesia or silica / magnesia type containing approximately 5 to 10% by weight of magnesia.
  • steps (a) and (c) of the process are conventional. These catalysts work mainly, during operation, in sulfurized form; their sulfurization may be prior to the treatment of the load or result from the passage of the latter.
  • active metals for example Mo, W, Ni, Co, Fe
  • a mixture of asphaltic heavy oil and hydrogen is sent by line 1 to the catalytic hydrodemetallization reactor 2, then by line 3 to the water reduction reduction reactor 4.
  • the effluent is sent by line 5 preferably in the presence a supply of hvdroqene supplied by line 6 to the line in the presence of a supply of hydrogen supplied by line 6 to the reactor 7 containing a first bed of catalyst 8 and a second bed of catalyst 9.
  • the final product is drawn off by line 10.
  • the fillers which can be treated according to the invention are, for example, crude oils, vacuum residues, atmospheric residues, shale oil or oil sands oils or asphalts. Oils most often have a density greater than: ( ) 0.965, an API degree less than 15.1, an asphaltenes content (determined with n-heptane) greater than 5% by weight, a metal content (Ni + V) greater than 200 ppm by weight and a higher viscosity at 50 cSt (50 mm 2 / s) at 100 ° C.
  • FIG. 2 to 5 show photomicrographs of catalyst A taken using a JEOL brand scanning electron microscope, model JSM 35 CF, at respective magnifications 300, 3,000, 10,000 and 20,000.
  • the scales indicated on each photograph measure the dimensions of observable details.
  • the dark parts correspond to the porosity, while the light parts correspond to the catalytic material.
  • catalyst A does indeed have the "sea urchin" structure according to the invention, namely a juxtaposition of agglomerates having for the most part an average dimension of 3.5 micrometers, each agglomerate being formed of elongated needle-like plates, generally assembled radially with respect to the center of the agglomerates.
  • the dimensions of the acicular plates are measurable in particular in FIG.
  • FIG. 1 shows in particular the cumulative porous distribution curve of catalyst A.
  • This catalyst is a commercial catalyst sold by the French company PRO-CATALYSE under the name LD 145.
  • Its support is of the alumina y type, having a specific surface of 210 m 2 / g, the pore volume being 0.52 cm 3 / g; this support has a heat of neutralization by adsorption of NH 3 of 40 joules / g.
  • This catalyst is a commercial catalyst sold by the French company PRO-CATALYSE under the name HR 306.
  • the weight ratio of catalyst from the 2nd bed to the 1st bed is therefore 4.
  • the temperature in the reactor is between 370 and 400 ° C, the pressure being 140 bars.
  • the hourly flow rate of liquid charge is 0.5 m 3 / m 3 / h, the quantity of hydrogen relative to the charge is 1,200 Nm 3 / m 3 .
  • the process therefore made it possible to transform a heavy, viscous crude, non-transportable, with a high content of impurities, into a stable synthetic crude, easily transportable, with a low content of impurities.
  • the service life of the catalysts is exceptional, given the nature of the charge. The test was stopped after 2300 hours, while the activity of the catalyst in step (a) still represented 50 % of the initial activity. The retention power of this catalyst is exceptional (130 g of fixed metals per 100 g of fresh catalyst).

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
EP83402494A 1982-12-30 1983-12-21 Behandlung von Schwerölen oder Schwerölfraktionen zur Umwandlung in leichtere Fraktionen Expired EP0113283B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8222209 1982-12-30
FR8222209A FR2538811A1 (fr) 1982-12-30 1982-12-30 Procede de traitement d'une huile lourde ou d'une fraction d'huile lourde pour les convertir en fractions plus legeres

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EP0113283A1 true EP0113283A1 (de) 1984-07-11
EP0113283B1 EP0113283B1 (de) 1987-05-13

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US (1) US4511458A (de)
EP (1) EP0113283B1 (de)
JP (1) JPS59166589A (de)
CA (1) CA1226842A (de)
DE (1) DE3371535D1 (de)
FR (1) FR2538811A1 (de)
ZA (1) ZA839686B (de)

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EP0219080A2 (de) * 1985-10-15 1987-04-22 Hoechst Aktiengesellschaft Wasserlösliche Disazoverbindungen, Verfahren zu deren Herstellung und ihre Verwendung als Farbstoffe
EP0537500A2 (de) * 1991-10-09 1993-04-21 Idemitsu Kosan Company Limited Methode zur Behandlung eines schweren Kohlenwasserstofföls
EP0584369A1 (de) * 1992-02-21 1994-03-02 Idemitsu Kosan Company Limited Verfahren zur hydrobehandlung von schwerem kohlenwasserstofföl

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US4626340A (en) * 1985-09-26 1986-12-02 Intevep, S.A. Process for the conversion of heavy hydrocarbon feedstocks characterized by high molecular weight, low reactivity and high metal contents
US5024750A (en) * 1989-12-26 1991-06-18 Phillips Petroleum Company Process for converting heavy hydrocarbon oil
US6569318B2 (en) * 2000-02-23 2003-05-27 Institut Francais Du Petrole Process for conversion of hydrocarbons on a catalyst with controlled acidity
JP4537713B2 (ja) * 2002-02-06 2010-09-08 株式会社ジャパンエナジー 水素化精製触媒の製造方法
US7095867B2 (en) * 2004-04-30 2006-08-22 Altec Lansing Technologies, Inc. Portable audio reproduction system
WO2009073436A2 (en) 2007-11-28 2009-06-11 Saudi Arabian Oil Company Process for catalytic hydrotreating of sour crude oils
US8372267B2 (en) 2008-07-14 2013-02-12 Saudi Arabian Oil Company Process for the sequential hydroconversion and hydrodesulfurization of whole crude oil
US9260671B2 (en) 2008-07-14 2016-02-16 Saudi Arabian Oil Company Process for the treatment of heavy oils using light hydrocarbon components as a diluent
US8480881B2 (en) 2009-06-11 2013-07-09 Board Of Regents, The University Of Texas System Synthesis of acidic silica to upgrade heavy feeds
EP2445997B1 (de) 2009-06-22 2021-03-24 Saudi Arabian Oil Company Entmetallisierung und entschwefelung rohes erdöl zur delayed coking
CN111097547A (zh) * 2018-10-26 2020-05-05 中国石油化工股份有限公司 渣油加氢处理催化剂载体、催化剂及其制备方法
CN111100676A (zh) * 2018-10-26 2020-05-05 中国石油化工股份有限公司 一种催化剂级配方法及其在渣油加氢处理方法中的应用
CN111100678A (zh) * 2018-10-26 2020-05-05 中国石油化工股份有限公司 一种利用上流式反应器加氢处理渣油的方法

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Publication number Priority date Publication date Assignee Title
US3730875A (en) * 1971-02-16 1973-05-01 Universal Oil Prod Co Combination process for black oil conversion
FR2268860A1 (de) * 1974-04-24 1975-11-21 Inst Francais Du Petrole
FR2277140A1 (fr) * 1974-07-04 1976-01-30 Leuna Werke Veb Procede de fabrication de fuels ainsi que de distillats moyens et d'essences pauvres en soufre a partir de residus de la distillation du petrole
DE3020518A1 (de) * 1980-05-30 1981-12-10 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur aufarbeitung von schweren, asphalten- und gegebenenfalls auch hochmetallhaltigen kohlenwasserstoff-oelen
EP0055164A1 (de) * 1980-12-23 1982-06-30 Rhone-Poulenc Specialites Chimiques Verfahren zur Herstellung von Aluminiumoxyd-Agglomeraten
FR2508898A1 (fr) * 1981-07-03 1983-01-07 Inst Francais Du Petrole Procede de conversion de coupes riches en hydrocarbures polyaromatiques en methane, ethane et eventuellement benzene
FR2516932A1 (fr) * 1981-11-24 1983-05-27 Inst Francais Du Petrole Procede de conversion d'huiles lourdes ou de residus petroliers en hydrocarbures gazeux et distillables
FR2528721A1 (fr) * 1982-06-17 1983-12-23 Pro Catalyse Ste Fse Prod Cata Catalyseur supporte presentant une resistance accrue aux poisons et son utilisation en particulier pour l'hydrotraitement de fractions petrolieres contenant des metaux

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0219080A2 (de) * 1985-10-15 1987-04-22 Hoechst Aktiengesellschaft Wasserlösliche Disazoverbindungen, Verfahren zu deren Herstellung und ihre Verwendung als Farbstoffe
EP0219080A3 (en) * 1985-10-15 1987-10-14 Hoechst Aktiengesellschaft Water soluble disazo compounds, process for their preparation and their use as dyestuffs
EP0537500A2 (de) * 1991-10-09 1993-04-21 Idemitsu Kosan Company Limited Methode zur Behandlung eines schweren Kohlenwasserstofföls
EP0537500A3 (en) * 1991-10-09 1993-05-12 Idemitsu Kosan Company Limited A method of treatment of heavy hydrocarbon oil
US5382349A (en) * 1991-10-09 1995-01-17 Idemitsu Kosan Co., Ltd. Method of treatment of heavy hydrocarbon oil
SG91789A1 (en) * 1991-10-09 2002-10-15 Idemitsu Kosan Co A method of treatment of heavy hydrocarbon oil
EP0584369A1 (de) * 1992-02-21 1994-03-02 Idemitsu Kosan Company Limited Verfahren zur hydrobehandlung von schwerem kohlenwasserstofföl
EP0584369A4 (en) * 1992-02-21 1994-06-29 Idemitsu Kosan Co Process for hydrotreating heavy hydrocarbon oil
US5376258A (en) * 1992-02-21 1994-12-27 Idemitsu Kosan Co., Ltd. Process for hydrogenating treatment of heavy hydrocarbon oil

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ZA839686B (en) 1985-08-28
EP0113283B1 (de) 1987-05-13
CA1226842A (fr) 1987-09-15
US4511458A (en) 1985-04-16
FR2538811B1 (de) 1985-03-15
JPS59166589A (ja) 1984-09-19
DE3371535D1 (en) 1987-06-19
FR2538811A1 (fr) 1984-07-06

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