EP0233116B1 - Katalytisches Reformierverfahren mit wenigstens zwei Katalysatorbetten - Google Patents

Katalytisches Reformierverfahren mit wenigstens zwei Katalysatorbetten Download PDF

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Publication number
EP0233116B1
EP0233116B1 EP87400221A EP87400221A EP0233116B1 EP 0233116 B1 EP0233116 B1 EP 0233116B1 EP 87400221 A EP87400221 A EP 87400221A EP 87400221 A EP87400221 A EP 87400221A EP 0233116 B1 EP0233116 B1 EP 0233116B1
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EP
European Patent Office
Prior art keywords
catalyst
platinum
metal
carrier
process according
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Expired
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EP87400221A
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English (en)
French (fr)
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EP0233116A1 (de
Inventor
Jean-Pierre Franck
Jean-Paul Bournonville
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
    • C10G35/09—Bimetallic catalysts in which at least one of the metals is a platinum group metal
    • 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
    • C10G59/00—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha
    • C10G59/02—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha plural serial stages only

Definitions

  • alumina catalysts containing, in addition to a noble metal from group VIII (generally platinum), a promoter metal which is known rhenium (US-A-3,415,737).
  • a noble metal from group VIII generally platinum
  • a promoter metal which is known rhenium
  • Other types of catalyst are also known based on a noble metal from group VIII (generally platinum) and containing as promoter metal, for example tin, lead, indium or thallium ( US-A-3,700,588, US-A-2,814,599).
  • platinum-rhenium catalyst has excellent stability but does not allow maximum selectivity to be observed. in obtaining good quality essences.
  • platinum-tin, or platinum-indium or platinum-thallium catalysts make it possible to obtain excellent selectivity, but the stability of these catalysts leaves something to be desired.
  • FR-A-2 163 683 describes a reforming process in which the charge passes successively through at least two reforming zones, which process is characterized in that the catalyst of the second zone comprises a small proportion of gallium, introduced for example into the using a gallium nitrate solution.
  • the catalysts can be arranged in one or more fixed beds, or in mobile beds, or in turbulent beds.
  • EP-A-153-891 describes a catalytic reforming process in which the hydrocarbon charge successively passes through at least two fixed beds of catalysts.
  • the catalyst of the first bed traversed by the charge contains a support based on alumina, platinum, thenium.
  • the catalysts of the other beds each contain a support based on alumina, platinum, at least one promoter metal chosen from the group consisting of tin, thallium and indium. The preparation of the catalysts is not described in this document.
  • FR-A-2 545 480 relates to a process for the production of hydrocarbon conversion catalysts, in particular reforming catalysts, containing a support, at least one noble metal of the platinum family, at least one additional metal chosen from tin, germanium and lead.
  • the additional metal is introduced onto the support in the form of at least one organic compound, in particular in solution in a hydrocarbon solvent.
  • the object of the invention is an improved process for the catalytic reforming of hydrocarbons which makes it possible to obtain quality gasolines for long periods (therefore with good stability) and with very satisfactory selectivity.
  • This process consists in circulating the hydrocarbon charge under reforming conditions, in contact with a first catalyst then a second catalyst and then in collecting the reforming product; in this process said first catalyst, arranged in at least one fixed bed, comprises (a) a support, (b) at least one noble metal of the family of platinum, one.
  • said second catalyst different from the first catalyst and arranged in at least one moving bed, contains (a) a support, (b ) at least one noble metal from the platinum family, at least one of these noble metals being platinum, (c) at least one additional metal M chosen from the group consisting of tin, gallium, germanium, indium, lead and thallium and (d) at least one halogen; said metal M having been introduced onto the support using a solution in an organic solvent of at least one organic compound chosen from the group consisting of hydrocarbylmetals, halohydrocarbylmetals and polyketonic complexes of said metal M and the proportion by weight said second catalyst generally being from 25 to 5% relative to the total catalytic mass.
  • the charge of hydrocarbons will successively pass through at least two separate beds of said first catalyst, the catalytic mass of all of these beds of said first catalyst, representing from 45 to 75% by weight of the total mass catalytic used in all catalytic beds.
  • the arrangement according to the present invention in which the first catalyst operates at low severity (research octane number (NOR) of the product obtained at the outlet of the first bed and preferably in two first beds from 85 to 95 and more particularly from 87 to 92) and in which the second catalyst is placed in a reactor with continuous regeneration of the catalyst and operates at high severity, makes it possible to obtain a final reformate having a high NOR, in general greater than 95 and in the majority of cases greater to 98.
  • NOR search octane number
  • All of the reactors preferably operate at low pressure so as to take advantage of the efficiency gains that can be expected when operating at low pressure.
  • the pressure is generally from 0.5 to 2.5 MPa and more advantageously from 0.7 to 1.2 MPa.
  • the first catalyst then represents from 45 to 75% by weight and preferably from 45 to 60% by weight relative to the total catalytic mass used in all of the catalytic beds; this first catalyst is preferably distributed in at least two separate beds, the first bed generally representing approximately 15 to 25% by weight and preferably around 15 to 20% relative to the total catalytic mass used in all of the catalytic beds and the second bed generally representing, relative to this same total mass, about 30 to 50% by weight and preferably about 30 to 40% by weight.
  • the various arrangements of catalytic beds known to those skilled in the art can be envisaged; one of the essential points being that the hydrocarbon charge passes through at least one bed and preferably at least two successive beds of the first catalyst containing platinum and rhenium.
  • the first bed through which the charge passes will most advantageously be a fixed bed of the first catalyst containing platinum and rhenium, and preferably the first two beds will be fixed beds.
  • alumina As support for the catalysts, it is generally preferred to use alumina as support for the catalysts.
  • the alumina used may be of any variety, but cubic or eta gamma alumina will generally be used or a mixture of these two varieties.
  • the same support will be used for the first and for the second catalyst and preferably alumina of cubic gamma variety will be chosen.
  • the second catalyst used in the context of the present invention will advantageously contain in addition to platinum, another noble metal from group VIII and preferably iridium.
  • the amount of iridium will advantageously be less than 0.5% by weight relative to the support and generally from 0.005 to 0.3%.
  • a second supported catalyst containing in addition to a halogen the following metal associations: platinum-tin, platinum-gallium, platinum -germanium, platinum-indium, platinum-lead, platinum-thallium, platinum-indium-tin, platinum-iridium-germanium, platinum-iridium-indium, platinum-iridium-lead, platinum-iridium-tin.
  • catalysts containing the platinum-tin, platinum-indium, platinum-germanium, platinum-lead and platinum-iridium-indium associations will be used.
  • the most preferred combinations are platinum-tin, platinum-indium and platinum-iridium-indium.
  • the catalytic reforming catalysts employed in the present invention are generally prepared according to conventional methods consisting in impregnating the support by means of solutions of compounds of the metals which it is desired to introduce. Either a common solution of these metals is used, or separate solutions for each metal.
  • intermediate drying and / or calcination can be carried out. It usually ends with a calcination, for example between about 450 and 1000 ° C., preferably in the presence of free oxygen, for example by carrying out an air sweep.
  • Platinum and possibly another noble metal of the platinum family
  • Platinum is generally introduced into the support in the form of chloroplatinic acid or in the form of organic platinum compounds in particular.
  • organic platinum compounds in the form of polyketonic complexes of platinum, for example of platinum acetylacetonate, of halogeno polyketonic complexes of platinum, of amine complexes of platinum, of haloamino complexes of platinum and of the salts of these compounds.
  • organic platinum compounds may be used to introduce this metal onto the support for the second catalyst.
  • the rhenium can be incorporated into the support by impregnation of this support using an adequate aqueous solution containing a salt or a rhenium compound.
  • the two preferred precursors are ammonium perrhenate and perrhenic acid.
  • the halogen of the catalyst can come from one of the metal halides, if at least one of the metals is introduced by means of a halide, or can be introduced in the form of hydrohalic acid, ammonium halide, halogen gas, or halogenated organic compounds.
  • the halogen will preferably be chlorine or fluorine.
  • Examples of compounds which can be used to introduce halogen include hydrochloric acid, hydrofluoric acid, ammonium chloride and fluoride, chlorine gas, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dihloromethane, 1,2-dichloroethane and 1,1-dichloroethane.
  • the additional metal or promoter M is introduced into the support of the second catalyst by means of a solution in an organic solvent of an organic compound of this metal chosen from the group consisting of hydrocarbylmetals, hanohydrocarbylmetals and polyketonic metal complexes.
  • Organohalogenated compounds of the metals M can also be used.
  • tetrabutyltin tetramethyltin, diphenyltin, triethylgallium, gallium acetylacetonate, trimethylindium, indium acetylacetonate, tetrapropyl germanium, diphenylgermanium, tetraethyl lead. tetraphenyl lead, triethylthallium, cyclopentadienylthallium.
  • the impregnating solvent is generally chosen from the group consisting of paraffinic, naphthenic or aromatic hydrocarbons containing from 6 to 12 carbon atoms per molecule and by halogenated hydrocarbons having from 1 to 12 atoms per molecule.
  • organic solvents examples include n-heptane, methylcyclohexane, toluene and chloroform. It is also possible to use mixtures of the solvents defined above.
  • the catalysts used in the context of the present invention are preferably at the end of their preparation calcined at a temperature of approximately 450 to 1000 ° C. and can advantageously undergo before their use, before their introduction into the reactors or in-situ an activation treatment under hydrogen at high temperature, for example 300 to 500 ° C.
  • the procedure for this treatment under hydrogen consists, for example, of a slow rise in temperature under a stream of hydrogen up to the maximum reduction temperature chosen, for example between 300 and approximately 500 ° C. and preferably approximately 350 to 480 ° C, followed by holding for about 1 to about 6 hours at this temperature.
  • the reforming operations are started by adjusting, under the operational conditions, the hydrogen and supply flow rates as well as the temperature and the pressure.
  • the general conditions of reforming are well known to those skilled in the art, generally the catalytic reforming is carried out at a temperature of 400 to 600 ° C., under an absolute pressure of 0.1 to 3.5 MPa, with an hourly speed (VVH) of 0.1 to 10 volumes of feed per volume of catalyst and per hour, and a ratio molar hydrogen / hydrocarbons (H 2 / HC) of 1. 1 to 20: 1.
  • the preferred conditions are: temperature 460 to 580 ° C, pressure 0.5 to 2.5 MPa and more advantageously 0.7 to 1.2 MPa, VVH from 1 to 10 and more advantageously from 1 to 6 and H a / HC from 2: 1 to 10: 1.
  • the hydrocarbon charge is generally a naphtha distilling between about 60 ° C and about 220 ° C, in particular a direct distillation naphtha.
  • the charge flows successively through 3 reactors in series.
  • the first two reactors each containing a fixed bed of catalyst A and the third reactor with continuous regeneration of the catalyst contains a movable bed of type B catalyst.
  • Catalyst A represents 50% by weight of the total quantities of catalyst used in the three reactors (catalyst B therefore representing 50% by weight of the total catalytic mass).
  • B 1 comparative catalyst not according to the invention
  • B 2 tin is introduced in accordance with the invention from tetrabutyltin in solution in n-heptane.
  • the operation is carried out for 300 hours for the arrangement of catalyst A - catalyst B 1 .
  • Catalyst A does not undergo any regeneration.
  • the catalyst B 1 used in the form of a moving bed, is withdrawn continuously from the reactor which contains it with a speed calculated so as to be completely withdrawn, regenerated and reintroduced continuously in the third reactor in 300 hours.
  • the association of catalysts AB 1 has for 300 hours a relative stability equal to 1 and a regeneration frequency equal to 1.
  • the stability criterion adopted is the time after which the yield of C 5 + expressed in% by weight relative to the charge decreased by 2% compared to its initial value.
  • Example 1 is repeated (combination of catalyst A and catalyst B 2 ) but catalyst A represents only 20% by weight of the total quantities of catalyst used in the three reactors (catalyst B 2 therefore representing 80% by weight of the total catalytic mass).
  • Catalyst A is loaded into a fixed bed in the first reactor and catalyst B 2 is distributed in the following two reactors operating with continuous regeneration of the catalyst, each reactor containing a moving bed of catalyst B 2 .
  • Example 1 is repeated (combination of catalyst A and B 2 ) but the third reactor is loaded in a fixed bed with catalyst B 2 ). The test is continued as long as the loss of yield in C 5 + does not exceed 2% relative to its initial value, which causes the test to stop after 180 hours of operation.
  • Example 1 is repeated, replacing the catalysts B 1 and B 2 respectively with the catalysts Ci and. C 2 and by the catalysts D 1 and D 2 containing the same support and the compositions of which are specified in Table 2 below.
  • Example 1 shows a slight superiority of the process when the catalyst of the third reactor contains platinum and tin compared to the case where it contains platinum. and germanium and platinum and lead.
  • the catalyst E 1 is prepared from indium nitrate and the catalyst E 2 from indium acetylacetonate.
  • the use in the third reactor of a catalyst into which indium has been introduced using an organometallic compound therefore makes it possible to obtain an activity and a selectivity higher than those obtained when used in the third reactor.
  • a catalyst into which indium has been introduced using a mineral compound therefore makes it possible to obtain an activity and a selectivity higher than those obtained when used in the third reactor.

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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)

Claims (9)

1. Verfahren zum katalytischen Reformieren, bei dem man eine Kohlenwasserstoffcharge unter Reformierungsbedingungen in Kontakt mit einem ersten Katalysator, dann einem zweiten Katalysator strömen läßt und dann das Reformierungsprodukt sammelt, dadurch gekennzeichnet, daß der in wenigstens einem festen Bett angeordnete Katalysator umfaßt: (a) einen Träger, (b) wenigstens ein Edelmetall der Platinfamilie, wobei wenigstens eines dieser Edelmetalle Platin ist, (c) Rhenium und (d) wenigstens ein Halogen und daß der zweite Katalysator, der sich vom ersten Katalysator unterscheidet und in wenigstens einem beweglichen Bett angeordnet ist, umfaßt: (a) einen Träger, (b) wenigstens ein Edelmetall der Plaünfamilie, wobei wenigstens eines dieser Edelmetalle Platin ist, (c) wenigstens ein zusätzliches Metall M, welches gewählt ist aus der Gruppe, die gebildet wird durch Zinn, Gallium, Germanium, Indium, Blei und Thallium sowie (d) wenigstens ein Halogen, wobei dieses Metall M auf den Träger mit Hilfe einer Lösung in einem organischen Lösungsmittel wenigstens einer organischen Verbindung eingeführt wird, die gewählt ist aus der Gruppen, die besteht aus den Kohlenwasserstoffmetallen, den Halogenkohlenwasserstoffmetallen und den Polyketonkomplexen dieses Metalls M und wobei der Gewichtsanteil dieses zweiten Katalysators 25 bis 55 % bezogen auf die gesamte katalytische Masse ist.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Charge nacheinander wenigstens zwei unterschiedliche Betten dieses ersten Katalysators durchsetzt.
3. Verfahren nach einem der Ansprüche 1 und 2, bei dem der zweite Katalysator Platin, Iridium und wenigstens ein zusätzliches Metall M umfaßt.
4. Verfahren nach einem der Ansprüche 1 bis 3, bei dem der zweite Katalysator dadurch erhalten wird, daß auf den Träger Platin mit Hilfe wenigstens einer organischen Verbindung des Platins gegeben wird.
5. Verfahren nach einem der Ansprüche 1 bis 4, bei dem das Zusatzmetall M des zweiten Katalysators gewählt ist aus der Gruppe, die gebildet wird durch Zinn, Indium, Germanium und Blei. ,
6. Verfahren nach einem der Ansprüche 1 bis 5, bei dem das Zusatzmetall M des zweiten Katalysators gewählt ist aus der Gruppe, die aus Zinn und Indium gebildet wird.
7. Verfahren nach einem der Ansprüche 1 bis 6, bei dem der erste Katalysator, bezogen auf den Träger, zwischen 0,01 bis 2 Gew: % wenigstens eines Edelmetalls der Platinfamilie, zwischen 0,005 bis 3 Gew.-% Rhenium und zwischen 0,1 bis 15 Gew.-% wenigstens eines Halogens einschließt.
8. Verfahren nach einem der Ansprüche 1 bis 7, bei dem der zweite Katalysator, bezogen auf den Träger zwischen 0,01 und 2 Gew.-% wenigstens eines Edelmetalls der Platinfamilie, zwischen 0,005 bis 3 Gew.-% wenigstens eines Zusatzmetalls M und zwischen 0,1 und 15 Gew.-% wenigstens eines Halogens einschließt.
9. Verfahren nach einem der Ansprüche 1 bis 8, bei dem der Träger des ersten und des zweiten Katalysators ein Träger auf der Basis von Aluminiumoxid ist.
EP87400221A 1986-02-03 1987-01-30 Katalytisches Reformierverfahren mit wenigstens zwei Katalysatorbetten Expired EP0233116B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8601551 1986-02-03
FR8601551A FR2593824B1 (fr) 1986-02-03 1986-02-03 Procede de reformage catalytique a travers au moins trois lits de catalyseur

Publications (2)

Publication Number Publication Date
EP0233116A1 EP0233116A1 (de) 1987-08-19
EP0233116B1 true EP0233116B1 (de) 1989-08-09

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US (1) US4737262A (de)
EP (1) EP0233116B1 (de)
JP (1) JP2544917B2 (de)
CA (1) CA1293467C (de)
DE (1) DE3760424D1 (de)
ES (1) ES2011050B3 (de)
FR (1) FR2593824B1 (de)
GR (1) GR3000138T3 (de)

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US4935566A (en) * 1987-11-17 1990-06-19 Mobil Oil Corporation Dehydrocyclization and reforming process
EP0393099B1 (de) * 1987-11-17 1994-02-23 Mobil Oil Corporation Dehydrogenierungskatalysator und dessen verwendung
US4985132A (en) * 1989-02-06 1991-01-15 Uop Multizone catalytic reforming process
US4929333A (en) * 1989-02-06 1990-05-29 Uop Multizone catalytic reforming process
US4929332A (en) * 1989-02-06 1990-05-29 Uop Multizone catalytic reforming process
US5221465A (en) * 1990-12-14 1993-06-22 Exxon Research And Engineering Company High activity, high yield tin modified platinum-iridium catalysts, and reforming process utilizing such catalysts
US5269907A (en) * 1990-12-14 1993-12-14 Exxon Research And Engineering Co. Process for reforming at low severities with high-activity, high-yield, tin modified platinum-iridium catalysts
CA2055929A1 (en) * 1990-12-14 1992-06-15 William C. Baird, Jr. Process for reforming at low severities with high activity, high yield tin modified platinum-iridium catalysts
US5106809A (en) * 1990-12-14 1992-04-21 Exxon Research And Engineering Company High activity, high yield tin modified platinum-iridium catalysts, and reforming process utilizing such catalysts
US5203988A (en) * 1991-08-19 1993-04-20 Exxon Research & Engineering Company Multistage reforming with ultra-low pressure cyclic second stage
US5190638A (en) * 1991-12-09 1993-03-02 Exxon Research And Engineering Company Moving bed/fixed bed two stage catalytic reforming
US5190639A (en) * 1991-12-09 1993-03-02 Exxon Research And Engineering Company Multiple fixed-bed reforming units sharing common moving bed reactor
US5211838A (en) * 1991-12-09 1993-05-18 Exxon Research & Engineering Company Fixed-bed/moving-bed two stage catalytic reforming with interstage aromatics removal
US5196110A (en) * 1991-12-09 1993-03-23 Exxon Research And Engineering Company Hydrogen recycle between stages of two stage fixed-bed/moving-bed unit
DE69229875T2 (de) * 1991-12-09 2000-04-20 Exxon Research Engineering Co Reformierung mit zwei festbetteinheiten; jede mit einem wanderbettendreaktor, die einen gemeinsamen regenerator teilen
US5354451A (en) * 1991-12-09 1994-10-11 Exxon Research And Engineering Company Fixed-bed/moving-bed two stage catalytic reforming
FR2704864B1 (fr) 1993-05-06 1995-11-17 Inst Francais Du Petrole Procede d'hydroreformage catalytique.
FR2735487B1 (fr) * 1995-06-16 1997-08-22 Inst Francais Du Petrole Procede de transformation catalytique d'hydrocarbures en composes aromatiques avec un catalyseur contenant des metaux alcalins ou alcalino-terreux
US5858205A (en) * 1997-05-13 1999-01-12 Uop Llc Multizone catalytic reforming process
FR2770521B1 (fr) * 1997-10-31 1999-12-10 Inst Francais Du Petrole Procede de deshydrogenation d'hydrocarbures aliphatiques satures en hydrocarbures olefiniques
FR2770520B1 (fr) * 1997-10-31 1999-12-10 Inst Francais Du Petrole Procede d'hydrogenation selective des composes insatures
FR2770421B1 (fr) * 1997-10-31 1999-12-10 Inst Francais Du Petrole Procede de preparation de catalyseurs utilisables dans les reactions de transformation de composes organiques
FR2770535B1 (fr) * 1997-10-31 1999-12-10 Inst Francais Du Petrole Procede d'hydroreformage catalytique
US6190534B1 (en) * 1999-03-15 2001-02-20 Uop Llc Naphtha upgrading by combined olefin forming and aromatization
US6406614B1 (en) 1999-12-22 2002-06-18 Phillips Petroleum Company Method for zeolite platinization
US7267987B2 (en) * 2003-01-06 2007-09-11 Uop Llc Process and assembly for simultaneously evaluating a plurality of catalysts
US7803326B2 (en) * 2007-08-01 2010-09-28 Uop Llc Hydrocarbon conversion unit including a reaction zone receiving transferred catalyst
US7811447B2 (en) * 2007-08-01 2010-10-12 Uop Llc Method of transferring particles from one pressure zone to another pressure zone
US7799729B2 (en) * 2009-02-23 2010-09-21 Uop Llc Reforming catalyst
EP2725094A1 (de) 2012-10-29 2014-04-30 Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO Epithelgewebemodell

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FR2560205B1 (fr) * 1984-02-23 1988-07-15 Inst Francais Du Petrole Procede de reformage catalytique

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Publication number Publication date
US4737262A (en) 1988-04-12
FR2593824B1 (fr) 1988-11-04
EP0233116A1 (de) 1987-08-19
GR3000138T3 (en) 1990-11-29
FR2593824A1 (fr) 1987-08-07
JP2544917B2 (ja) 1996-10-16
CA1293467C (fr) 1991-12-24
ES2011050B3 (es) 1989-12-16
JPS62192488A (ja) 1987-08-24
DE3760424D1 (en) 1989-09-14

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