EP0388325A1 - Process for improving the cetane number of straight new gasoils - Google Patents

Process for improving the cetane number of straight new gasoils Download PDF

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Publication number
EP0388325A1
EP0388325A1 EP19900420120 EP90420120A EP0388325A1 EP 0388325 A1 EP0388325 A1 EP 0388325A1 EP 19900420120 EP19900420120 EP 19900420120 EP 90420120 A EP90420120 A EP 90420120A EP 0388325 A1 EP0388325 A1 EP 0388325A1
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EP
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Prior art keywords
hydrogen peroxide
acid
carboxylic acid
cetane number
diesel
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EP19900420120
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German (de)
French (fr)
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EP0388325B1 (en
Inventor
Bernard Dubreux
Jacques Kervennal
Philippe Mulard
Michèle Pralus
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Arkema France SA
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Elf Atochem SA
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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
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
    • C10G27/12—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B3/00—Engines characterised by air compression and subsequent fuel addition
    • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B47/00—Methods of operating engines involving adding non-fuel substances or anti-knock agents to combustion air, fuel, or fuel-air mixtures of engines

Definitions

  • the present invention relates to a method for improving the cetane number of direct distillation gas oils.
  • Direct distillation diesel or direct diesel or even diesel itself is the middle distillate, intermediate between light distillates, gas and petrol, aviation fuels on the one hand and heavy residue on the other hand, in distillation at atmospheric pressure which begins the refining of crude oils.
  • the composition like the properties of a direct diesel, differentiate it in a known manner from the visbreaking or catalytic cracking diesel obtained after the vacuum distillation of the above heavy residue.
  • the distillation interval at atmospheric pressure of a direct diesel oil generally ranges between approximately 150 ° C, 200 ° C on the one hand and 350 ° C, 450 ° C on the other hand.
  • Direct gas oils are mainly used to supply diesel engines and domestic heating.
  • Direct gas oils with improved cetane number according to the present invention may give rise to marketing as is or otherwise serve to raise the cetane number of gas oils with a lower cetane number.
  • the process according to the invention for improving the cetane number of a direct distillation diesel is characterized in that said diesel is brought into contact either with hydrogen peroxide in the presence of a carboxylic acid, or with an acid percarboxylic in the presence or not of hydrogen peroxide.
  • the quantity of hydrogen peroxide used per kilogram of direct diesel fuel is, for safety and economic reasons, less than 300 g. ; most often said quantity which makes it possible to achieve the desired result does not exceed 50 g. about.
  • the carboxylic acid is in practice chosen from formic acid, acetic acid and propionic acid; formic acid is preferred.
  • the molar ratio of carboxylic acid / hydrogen peroxide is preferably between approximately 0.01 and 1, and better still, between approximately 0.1 and 0.5, the temperature at which the contact according to the invention is made is most often between approximately 50 ° C.
  • the hydrogen peroxide can be used in the form of an aqueous solution containing for example, and most often between about 50% and 70% by weight of hydrogen peroxide, the duration of the contact according to the invention depends on the other parameters chosen; it is preferably sufficient, combined with these other parameters, to ensure the most complete possible disappearance of the engaged peroxide.
  • the contacting is carried out with stirring in a reactor resistant to acid corrosion and essentially provided with an effective stirring system, heating means, measurement and temperature control.
  • the percarboxylic acid is chosen in practice from performic acid, peracetic acid and perpropionic acid, and manufactured in a known manner, for example as regards perpropionic acid, according to the methods described in the applications French patent published under the numbers 2460927 and 2464947.
  • the percarboxylic acid acts in the absence of hydrogen peroxide, it is used in the same molar quantities as the hydrogen peroxide in the first embodiment of the invention described above, - If the percarboxylic acid acts in the presence of hydrogen peroxide, the cumulative molar amounts of percarboxylic acid and hydrogen peroxide are the same as those of hydrogen peroxide used according to the first embodiment of the invention . - The conditions of temperature, duration and other production parameters are the same as in the first embodiment of the invention.
  • the process of the invention is suitable for direct gas oils before or after desulfurization, for example hydrodesulfurization, which reduces their sulfur content to a value corresponding to or lower than that required by their applications. It applies for example to direct diesel ready to be used as engine diesel.
  • cetane number is measured according to standard ASTM D-613.
  • the organic phase which is then separated by decantation from the mixture, which is left to stand and cooled, is washed so that the hydrogen peroxide and formic acid which may remain in the gas oil after treatment are removed from it. Washing is most commonly done using water.
  • the cetane number of the direct distillation starting diesel oil is equal to 58. That of direct diesel after application of the process according to the invention is 64.

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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)
  • Fats And Perfumes (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Improvement in the cetane number of straight distillation gas oils by bringing the said gas oils into contact either with hydrogen peroxide in the presence of a carboxylic acid or with a percarboxylic acid in the presence or absence of hydrogen peroxide.

Description

La présente invention concerne un procédé d'amélio­ration de l'indice de cétane des gazoles de distillation directe.The present invention relates to a method for improving the cetane number of direct distillation gas oils.

Le gazole de distillation directe ou gazole direct ou encore gazole proprement dit est le distillat moyen, intermédiaire entre les distillats légers, gaz et essences, carburants pour aviation d'une part et le résidu lourd d'autre part, dans la distillation à pression atmosphérique par laquelle débute le raffinage des pétroles bruts. La composition comme les propriétés d'un gazole direct le différencient de façon connue des gazoles de viscoréduction ou de craquage catalytique obtenus après la distillation sous vide du résidu lourd ci-dessus. L'intervalle de distillation à pression atmosphérique d'un gazole direct s'étend le plus souvent entre environ 150°C, 200°C d'une part et 350°C, 450°C d'autre part.Direct distillation diesel or direct diesel or even diesel itself is the middle distillate, intermediate between light distillates, gas and petrol, aviation fuels on the one hand and heavy residue on the other hand, in distillation at atmospheric pressure which begins the refining of crude oils. The composition, like the properties of a direct diesel, differentiate it in a known manner from the visbreaking or catalytic cracking diesel obtained after the vacuum distillation of the above heavy residue. The distillation interval at atmospheric pressure of a direct diesel oil generally ranges between approximately 150 ° C, 200 ° C on the one hand and 350 ° C, 450 ° C on the other hand.

Les gazoles directs sont essentiellement destinés à l'alimentation des moteurs diesel et au chauffage domestique.Direct gas oils are mainly used to supply diesel engines and domestic heating.

Ils doivent avoir une aptitude à l'ignition par compression suffisamment élevée, traduite par leur indice de cétane.They must have a sufficiently high capacity for ignition by compression, reflected by their cetane number.

L'utilité pour l'industrie de disposer de tels gazoles d'indice de cétane élevé est récemment rappelée par exemple dans le brevet européen publié sous le numéro 0252606. Sont visés à ce jour des indices de cétane supérieurs à environ 45, de préférence supérieurs à 50.The usefulness for the industry of having such gas oils with a high cetane index is recently recalled for example in the European patent published under the number 0252606. To date, cetane numbers greater than about 45, preferably greater, are targeted. at 50.

La solution qui peut être adoptée pour assurer aux gazoles directs un indice de cétane satisfaisant est de leur incorporer un additif. L'inconvénient d'une telle méthode est de contraindre au choix d'un additif qui doit être à la fois relativement insoluble dans l'eau et chimiquement stable par rapport à elle, suffisamment soluble dans le gazole aux condi­tions d'emploi préférées, stable dans le gazole à toutes tempé­ratures de stockage de celui-ci, enfin non corrosif et non toxique.The solution which can be adopted to ensure that direct gas oils have a satisfactory cetane number is to incorporate an additive therein. The disadvantage of such a method is that it forces the choice of an additive which must be both relatively insoluble in water and chemically stable with respect to it, sufficiently soluble in diesel under the preferred conditions of use, stable. in diesel fuel at all storage temperatures, finally non-corrosive and non-toxic.

Pour ce qui est de la définition des termes utili­sés, tels que gazole moteur, indice de cétane, on peut se reporter par exemple aux ouvrages "Le langage pétrolier", GAUTHIER-VILLARS, Paris, 1964, "Le Pétrole, raffinage et génie chimique" écrit sous la direction de Pierre WUITHIER, 2ème édition, 1972, Technip ed., p.16, 17, 29, 30, ou à l'article de D. INDRITZ, "Preprints, Symposium of the Chemistry of Cetane number improvement", Miami Beach, 28 avril - 3 Mai 1985, pp.282-286.With regard to the definition of terms used, such as diesel fuel, cetane number, one can refer for example to the works "The language of petroleum", GAUTHIER-VILLARS, Paris, 1964, "Petroleum, refining and chemical engineering "written under the supervision of Pierre WUITHIER, 2nd edition, 1972, Technip ed., p.16, 17, 29, 30, or to the article by D. INDRITZ," Preprints, Symposium of the Chemistry of Cetane number improvement " , Miami Beach, April 28 - May 3, 1985, pp. 282-286.

Les gazoles directs d'indice de cétane amélioré selon la présente invention peuvent donner lieu à commerciali­sation en l'état ou autrement servir à relever l'indice de cétane de gazoles de moindre indice de cétane.Direct gas oils with improved cetane number according to the present invention may give rise to marketing as is or otherwise serve to raise the cetane number of gas oils with a lower cetane number.

Le procédé selon l'invention pour améliorer l'indice de cétane d'un gazole de distillation directe est caractérisé en ce que ledit gazole est mis en contact soit avec du peroxy­de d'hydrogène en présence d'un acide carboxylique, soit avec un acide percarboxylique en présence ou non de peroxyde d'hydrogène.The process according to the invention for improving the cetane number of a direct distillation diesel is characterized in that said diesel is brought into contact either with hydrogen peroxide in the presence of a carboxylic acid, or with an acid percarboxylic in the presence or not of hydrogen peroxide.

Dans le cas où le gazole direct est mis en contact avec du peroxyde d'hydrogène en présence d'un acide carboxyli­que :
- la quantité de peroxyde d'hydrogène engagé par kilogramme de gazole direct est, pour des raisons de sécurité comme d'économie, inférieure à 300 g. ; le plus souvent ladite quantité qui permet d'atteindre le résultat visé n'excède pas 50 g. environ.
- l'acide carboxylique est en pratique choisi parmi l'acide formique, l'acide acétique et l'acide propionique ; l'acide formique est préféré. Le rapport molaire acide carbo­xylique/peroxyde d'hydrogène est compris de préférence entre environ 0,01 et 1, et mieux encore, entre environ 0,1 et 0,5,
- la température à laquelle est réalisé le contact selon l'invention est le plus souvent comprise entre environ 50°C et 100°C,
- le peroxyde d'hydrogène peut être engagé sous forme d'une solution aqueuse contenant par exemple, et le plus souvent, entre environ 50 % et 70 % en poids de peroxyde d'hydrogène,
- la durée du contact selon l'invention dépend des autres paramètres choisis ; elle est de préférence suffisante, combinée à ces autres paramètres, pour assurer la disparition la plus complète possible du peroxyde engagé.
- la mise en contact est réalisée sous agitation dans un réacteur résistant à la corrosion acide et essentiel­lement muni d'un système d'agitation efficace, de moyens de chauffage, de mesure et de contrôle de la température.In the case where the direct diesel fuel is brought into contact with hydrogen peroxide in the presence of a carboxylic acid:
- the quantity of hydrogen peroxide used per kilogram of direct diesel fuel is, for safety and economic reasons, less than 300 g. ; most often said quantity which makes it possible to achieve the desired result does not exceed 50 g. about.
- The carboxylic acid is in practice chosen from formic acid, acetic acid and propionic acid; formic acid is preferred. The molar ratio of carboxylic acid / hydrogen peroxide is preferably between approximately 0.01 and 1, and better still, between approximately 0.1 and 0.5,
the temperature at which the contact according to the invention is made is most often between approximately 50 ° C. and 100 ° C.,
- the hydrogen peroxide can be used in the form of an aqueous solution containing for example, and most often between about 50% and 70% by weight of hydrogen peroxide,
the duration of the contact according to the invention depends on the other parameters chosen; it is preferably sufficient, combined with these other parameters, to ensure the most complete possible disappearance of the engaged peroxide.
- The contacting is carried out with stirring in a reactor resistant to acid corrosion and essentially provided with an effective stirring system, heating means, measurement and temperature control.

Dans le cas où le gazole direct est mis en contact avec un acide percarboxylique :
- l'acide percarboxylique est choisi en pratique parmi l'acide performique, l'acide peracétique et l'acide perpropionique, et fabriqué de façon connue comme par exemple, en ce qui concerne l'acide perpropionique, selon les procédés décrits dans les demandes de brevet français publiées sous les numéros 2460927 et 2464947.
- si l'acide percarboxylique agit en absence de peroxyde d'hydrogène, il est engagé aux mêmes quantités molaires que le peroxyde d'hydrogène dans la première forme de réalisation de l'invention exposée plus haut,
- si l'acide percarboxylique agit en présence de peroxyde d'hydrogène, les quantités molaires cumulées d'acide percarboxylique et de peroxyde d'hydrogène sont les mêmes que celles de peroxyde d'hydrogène engagé selon la première forme de réalisation de l'invention.
- les conditions de température, durée et autres paramètres de réalisation sont les mêmes que dans la première forme de réalisation de l'invention.In the case where the direct diesel fuel is brought into contact with a percarboxylic acid:
the percarboxylic acid is chosen in practice from performic acid, peracetic acid and perpropionic acid, and manufactured in a known manner, for example as regards perpropionic acid, according to the methods described in the applications French patent published under the numbers 2460927 and 2464947.
if the percarboxylic acid acts in the absence of hydrogen peroxide, it is used in the same molar quantities as the hydrogen peroxide in the first embodiment of the invention described above,
- If the percarboxylic acid acts in the presence of hydrogen peroxide, the cumulative molar amounts of percarboxylic acid and hydrogen peroxide are the same as those of hydrogen peroxide used according to the first embodiment of the invention .
- The conditions of temperature, duration and other production parameters are the same as in the first embodiment of the invention.

Le procédé de l'invention convient aux gazoles directs avant ou après une désulfuration, par exemple une hydrodésulfuration, qui ramène leur teneur en soufre à une valeur correspondante ou inférieure à celle réclamée par leurs applications. Il s'applique par exemple à un gazole direct prêt à être utilisé comme gazole moteur.The process of the invention is suitable for direct gas oils before or after desulfurization, for example hydrodesulfurization, which reduces their sulfur content to a value corresponding to or lower than that required by their applications. It applies for example to direct diesel ready to be used as engine diesel.

Il présente de plus l'avantage de ne pas faire appel à des catalyseurs à base de métaux.It also has the advantage of not using metal-based catalysts.

Les exemples suivants, donnés à titre indicatif mais non limitatif, illustrent le procédé de l'invention. Dans ces exemples l'indice de cétane est mesuré selon la norme ASTM D-­613.The following examples, given as an indication but not limiting, illustrate the process of the invention. In these examples the cetane number is measured according to standard ASTM D-613.

Exemple 1 : Example 1 :

Dans un réacteur agité de 3 l, sont introduits 1000 g. de gazole de distillation directe puis 0,07 mole d'acide formique. Le mélange agité est porté à 70°C et est maintenu à cette température sous agitation d'abord pendant l'addition, en 1 heure, de 0,7 mole de peroxyde d'hydrogène engagé sous forme de 34 g. de solution aqueuse contenant 70 % de peroxyde d'hydrogène en poids, puis pendant 5 heures à partir de la fin de l'addition du peroxyde d'hydrogène.1000 g are introduced into a stirred reactor of 3 l. direct distillation diesel then 0.07 mole of formic acid. The stirred mixture is brought to 70 ° C. and is kept at this temperature with stirring first during the addition, over 1 hour, of 0.7 mole of hydrogen peroxide used in the form of 34 g. of aqueous solution containing 70% hydrogen peroxide by weight, then for 5 hours from the end of the addition of hydrogen peroxide.

La phase organique séparée ensuite par décantation du mélange mis au repos et refroidi, est lavée de façon à ce que le peroxyde d'hydrogène et l'acide formique qui pourraient subsister dans le gazole après traitement, soient éliminés de celui-ci. Le lavage est le plus couramment réalisé à l'aide d'eau.The organic phase, which is then separated by decantation from the mixture, which is left to stand and cooled, is washed so that the hydrogen peroxide and formic acid which may remain in the gas oil after treatment are removed from it. Washing is most commonly done using water.

L'indice de cétane du gazole de distillation directe de départ est égal à 58. Celui du gazole direct après applica­tion du procédé selon l'invention est de 64.The cetane number of the direct distillation starting diesel oil is equal to 58. That of direct diesel after application of the process according to the invention is 64.

Un résultat pratiquement semblable est encore atteint en engageant deux fois moins de peroxyde d'hydrogène que ci-dessus.A practically similar result is still achieved by using twice as little hydrogen peroxide as above.

Exemple 2 : Example 2 :

En procédant comme dans l'exemple 1 mais avec un gazole moteur prêt à l'emploi d'indice de cétane égal à 53 et en engageant, pour 1000 g. dudit gazole 0,7 mole de peroxyde d'hydrogène, le gazole qui résulte du traitement selon l'inven­tion à un indice de cétane égal à 57,5.By proceeding as in Example 1 but with a ready-to-use engine diesel fuel with a cetane index equal to 53 and committing, for 1000 g. of said diesel 0.7 mole of hydrogen peroxide, the diesel which results from the treatment according to the invention with a cetane number equal to 57.5.

Claims (9)

1. Procédé pour améliorer l'indice de cétane d'un gazole de distillation directe, caractérisé en ce que ledit gazole est mis en contact soit avec du peroxyde d'hydrogène en présence d'un acide carboxylique, soit avec un acide percarbo­xylique en présence ou non de peroxyde d'hydrogène.1. A method for improving the cetane number of a direct distillation gas oil, characterized in that said gas oil is brought into contact either with hydrogen peroxide in the presence of a carboxylic acid, or with a percarboxylic acid in the presence or not hydrogen peroxide. 2. Procédé selon la revendication 1, caractérisé en ce que, dans le cas où le peroxyde d'hydrogène est en présence d'un acide carboxylique, la quantité de peroxyde d'hydrogène engagé par kilogramme de gazole de distillation directe est inférieure à 300 g.2. Method according to claim 1, characterized in that, in the case where the hydrogen peroxide is in the presence of a carboxylic acid, the quantity of hydrogen peroxide used per kilogram of direct distillation diesel is less than 300 g. 3. Procédé selon la revendication 2, caractérisé en ce que la quantité de peroxyde d'hydrogène engagé par kilogram­me de gazole de distillation directe n'excède pas environ 50g.3. Method according to claim 2, characterized in that the quantity of hydrogen peroxide used per kilogram of direct distillation diesel does not exceed about 50g. 4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que l'acide carboxylique est choisi parmi l'acide formique, l'acide acétique et l'acide propionique.4. Method according to one of claims 1 to 3, characterized in that the carboxylic acid is chosen from formic acid, acetic acid and propionic acid. 5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que le rapport molaire acide carboxylique/­peroxyde d'hydrogène est compris entre 0,01 et 1.5. Method according to one of claims 1 to 4, characterized in that the molar ratio of carboxylic acid / hydrogen peroxide is between 0.01 and 1. 6. Procédé selon la revendication 5, caractérisé en ce que le rapport molaire acide carboxylique/peroxyde d'hydro­gène est compris entre 0,1 et 0,5.6. Method according to claim 5, characterized in that the molar ratio of carboxylic acid / hydrogen peroxide is between 0.1 and 0.5. 7. Procédé selon la revendication 1, caractérisé en ce que l'acide percarboxylique est choisi parmi l'acide perfor­mique, l'acide peracétique, l'acide perpropionique.7. Method according to claim 1, characterized in that the percarboxylic acid is chosen from performic acid, peracetic acid, perpropionic acid. 8. Procédé selon l'une des revendications 1 et 7, caractérisé en ce que les quantités molaires d'acide percarbo­xylique ou, cumulativement, dudit acide et du peroxyde d'hydro­gène présent avec lui, sont celles de peroxyde d'hydrogène quand celui-ci est en présence d'un acide carboxylique.8. Method according to one of claims 1 and 7, characterized in that the molar amounts of percarboxylic acid or, cumulatively, of said acid and of the hydrogen peroxide present with it, are those of hydrogen peroxide when this- this is in the presence of a carboxylic acid. 9. Procédé selon l'une des revendications 1 à 8, caractérisé en ce que la température à laquelle est réalisée la mise en contact du gazole de distillation directe soit avec le peroxyde d'hydrogène en présence de l'acide carboxylique, soit avec l'acide percarboxylique en présence ou non de pero­xyde d'hydrogène, est comprise entre 50°C et 100°C.9. Method according to one of claims 1 to 8, characterized in that the temperature at which the direct distillation diesel fuel is brought into contact either with hydrogen peroxide in the presence of the carboxylic acid, or with l percarboxylic acid in the presence or absence of hydrogen peroxide is between 50 ° C and 100 ° C.
EP90420120A 1989-03-14 1990-03-07 Process for improving the cetane number of straight new gasoils Expired - Lifetime EP0388325B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8903576A FR2644471B1 (en) 1989-03-14 1989-03-14 PROCESS FOR IMPROVING THE CETANE INDEX OF DIRECT DISTILLATION GASOLES
FR8903576 1989-03-14

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EP0388325A1 true EP0388325A1 (en) 1990-09-19
EP0388325B1 EP0388325B1 (en) 1993-02-17

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US (1) US5114433A (en)
EP (1) EP0388325B1 (en)
JP (1) JPH0649872B2 (en)
AT (1) ATE85807T1 (en)
CA (1) CA2012084C (en)
DE (2) DE69000918T2 (en)
DK (1) DK0388325T3 (en)
ES (1) ES2018126T3 (en)
FR (1) FR2644471B1 (en)
GR (1) GR900300183T1 (en)

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CN103074099B (en) * 2013-01-25 2016-01-20 陕西师范大学 A kind of catalytic oxidation desulfurization method of oil fuel

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JPH02281095A (en) 1990-11-16
US5114433A (en) 1992-05-19
JPH0649872B2 (en) 1994-06-29
ES2018126A4 (en) 1991-04-01
DE69000918T2 (en) 1993-06-24
DE388325T1 (en) 1991-02-28
DE69000918D1 (en) 1993-03-25
GR900300183T1 (en) 1991-10-10
FR2644471A1 (en) 1990-09-21
ES2018126T3 (en) 1993-07-16
FR2644471B1 (en) 1991-06-07
ATE85807T1 (en) 1993-03-15
EP0388325B1 (en) 1993-02-17
CA2012084C (en) 1996-03-26
CA2012084A1 (en) 1990-09-14
DK0388325T3 (en) 1993-03-29

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