EP0416979B1 - Verfahren zum Süssen von Petroleumschnitten im festen Bett - Google Patents

Verfahren zum Süssen von Petroleumschnitten im festen Bett Download PDF

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Publication number
EP0416979B1
EP0416979B1 EP90402387A EP90402387A EP0416979B1 EP 0416979 B1 EP0416979 B1 EP 0416979B1 EP 90402387 A EP90402387 A EP 90402387A EP 90402387 A EP90402387 A EP 90402387A EP 0416979 B1 EP0416979 B1 EP 0416979B1
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EP
European Patent Office
Prior art keywords
charge
temperature
support
process according
water
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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
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EP90402387A
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English (en)
French (fr)
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EP0416979A1 (de
Inventor
Jean-Michel Orgebin
Claude Marty
Patrick Ansquer
Pierre Maroy
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TotalEnergies Marketing Services SA
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Total Raffinage Distribution 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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • 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
    • C10G27/10—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen in the presence of metal-containing organic complexes, e.g. chelates, or cationic ion-exchange resins

Definitions

  • the present invention relates to the softening in a fixed bed of petroleum fractions, by catalytic oxidation to disulphides of the mercaptans which they contain.
  • such an oxidation can be obtained simply by mixing the petroleum fraction to be treated and an aqueous solution of an alkaline base, to which a catalyst based on a metal chelate is added, in the presence of an oxidizing agent.
  • the petroleum cut and the aqueous solution of the alkaline base are not miscible and it is at the interface of the two liquid phases that the mercaptans are converted to disulfides (see French patent No. 1,249,134).
  • the oxidizing agent generally air, is mixed with the cut to be softened.
  • the alkaline base usually an aqueous sodium hydroxide solution, is introduced either continuously or intermittently into the reaction medium, to maintain the alkaline conditions and the aqueous phase necessary for the oxidation reaction.
  • the metal chelate used as a catalyst, is generally a metal phthalocyanine (see French patent n ° 1,301,844).
  • the reaction is carried out at a pressure generally between 5 and 30 ⁇ 10 5 Pascals, at a temperature between 20 and 40 ° C.
  • a pressure generally between 5 and 30 ⁇ 10 5 Pascals, at a temperature between 20 and 40 ° C.
  • aqueous sodium hydroxide or a strong base
  • US-A-3686094 describes a catalyst for a fixed-bed softening process for distillation cups which is composed of a mixture of anhydrous phthalocyanine, carbon, soda or potassium hydroxide and a binder. This mixture makes it possible to soften the fillers when the water content of the mixture is maintained between 5 and 25% by weight and the reaction temperature between 10 and 70 ° C, preferably between 20 and 25 ° C.
  • the present invention aims to remedy all these drawbacks by proposing a process for softening an oil cut, by catalytic oxidation of mercaptans, requiring neither the use of an inorganic or organic anhydrous base, nor the use of a desiccant mixed with the support, nor the periodic drying of the support using a solvent.
  • the present invention aims to remedy all these drawbacks by proposing a process for softening an oil cut, by catalytic oxidation of mercaptans, requiring neither the use of an inorganic or organic anhydrous base, nor the use of a desiccant mixed with the support, nor the periodic drying of the support using a solvent.
  • the subject of the invention is therefore a process for softening an oil cut in the presence of an oxidizing agent, by catalytic oxidation of the mercaptans which it contains, in the presence of a support in a fixed bed impregnated with a metal chelate.
  • this process being characterized in that the softening reaction is carried out in the absence of a strong soluble base and in that, the temperature of the charge being greater than 30 ° C., the water content of the support is measured and, when this content deviates from a set value, between 0.1 and 50% by weight of the support and, preferably, between 1 and 25% by weight of the support ci, we raise or, respectively, lower the temperature of the load, in order to lower the water content of the support or, respectively, to increase it, to bring it back to the set value.
  • the predetermined range of water contents of the support will, of course, depend on the nature of the catalytic support used during the softening reaction. Indeed, the Applicant has established that, if numerous catalytic supports are capable of being used without aqueous sodium hydroxide (or without base), their activity will only manifest themselves when their water content (also called hydration level of the support) is kept within a relatively narrow range of values, variable depending on the supports, but apparently linked to the content of the silicate support and to the structure of its pores.
  • the temperature of the petroleum cut will generally be kept above 30 ° C and preferably between 40 and 140 ° C; the necessary heat can be provided by any means of a type known per se, but preferably it will be provided by heat exchange upstream of the reaction zone.
  • the catalytic oxidation reaction will be advantageously carried out at a higher temperature. at 30 ° C and preferably between 40 and 120 ° C. These conditions are aimed in particular at the softening of petroleum fractions such as kerosene or so-called catalytic or direct distillation gasolines.
  • the catalytic oxidation reaction will be carried out at a temperature higher than 40 ° C and preferably between 50 and 140 ° C. These conditions are aimed in particular at the softening of petroleum cuts such as light petrol.
  • the optimum rate of hydration of the support on which the catalytic activity depends will be maintained at a determined value, generally between 1 and 25% by weight, despite the possible variations in the charge, for example by fluctuating the temperature of a few degrees around an equilibrium temperature, depending on whether the support itself tends to hydrate or dehydrate.
  • This rate can also be maintained by raising the reaction temperature substantially and by injecting a certain amount of water, which can vary depending on the water and mercaptan contents of the feed.
  • a possible alternative will consist, for example, in carrying out the reaction at a temperature a few degrees lower than the equilibrium temperature mentioned above and in sending, periodically, or continuously, a determined quantity of poorly hydrated filler to a higher temperature.
  • means will be used to measure the water content of the feed and of the effluent, or of the catalytic support, as well as the mercaptan contents of the feed. and effluent.
  • the means for measuring the water content of the support one can use, on the one hand, systems allowing, in a manner known per se, the taking of samples of catalytic support without stopping the unit. From these samples, it is easy to measure, by the Karl FISCHER method, the hydration rate of the support and then to bring this rate back to its optimal value by temperature regulation, in accordance with the present invention. It is also possible to use a probe system placed directly inside the catalytic bed.
  • Another means, easy to implement, consists in using two probes for continuous measurement of the water content of the feed, the first being located upstream of the catalytic bed, the second downstream of the latter.
  • the probes making it possible to continuously measure the water content of the feed, it is possible to use commercial probes, such as those sold by the Endress Hauser company, or capacitive probes of the type described in French patent application No. 2.512 .958.
  • the difference between the content measured downstream and that measured upstream then makes it easy to determine, taking into account the quantity of mercaptans transformed into disulfides, by how much the water content of the support increases or decreases.
  • a modification of the reaction temperature (or of the quantity of additional water injected) then makes it possible to make the water content of the catalytic support in the reactor substantially constant.
  • a first advantage of the present invention follows from the very principle of the reaction, which is linked to the absence of base or of caustic solution in the feed and in the effluents: on the one hand, there is no longer any need to separate the bases, neither to reprocess them, nor to have an expensive unit of destruction of these; on the other hand, the absence of base, even in trace amounts in the petroleum charges treated, makes them excellent products for subsequent direct use.
  • a second advantage of the present invention results from the fact that the reaction water is entrained by the petroleum charge itself during the softening. There is therefore no longer any need for costly drying of the support by injecting solvents into the feed, or by using a desiccant in the catalytic bed.
  • a third advantage of the present invention results from the fact that the softening reaction is carried out at a higher temperature than according to the prior art: the kinetics of the reaction are improved, and it becomes possible to carry out the reaction continuously at a hourly space velocity greater than that of the prior art.
  • This hourly space speed may be of the order of 1 to 8 v.v.h. (charge volume per catalyst volume and per hour) for kerosene type charges and of the order of 1 to 10 v.v.h. for petrol type loads.
  • the reaction kinetics being improved, it is also possible to treat more refractory or heavier fillers which are difficult to soften according to the prior art, or to carry out the softening of the mercaptans continuously where only batch techniques were applicable. until now.
  • a fourth advantage of the present invention finally results from the fact that the softening reaction is carried out in homogeneous phase, without the formation of gums, which leads to a reduction in washing and maintenance costs, and a simplification of the equipment located downstream. of unity.
  • the process according to the invention is well suited to the softening of all petroleum cuts and, in particular, the softening of petrol and kerosene. Indeed, these petroleum fractions contain only very little water (an amount generally less than 500 ppm) and, consequently, the rise in temperature necessary to dissolve the water molecules generated in situ during the reaction of softening will be kept within acceptable limits.
  • the petroleum charge to be treated contains relatively large quantities of mercaptans, for example for charges whose mercaptan content is greater than 300 ppm, it will be possible to compensate for the formation in situ of a corresponding quantity of molecules d water, for example by drying the charge beforehand on molecular sieves, (or by cooling it, then by decanting it), in order to limit as much as possible its initial water content.
  • supports based on activated carbon on alumina, of clay, aluminosilicates, silicates or mixtures of these.
  • any chelate used for this purpose in the prior art in particular phthalocyanines, porphyrins or metal corrines, can be deposited on the support.
  • phthalocyanines in particular phthalocyanines, porphyrins or metal corrines
  • cobalt phthalocyanine and vanadium phthalocyanine are particularly preferred.
  • metallic phthalocyanine is used in the form of a derivative of the latter, with particular preference for their commercially available sulfonates, such as, for example, cobalt phthalocyanine disulphonate and mixtures thereof. this.
  • This figure represents a diagram of continuous implementation of the method according to the invention.
  • the supply of the reactor 1 in the petroleum cut to be softened takes place via line 2, into which the oxidizing agent, air for example, is introduced directly by line 3.
  • the treated petroleum cut is evacuated via line 4, which feeds a filter system 5, intended to eliminate traces of water and of emerging sulfur often produced during the oxidation of mercaptans and not retained by the support.
  • the treated charge is then transferred by line 6 to a storage enclosure 7.
  • measurement probes 8 and 9 placed respectively upstream and downstream of the reactor, make it possible to permanently determine the water and mercaptan contents at the inlet and at the outlet of the reactor 1. It is thus it is possible to continuously check whether the water content of the catalytic support increases or decreases.
  • a corrective action can then be carried out by modifying the quantity of heat supplied to the load by a heat exchanger 10 placed on the line 2 upstream of the reactor 1. Part of the heat supplied by the exchanger 10 can then be recovered using the exchanger 11 placed on the line 4 downstream of the reactor 1 and from the water formed eliminated at 5.
  • Water can optionally be injected into the feed through line 12, placed here between the temperature regulation phase at 10 and the catalytic oxidation phase at 1 of the petroleum cut.
  • the temperature of the charge at the outlet of the exchanger 10 will be slightly higher than that required to maintain the water content of the support equal to its set value, and an additional d water will, for example, be introduced via line 12 to make this content equal to the set value, despite fluctuations in the contents of water and mercaptans or those of the temperature of the charge.
  • This embodiment of the invention has the advantage that it is easier to ensure regulation by varying the quantity of water injected than by varying the temperature of the charge.
  • the catalytic support used in this example was prepared as described in European patent application No. 252,853. After impregnation of the support with a sulfonated cobalt phthalocyanine of the type marketed by the French company PROCATALYSE under the name "LCPS", this catalyst is in the form of an aggregate (with a specific surface of approximately 50 m 2 / g, which mainly contains approximately 1.5 kg of chelate per m 3 of support. This support contains approximately 10% by weight of carbon, 20% by weight of silicon, and 8 to 9% by weight of potassium salts in the form of insoluble salts .
  • Air is used as the oxidizing agent, and no basic aqueous solution is used.
  • the mercaptan content of the treated feedstock C 1 is less than 5 ppm for the first sixty days approximately, then that the mercaptan content of the effluents rises gradually and exceeds 10 ppm after 90 days , due to the progressive saturation in water of the catalytic support; it is then easy to see that the reaction water has been captured by the support, the hydration rate of which has risen to more than 10%.
  • the T2 test is then carried out, increasing the temperature of the load to 80 ° C and passing the hourly space speed to 4 vvh. It is found that the mercaptan content of the treated charge C 1 becomes again less than 5 ppm, during the first 6 days, then that this content rises sharply and exceeds 10 ppm after 7 days, this time due to the dehydration of the support catalytic, whose hydration rate has become less than 1%.
  • the operating conditions are then modified to carry out the T3 test in accordance with the method according to the invention: it is found that the mercaptan content of the treated charge C 1 always remains less than 5 ppm, after 300 days of operation. In fact, the hydration rate of the support has remained substantially constant, due to the rise in temperature from 40 to 45 ° C, which makes it possible to remove with the charge all the reaction water from the conversion of mercaptans to disulfides .
  • reaction conditions are again modified to carry out the T4 test, also in accordance with the method according to the invention: it is also noted that the mercaptan content of the treated charge C 1 always remains less than 5 ppm, even after 300 days of operation .
  • the hydration rate of the support is maintained at a constant value of around 6%, despite the sharp increase in temperature from (45 to 80 ° C) and in hourly space speed (from 1 to 4 vvh) by injecting sufficient water into the feed (+ 577 ppm) so that, despite the significant increase in its solvent power at 80 ° C, the feed can no longer dissolve in the reactor except the amount of reaction water produced.
  • reaction conditions are therefore modified to use those described in T 6 , and it can be seen that, as with kerosene feeds, the process according to the invention makes it possible to keep the mercaptan content constantly below 10 ppm. , by an action on the solvent power of the load as a function of the temperature, similar to the T4 test described previously.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Detergent Compositions (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Fats And Perfumes (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (10)

  1. Verfahren zum Süssen einer Erdölfraktion in Gegenwart eines Oxidationsmittels durch katalytische Oxidation der in der Fraktion enthaltenen Mercaptane in Gegenwart eines mit einem Metallchelat imprägnierten Supportes im Festbett, dadurch gekennzeichnet, daß die Süssungsreaktion in Abwesenheit von starker löslicher Base durchgeführt wird und daß bei einer Temperatur der Charge höher als 30° C der Wassergehalt des Supportes gemessen wird und dann, wenn dieser Gehalt von einem Sollwert abweicht, der zwischen 0,1 und 50 Gewichtsprozent des Supportes, vorzugsweise zwischen 1 und 25 Gewichtsprozent des Supportes, liegt, die Temperatur der Charge erhöht oder erniedrigt wird, um den Wassergehalt des Supportes zu verringern bzw. zu vergrößern und ihn wieder auf den Sollwert zu bringen.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Wärme, welche erforderlich ist, um die Charge auf die zum Lösen des Reaktionswassers gewünschte Temperatur zu bringen, der Charge durch Wärmeaustausch vor der Reaktionszone zugeführt wird.
  3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Temperatur der zu behandelnden Charge auf einem Wert zwischen 40 und 140°C gehalten wird.
  4. Verfahren nach einem der Ansprüche 1 bis 3, angewendet auf das Süssen einer Charge, welche zwischen 20 und 300 p. p. m. Mercaptane enthält, dadurch gekennzeichnet, daß die Temperatur der zu behandelnden Charge auf einem Wert höher als 30 °C, vorzugsweise zwischen 40 und 120 °C, gehalten wird.
  5. Verfahren nach einem der Ansprüche 1 bis 3, angewendet auf das Süssen einer Charge. welche zwischen 300 und 3000 p. p. m. Mercaptane enthält, dadurch gekennzeichnet, daß die Temperatur der zu behandelnden Charge auf einem Wert höher als 40 °C, vorzugsweise zwischen 50 und 140 °C, gehalten wird.
  6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die stündliche räumliche Geschwindigkeit der Charge zwischen 1 und 10 v. v. h. (Chargenvolumen pro Katalysatorvolumen und pro Stunde) liegt.
  7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Regulierung der Temperatur der zu behandelnden Charge einem System zur Messung der Differenz des Wassergehaltes der Charge vor und hinter der katalytischen Oxidationsphase unterworfen ist.
  8. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Regulierung der Temperatur der zu behandelnden Charge einem Mittel zur Messung des Wassergehaltes des Supportes im Festbett unterworfen ist.
  9. Verfahren nah einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß der Support im Festbett aus der Gruppe bestehend aus den Aktivkohlen, den Aluminiumoxiden den Tonen, den Aluminosilicaten, den Silicaten und deren Mischungen ausgewählt ist.
  10. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß das Metallchelat aus der Gruppe bestehend aus den Phthalocyaninen, den Porphyrinen und den Metallcorrinen ausgewählt ist.
EP90402387A 1989-09-08 1990-08-29 Verfahren zum Süssen von Petroleumschnitten im festen Bett Expired - Lifetime EP0416979B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8911781 1989-09-08
FR8911781A FR2651791B1 (fr) 1989-09-08 1989-09-08 Procede d'adoucissement en lit fixe de coupes petrolieres.

Publications (2)

Publication Number Publication Date
EP0416979A1 EP0416979A1 (de) 1991-03-13
EP0416979B1 true EP0416979B1 (de) 1997-10-29

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EP90402387A Expired - Lifetime EP0416979B1 (de) 1989-09-08 1990-08-29 Verfahren zum Süssen von Petroleumschnitten im festen Bett

Country Status (8)

Country Link
US (1) US5069777A (de)
EP (1) EP0416979B1 (de)
JP (1) JPH03174493A (de)
KR (1) KR910006460A (de)
CA (1) CA2024834A1 (de)
DE (1) DE69031644D1 (de)
FR (1) FR2651791B1 (de)
ZA (1) ZA906770B (de)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2666344B1 (fr) * 1990-09-03 1992-12-18 Total France Procede d'adoucissement en lit fixe de distillats petroliers acides de temperatures de coupe comprises entre environ 125 et environ 350 degre c.
US5633216A (en) * 1992-03-03 1997-05-27 Institut Francais Du Petrole Process for sweetening petroleum cuts without regular addition of alkaline solution using a basic solid catalyst
FR2688223B1 (fr) * 1992-03-05 1994-05-20 Institut Francais Petrole Nouveau procede d'adoucissement de coupes petrolieres sans adjonction reguliere de solution aqueuse alcaline, utilisant un catalyseur solide basique.
EP0638628B1 (de) * 1993-08-04 1998-12-16 Institut Francais Du Petrole Verfahren zum Süssen von Petroleumfraktionen ohne kontinuierliche Beimischung einer wässrigen alkalischen Lösung, unter Verwendung eines basischen Katalysators
US5413701A (en) * 1993-11-15 1995-05-09 Uop Process for sweetening a sour hydrocarbon fraction using a supported metal chelate and a solid base
US6709639B1 (en) * 1996-09-24 2004-03-23 Institut Francais Du Petrole Apparatus for purification of raw gasoline from catalytic cracking
CN104266176A (zh) * 2014-09-09 2015-01-07 翟永才 一种节能环保锅炉

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3230180A (en) * 1963-02-07 1966-01-18 Universal Oil Prod Co Metal phthalocyanine catalyst preparation
FR1602191A (de) * 1968-12-31 1970-10-19
US4207173A (en) * 1976-03-04 1980-06-10 Uop Inc. Sweetening of hydrocarbon distillates utilizing a tetra-alkyl guanidine with phthalocyanine catalyst
US4124531A (en) * 1977-01-03 1978-11-07 Uop Inc. Catalytic composite for the treatment of sour petroleum distillates
US4248694A (en) * 1979-05-17 1981-02-03 Uop Inc. Process for treating a sour petroleum distillate
US4290917A (en) * 1979-10-01 1981-09-22 Uop Inc. Method of manufacturing a catalytic composite
US4298463A (en) * 1980-07-11 1981-11-03 Uop Inc. Method of treating a sour petroleum distillate
US4498978A (en) * 1983-11-29 1985-02-12 Uop Inc. Catalytic oxidation of mercaptan in petroleum distillate
US4574121A (en) * 1983-11-29 1986-03-04 Uop Inc. Metal chelate mercaptan oxidation catalyst
US4498977A (en) * 1983-11-29 1985-02-12 Uop Inc. Catalytic oxidation of mercaptan in petroleum distillate
US4502949A (en) * 1984-02-15 1985-03-05 Uop Inc. Catalytic oxidation of mercaptan in petroleum distillate
US4753722A (en) * 1986-06-17 1988-06-28 Merichem Company Treatment of mercaptan-containing streams utilizing nitrogen based promoters
US4913802A (en) * 1989-05-08 1990-04-03 Uop Process for sweetening a sour hydrocarbon fraction

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Publication number Publication date
FR2651791B1 (fr) 1994-05-20
EP0416979A1 (de) 1991-03-13
ZA906770B (en) 1991-06-26
JPH03174493A (ja) 1991-07-29
DE69031644D1 (de) 1997-12-04
CA2024834A1 (fr) 1991-03-09
FR2651791A1 (fr) 1991-03-15
US5069777A (en) 1991-12-03
KR910006460A (ko) 1991-04-29

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