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EP0556025B1 - Hydrogénation sélective de courants en C5 - Google Patents

Hydrogénation sélective de courants en C5 Download PDF

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Publication number
EP0556025B1
EP0556025B1 EP93300939A EP93300939A EP0556025B1 EP 0556025 B1 EP0556025 B1 EP 0556025B1 EP 93300939 A EP93300939 A EP 93300939A EP 93300939 A EP93300939 A EP 93300939A EP 0556025 B1 EP0556025 B1 EP 0556025B1
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EP
European Patent Office
Prior art keywords
distillation column
column reactor
distillation
hydrogen
process according
Prior art date
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Expired - Lifetime
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EP93300939A
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German (de)
English (en)
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EP0556025A1 (fr
Inventor
Edward Maurice Jones, Jr.
Lawrence Alfred Smith, Jr.
Dennis Hearn
Robert Phillip Arganbright
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Chemical Research and Licensing Co
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Chemical Research and Licensing Co
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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
    • C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
    • C10G70/02—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by hydrogenation
    • 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
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4087—Catalytic distillation

Definitions

  • the present invention relates to the selective hydrogenation of diolefins (dienes) contained in a refinery stream containing predominantly C 5 's and more specifically olefinic C 5 's. More particularly the invention relates to a process for the selective hydrogenation of the dienes utilizing a distillation column reactor containing a hydrogenation catalyst which also acts as a component in a distillation structure. Most specifically the invention relates to the selective hydrogenation of a C 5 feed stream for the production of tertiary amyl methyl ether (TAME).
  • TAME tertiary amyl methyl ether
  • olefinic compounds comprise ethylene, acetylene, propylene, propadiene, methylacetylene, butenes, butadiene, etc. Many of these compounds are valuable, especially as feed stocks for chemical products. Ethylene, especially is recovered. Additionally, propylene and the butenes are valuable.
  • the olefins having more than one double bond and the acetylenic compounds (having a triple bond) have lesser uses and are detrimental to many of the chemical process in which the single double bond compounds are used, for example polymerization.
  • Refinery streams are usually separated by fractional distillation, and because they often contain compounds that are very close in boiling points, such separations are not precise.
  • a C 5 stream may contain C 4 's and up to C 8 's.
  • These components may be saturated (alkanes), unsaturated (mono-olefins), or poly-unsaturated (diolefins). Additionally, the components may be any or all of the various isomers of the individual compounds.
  • Hydrogenation is the reaction of hydrogen with a carboncarbon multiple bond to "saturate" the compound. This reaction has long been known and is usually done at superatmospheric pressures and moderate temperatures using an excess of hydrogen over a metal catalyst.
  • metals known to catalyze the hydrogenation reaction are platinum, rhenium, cobalt, molybdenum, nickel, tungsten and palladium.
  • commercial forms of catalyst use supported oxides of these,metals. The oxide is reduced to the active form either prior to use with a reducing agent or during use by the hydrogen in the feed.
  • These metals also catalyze other reactions, most notably dehydrogenation at elevated temperatures. Additionally they can promote the ' reaction of olefinic compounds with themselves or other olefins to produce dimers or oligomers as residence time is increased.
  • FR-A-1302069 describes a process for the hydrogenation of a cracking fraction in the light naphtha range. During the process the entrained liquid in the liquid vapour mixture is removed by contact with a high surface area solid material.
  • the reaction should take place in a catalytic distillation system nor that the reaction could take place simultaneously with fractional distillation.
  • the C 5 refinery cut is valuable as a gasoline blending stock or as source of isoamylene to form an ether by reaction with lower alcohols.
  • Tertiary amyl methyl ether (TAME) is rapidly becoming valuable to refiners as a result of the recently passed Clean Air Act which sets some new limits on gasoline composition.
  • Some of these requirements are (1) to include a certain amount of "oxygenates”, such as methyl tertiary butyl ether (MTBE), TAME or ethanol, (2) to reduce the amount of olefins in gasoline, and (3) to reduce the vapor pressure (volatility).
  • the C 5 's in the feed to a TAME unit are contained in a single "light naphtha" cut which contains everything from C 5 'sthrough C 8 's and higher. This mixture can easily contain 150 to 200 components and thus identification and separation of the products is difficult. Usually the C 5 's and a small part of the C 6 's are separated for use in the TAME process. However, the incorporation of C 6 through C 8 tertiary olefins will allow the production of other valuable ether products. For this reason the TAME is not separated from heavier components, but all are used directly as octane blending stocks.
  • the present invention comprises feeding a light naphtha cut containing a mixture of hydrocarbons along with a hydrogen stream to a distillation column reactor containing a hydrogenation catalyst which is a component of a distillation structure and selectively hydrogenating the diolefins contained in the light naphtha.
  • the lighter components including the unreacted hydrogen, are distilled and separated as overheads from the partially hydrogenated light naphtha product.
  • a portion of the C 5 mono-olefins are isomerized to a more desirable feed for the TAME. Essentially all of the diolefins are converted to mono-olefins with very little hydrogenation of the mono-olefins.
  • the feed is predominately a C 5 stream
  • the light naphtha product is withdrawn as bottoms.
  • the overheads are passed to a condenser in which all of the condensibles are condensed and a portion refluxed to the top of the column.
  • the C 5 's are separated from the C 6 + components in the lower section of a distillation column reactor.
  • the C 6 + components are withdrawn as a bottoms stream while the C 5 's are boiled up into the upper section of the distillation column reactor which contains the catalytic distillation structure which selectively hydrogenates the diolefins.
  • the hydrogenated C 5 's are taken overheads along with the excess hydrogen and passed to the condenser in which all of the condensibles are condensed and subsequently separated from the uncondensibles (mostly hydrogen), for example in a reflux drum separator.
  • a portion of the liquid from the separator is returned to the distillation column reactor as reflux and the remainder withdrawn as product which may be directly charged to a TAME unit.
  • a further inert distillation section may be utilized above the catalytic distillation structure with a C 5 product side draw below to fractionate out the excess hydrogen along with any other light components such as air, water, etc. which might be troublesome in the downstream TAME unit.
  • the present invention is a process for the selective hydrogenation of diolefins contained in a light naphtha comprising the steps of:
  • Hydrogen is provided as necessary to support the reaction and to reduce the oxide and maintain it in the hydride state.
  • the distillation column reactor is operated at a pressure such that the reaction mixture is boiling in the bed of catalyst.
  • a "froth level" may be maintained throughout the catalyst bed by control of the bottoms and/or overheads withdrawal rate which improves the effectiveness of the catalyst thereby decreasing the height of catalyst needed.
  • the liquid is boiling and the physical state is actually a froth having a higher density than would be normal in a packed distillation column but less than the liquid without the boiling vapors.
  • the present process preferably operates at overhead pressure of said distillation column reactor in the range between 0 to 1723 kPag (0 and 250 psig) and temperatures within said distillation reaction zone in the range of 37 on to 149°C (100 to 300°F), preferably 54 to 133°C (130 to 270°F).
  • the C 5 feed and the hydrogen are preferably fed to the distillation column rector separately or they may be mixed prior to feeding.
  • a mixed feed is fed below the catalyst bed or at the lower end of the bed.
  • Hydrogen alone is fed below the catalyst bed and the C 5 stream is fed below the bed to about the mid one-third of the bed.
  • the pressure selected is that which maintains the dienes in the catalyst bed while allowing the propylene and lighter to distill overhead.
  • said hydrogenation catalyst comprising palladium oxide supported on alumina particles at an overhead pressure of the distillation column reactor in the range of 895 to 1447 kPag (130 to 210 psig) such that the temperature in said distillation reaction zone is between 110 and 133°C (230 and 270°F)
  • FIG. 1 is a simplified flow diagram of one embodiment of the present invention.
  • FIG. 2 is a simplified flow diagram of- a second embodiment of the present invention.
  • FIG. 3 is a simplified flow diagram of a third embodiment of the present invention.
  • FIG. 4 is a simplified flow diagram of a fourth embodiment of the present invention.
  • the advantages of utilizing a distillation column reactor in the instant selective hydrogenation process lie in the better selectivity of diolefin to olefin, conservation of heat and the separation by distillation which can remove some undesirable compound, e.g. heavy sulfur contaminants, from the feed prior to exposure to the catalyst and the distillation can concentrate desired components in the catalyst zone.
  • the diolefins contained in the C 5 cut are higher boiling than the other compounds and therefore can be concentrated in the catalyst zone while the mono-olefins are isomerized and removed in the upper part of the column.
  • the reactions of the C 5 's of interest are:
  • the first two reactions remove the undesirable components while the third is advantageous for feed to a TAME reactor.
  • the 3-methyl butene-1 does not react with methanol to produce TAME over the sulfonic acid catalyst while the two 2-methyl butenes do.
  • the catalytic material employed in the hydrogenation process must be in the form to serve as distillation packing.
  • the catalytic material is a component of a distillation system functioning as both a catalyst and distillation packing, i.e., a packing for a distillation column having both a distillation function and a catalytic function.
  • the reaction system can be described as heterogenous since the catalyst remains a distinct entity.
  • the catalyst may be employed as palladium oxide, preferably 0.1 to 1.0 weight %, supported on an appropriate support medium such as alumina, carbon or silica, preferably in containers as described herein or as conventional distillation packing shapes as Raschig rings, Pall rings, or saddles.
  • the cloth may be of any material which is not attacked by the hydrocarbon feeds or products or catalyst under the conditions of the reaction. Cotton or linen may be useful, but fiber glass cloth or TEFLON cloth is preferred.
  • a preferred catalyst system comprises a plurality of closed cloth pockets arranged and supported in the distillation column reactor by wire mesh intimately associated therewith.
  • Another suitable container consists of metal or plastic screen of suitable mesh size formed in a short cylinder, closed at each end, in which the catalyst is retained.
  • a plurality of these catalyst containing containers may be packed randomly or in a regular fashion into a bed within the distillation column reactor. There may be one or more of such beds, depending on the catalyst requirements of the process.
  • the particulate catalyst material may be a powder, small irregular chunks or fragments, small beads and the like.
  • the particular form of the catalytic material in the containers is not critical, so long as sufficient surface area is provided to allow a reasonable reaction rate.
  • the sizing of catalyst particles should be such that the catalyst is retained within the containers.
  • a catalyst suitable for the present process is 0.34 wt% Pd on 6.73 to 2.38 mm (3 to 8 mesh) Al 2 O 3 (alumina) spheres, supplied by United Catalysts Inc. designated as G-68C.
  • G-68C Typical physical and chemical properties of the catalyst as provided by the manufacturer are as follows: TABLE I Designation G-68C Form Sphere Nominal size 4.00 x 2.38mm (5x8 mesh) Pd. wt% 0.3 (0.27-0.33) Support High purity alumina
  • the catalyst is believed to be the hydride of palladium which is produced during operation.
  • the hydrogen rate to the reactor must be sufficient to maintain the catalyst in the active form because hydrogen is lost from the catalyst by hydrogenation.
  • the hydrogen rate must be adjusted such that it is sufficient to support the hydrogenation reaction and replace hydrogen lost from the catalyst but kept below that which would cause flooding of the column which is understood to be the "effectuating amount of hydrogen " as that term is used herein.
  • the mole ratio of hydrogen to diolefins in the feed to the fixed bed of the present invention will be at least 1.0 to 1.0 preferably 2.0 to 1.0.
  • the present invention carries out the method in a catalyst packed column which can be appreciated to contain a vapor phase ascending and some liquid phase as in any distillation. However since the liquid is held up within the column by artificial "flooding", it will be appreciated that there is an increased density over that when the liquid is simply descending because of what would be normal internal reflux.
  • FIG. 1 there is shown a simplified flow diagram in schematic of a preferred embodiment.
  • a distillation column reactor 10 containing a packing of suitable hydrogenation catalyst as part of a distillation structure 12, as in the wire mesh arrangement described above. the column may also have standard distillation structure 14.
  • the light naphtha is fed via line 1 to the distillation column reactor 10 below the catalyst packing.
  • the hydrogen is fed as a gas via flow line 2 at or near the bottom of the bed of catalyst packing.
  • Heat is added to the bottoms via flow line 4 by circulating through the reboiler 40 and back to the column via flow line 13. After the reaction has started the heat of reaction, which is exothermic, causes additional vaporization of the mixture in the bed.
  • Vapors are taken overhead through flow line 3 and passed to condenser 20 where substantially all of the condensible material is condensed to a temperature of 37°C (100°F).
  • the overheads are then passed to reflux drum 30 where the condensed material is collected and separated from non condensibles, such as the unreacted hydrogen.
  • a portion of the condensed materials collected in the reflux drum are returned to the top of the distillation column reactor 10 via flow line 6.
  • the distillate product, withdrawn through line 9 is a suitable feed for a TAME reactor.
  • the uncondensible material is vented from the reflux drum via flow line 7 and for economy the hydrogen can be recycled to the reactor (not shown).
  • Bottoms product containing essentially no C 5 diolefins is withdrawn via flow line 8 and may be sent to gasoline blending as stable gasoline.
  • the process is advantageous because the high heat of hydrogenation is absorbed by the vaporization of part of the liquid, so temperature control is achieved by adjusting the system pressure. All excess hydrogen is stripped from the bottoms product.
  • the unhydrogenated components are less volatile and tend to stay in the reactor for a longer time assisting in more complete reaction.
  • FIG. 2 there is shown a second embodiment of the invention wherein the light naphtha is fed to the column 10 above the catalytic distillation structure 12 via flow line 1'. Otherwise the arrangement is identical to FIG. 1.
  • FIG. 3 illustrates a third embodiment wherein the column includes additional conventional distillation structure 216 above the catalytic distillation structure 12 to separate any C 4 and lighter material, hydrogen, and other lower boiling components from the C 5 's which are withdrawn as side stream via flow line 209.
  • a three inch diameter 9 m (30 foot) tall steel column 310 with a reboiler 340, condenser 320 and reflux system 330 and 306 is used as shown in FIG. 4.
  • the middle 4.5 m (15 feet) are packed with a catalytic distillation structure 312 comprising 0.34 wt% palladium on 3.17 mm (1/8 inch) alumina spherical catalyst which is contained in the pockets of a fiber glass belt and twisted with stainless steel wire mesh.
  • the column is purged with nitrogen and pressure up to 137.8 kPag (20 psig).
  • Light naphtha feed which has been prefractionated to remove most of the C 6 + material is started to the column via line 301 at 22.5 kg/h (50 lbs/hr).

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Claims (12)

  1. Procédé d'hydrogénation sélective des dioléfines contenues dans un naphta léger, comprenant :
    (a) l'étape d'introduction (1) d'un premier courant comprenant un naphta léger contenant des dioléfines, et (2) d'un second courant contenant de l'hydrogène, dans un réacteur à colonne de distillation, au niveau d'une zone d'alimentation ;
    (b) concurremment, à l'intérieur dudit réacteur à colonne de distillation comportant des phases liquide et vapeur,
    - (i) l'étape de mise en contact du premier et du second courant à l'intérieur d'une zone de réaction/distillation, avec un catalyseur d'hydrogénation agissant comme une structure de distillation pour faire réagir ainsi lesdites dioléfines avec ledit hydrogène pour former des pentènes dans un mélange réactionnel, et
    - (ii) l'étape d'instauration dans le réacteur à colonne de distillation, d'une pression de tête qui est comprise entre 0 et 1.723 kPa.g (0 à 250 psig) de telle sorte que la température dans ladite zone de distillation est comprise entre 37 et 149°C (entre 100 et 300°F), et qu'une portion du mélange est vaporisée par la chaleur d'exothermicité de la réaction ;
    (c) l'étape de soutirage sous forme de «queues», à partir du réacteur à colonne de distillation, de la portion liquide issue de l'étape (b) (ii); et
    (d) l'étape de soutirage sous forme de «têtes», à partir du réacteur à colonne de distillation, de la portion vapeur issue de l'étape (b) (ii), en même temps que tout l'hydrogène n'ayant pas réagi.
  2. Procédé selon la revendication 1, dans lequel lesdites «têtes» sont refroidies afin de condenser tout produit condensable, et dans lequel ledit produit condensable est séparé dudit hydrogène n'ayant pas réagi, puis renvoyé sous forme de reflux, dans la partie supérieure dudit réacteur à colonne de distillation.
  3. Procédé selon la revendication 2, dans lequel la portion vapeur issue de l'étape (b) comprend une fraction légère en C5 à bas point d'ébullition, et le liquide issu de l'étape (b) comprend une fraction lourde en C6 à point d'ébullition élevé, et dans lequel le produit condensable contient des carbures en C5.
  4. Procédé selon la revendication 3, dans lequel une portion dudit produit condensable est soutiré sous forme de produit distillé.
  5. Procédé selon l'une quelconque des revendications 2 à 4 dans lequel ledit hydrogène séparé est recyclé dans ledit réacteur à colonne de distillation.
  6. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel ledit catalyseur d'hydrogénation comprend 0,34 % en poids d'oxyde de palladium supporté par des sphères d'aluminium de 3,17 mm (1/8 de pouce) formant une structure de distillation catalytique et est placé dans ledit réacteur à colonne de distillation.
  7. Procédé selon l'une quelconque des revendications 1 à 6 dans lequel l'hydrogène est contenu dans un second courant, en quantité assurant un ratio molaire entre l'hydrogène et lesdites dioléfines compris entre 1/1 et 2/1.
  8. Procédé selon l'une quelconque des revendications 1 à 7, dans lequel lesdits pentènes comprennent le 3-méthylbut-1-ène, et le 2-méthylbut-2-ène, et une portion dudit 3-méthylbut-1-ène est isomérisée en 2-méthylbut-2-ène.
  9. Procédé selon l'une quelconque des revendications 1 à 8 dans lequel un produit distillé contenant des composés en C5 est soutiré sous forme de courant latéral, au dessous du sommet dudit réacteur à colonne de distillation.
  10. Procédé selon l'une quelconque des revendications 1 à 9, contenant en plus, du 2-méthylbut-1-ène, du 2-méthylbuta-1,3-diène, du cis-penta-1,3-diène et du trans-penta-1,3-diène et faisant ainsi réagir lesdits 2-méthylbuta-1,3-diène, cis-penta-1,3-diène et trans-penta-1,3-diène avec ledit hydrogène pour former des pentènes, à une pression en tête d'environ 1,38 Mpa.g (200 psig) de telle sorte que le mélange au sein de ladite zone de réaction/distillation est à une température comprise entre 121 et 133°C (250 à 270°F).
  11. Procédé selon l'une quelconque des revendications 2 à 10 dans lequel l'hydrogène séparé est recyclé dans le réacteur à colonne de distillation.
  12. Procédé selon la revendication 1, dans lequel ledit catalyseur d'hydrogénation comprend de l'oxyde de palladium sur support de particules d'alumine, sous une pression en tête du réacteur à colonne de distillation comprise entre 895 et 1.447 kPa.g (130 à 210 psig) de sorte que la température dans ladite zone de réaction/distillation est comprise entre 110 et 133°C (230 à 270°F), comprenant les étapes
    (c) de soutirage sous forme de «queues», depuis ledit réacteur à colonne de distillation, d'une première portion du liquide issu de l'étape (b) (ii) ;
    (d) de soutirage sous forme d'un courant latéral, d'une seconde portion du liquide issu de l'étape (b);
    (e) de soutirage sous forme de «têtes», depuis ledit réacteur à colonne de distillation, d'une portion des vapeurs issues de l'étape (b) (ii), en même temps que tout l'hydrogène n'ayant pas réagi ;
    (f) de refroidissement desdites «têtes» à 37°C (110°F) pour condenser les composés condensables à cette température et sous des pressions dites « de tête » comprises entre 895 et 1.447 kPa.g (130 à 210 psig) ;
    (g) de séparation dudit produit condensé et de tout produit non condensé, dans lesdites «têtes», et de renvoi sous forme de reflux, dudit produit condensé, vers ledit réacteur à colonne de distillation ;
    (h) de soutirage sous forme de produit distillé, de la portion restante dudit produit condensé ; et
    (i) de recyclage vers le réacteur à colonne de distillation, de tout hydrogène n'ayant pas réagi, contenu dans ledit produit non condensé.
EP93300939A 1992-02-10 1993-02-09 Hydrogénation sélective de courants en C5 Expired - Lifetime EP0556025B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US83336092A 1992-02-10 1992-02-10
US833360 1992-02-10

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EP0556025A1 EP0556025A1 (fr) 1993-08-18
EP0556025B1 true EP0556025B1 (fr) 1997-11-26

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EP (1) EP0556025B1 (fr)
JP (1) JP3224444B2 (fr)
KR (1) KR100245018B1 (fr)
AU (1) AU654757B2 (fr)
BR (1) BR9300505A (fr)
CA (1) CA2089113C (fr)
DE (1) DE69315362T2 (fr)
MX (1) MX9300698A (fr)
MY (1) MY116459A (fr)
RU (1) RU2120931C1 (fr)

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FR2806093B1 (fr) * 2000-03-08 2002-05-03 Inst Francais Du Petrole Procede d'hydrogenation selective comprenant une separation partielle d'hydrogene par membrane en amont d'une colonne reactive
US6414205B1 (en) * 2000-03-24 2002-07-02 Catalytic Distillation Technologies Process for the removal of MAPD from hydrocarbon streams
DE10050711A1 (de) * 2000-10-13 2002-04-25 Basf Ag Verfahren zur Hydrierung von Aromaten mittels Reaktivdestillation
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DE69315362T2 (de) 1998-03-19
AU654757B2 (en) 1994-11-17
BR9300505A (pt) 1993-08-17
AU3280393A (en) 1993-08-12
MY116459A (en) 2004-02-28
KR930017847A (ko) 1993-09-20
JP3224444B2 (ja) 2001-10-29
DE69315362D1 (de) 1998-01-08
JPH05294851A (ja) 1993-11-09
RU2120931C1 (ru) 1998-10-27
MX9300698A (es) 1994-07-29
CA2089113C (fr) 2004-12-21
CA2089113A1 (fr) 1993-08-11
KR100245018B1 (ko) 2000-02-15
EP0556025A1 (fr) 1993-08-18

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