EP0271264B1 - Verfahren zur Oktanzahlsteigerung und zur Verringerung des Schwefelgehaltes von olefinischen Benzinen - Google Patents

Verfahren zur Oktanzahlsteigerung und zur Verringerung des Schwefelgehaltes von olefinischen Benzinen Download PDF

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Publication number
EP0271264B1
EP0271264B1 EP87310493A EP87310493A EP0271264B1 EP 0271264 B1 EP0271264 B1 EP 0271264B1 EP 87310493 A EP87310493 A EP 87310493A EP 87310493 A EP87310493 A EP 87310493A EP 0271264 B1 EP0271264 B1 EP 0271264B1
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EP
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Prior art keywords
zeolite
process according
olefinic
zsm
reforming
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Expired - Lifetime
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EP87310493A
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English (en)
French (fr)
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EP0271264A1 (de
Inventor
Randall David Partridge
Monique Anne Schorbert
Stephen Sui Fai Wong
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ExxonMobil Oil Corp
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Mobil Oil Corp
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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
    • C10G35/095—Catalytic reforming characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves

Definitions

  • This invention relates to a process for increasing the octane number while simultaneously reducing the sulfur content of olefinic gasolines derived from cracking processes, specifically catalytic cracking processes.
  • Certain hydrothermally stable catalysts such as those taught in U. S. Patent No. 3,493,519, employ an ammonium-Y crystalline aluminosilicate which is calcined in the presence of rapidly flowing steam.
  • the resultant steamed product is base-exchanged with an ammonium salt and treated with a chelating agent capable of combining with aluminum at pH between 7 and 9.
  • These aluminum-deficient catalysts are reported to exhibit enormously high activity (alpha value).
  • the resultant product has a silica-to-alumina mole ratios typically greater than 5 to 10, depending on the nature of the zeolite, preferably greater than 20, and more preferably greater than about 50.
  • An object of the present invention is therefore to provide such a reforming process.
  • the former specification discloses the conversion of hydrocarbon feeds containing sulfur and nitrogen contaminants with a catalyst comprising synthetic crystalline zeolite ZSM-20 combined with a hydrogenation function, in particular palladium. Particular applications of the process are polymerisation, aromitization, hydrocracking and catalytic cracking.
  • EP-A-0186479 discloses catalysts of highly developed shape selectivity based on zeolites typified by ZSM-5 and ZSM-11; such catalysts are disclosed to be particularly useful in aromatisation of paraffins.
  • the invention resides in a single-stage process for reducing the sulfur content and increasing the octane number of an olefinic containing feedstock
  • a catalyst comprising a large-pore crystalline zeolite intimately combined with 0.1 wt.% to 5 wt.% of a noble metal, said zeolite having a Constraint Index less than 2 and a framework silica to alumina molar ratio no less than 50:1, said contacting being conducted under a combination of conditions effective to form a product having a higher octane number than said feed, said conditions including a temperature of 700°-1000°F (370°-540°C), a pressure of 100-500 psig (790 to 3350 kPa), a LHSV of 2 to 16, and a hydrogen circulation rate of 1125 to 5260 SCF/bbl (200 to 1000 Nm3/m3).
  • the process of the present invention is directed to the reforming and desulfurization of olefinic gasolines derived from cracking processes, catalytic or otherwise. Without wishing to be limited to any set process, the description of the present invention will be directed to primarily catalytic cracking processes.
  • the olefinic gasoline may be processed at high temperatures and yield a product having increased octane number and reduced sulfur content.
  • reforming generally means a process of boosting the octane number of a naphtha or gasoline oil to an octane number that is acceptable for use.
  • straight run naphtha from crude oil might have an octane number of 40, too low for use as a gasoline. This unacceptable characteristic may be improved by reforming.
  • the naphtha may also contain an unacceptable level of sulfur, e.g., 50 parts per million (ppm), which is reduced by reforming under conditions set forth in this invention.
  • the present invention has a number of advantages over conventional reforming.
  • most of the reforming catalysts are limited to feedstocks having a 350°F (177°C) end point in the naphtha feedstock. Any feedstock higher than the 350°F (177°C) end point will tend to age the catalyst too rapidly.
  • the present catalyst may tolerate much higher end point feedstocks.
  • the feedstock for the present invention is generally a gasoline derived from catalytic cracking or thermocracking.
  • the catalytic cracking process may be either a fluid catalytic cracking (FCC) process or a thermofor catalytic cracking (TCC) process.
  • the feed stock may contain sulphur in concentrations greater than about 100 ppm, which normally would have to be reduced by hydrotreatment in order to allow the feed to be processed over a conventional reforming catalyst.
  • the feedstock contains olefins, which additionally would require hydrotreatment in order to be passed over a conventional reforming catalyst.
  • the feedstock for the present invention may have a boiling range which exceeds the boiling range of feedstocks conventionally processed over conventional reforming catalysts.
  • the catalysts used in the process of the invention are large pore zeolites having a Constraint Index less than 2 and a framework silica-to-alumina mole ratio of at least 50:1 and preferably greater than about 500:1.
  • Constraint Index is a convenient measure of the extent to which a zeolite provides control to molecules of varying sizes to its internal structure.
  • Zeolites which provide a highly restricted access to and egress from its internal structure have a high value for the Constraint Index, and zeolites of this kind usually have pores of small size, e.g., less than 5 Angstroms.
  • zeolites which provide relatively free access to the internal zeolite structure have a low value for the Constraint Index and usually pores of large size, i.e., greater than 8 Angstroms.
  • the method by which Constraint Index is determined is described fully in U. S. Patent No. 4,016,218.
  • Zeolites having a Constraint Index less than 2 are well known in the art and generally have a pore size in excess of 7 Angstom, that is sufficiently large to admit the vast majority of components normally found in a feed chargestock.
  • Suitable large pore zeolites for use in the present process are Zeolite Beta, Zeolite L, Zeolite Y (e.g. Ultrastable Y and Dealuminized Y), Mordenite, ZSM-3, ZSM-4, ZSM-18 and ZSM-20.
  • Constraint Index (CI) values for representative large pore zeolites are: CI (At Test Temperature) ZSM-4 0.5 (316°C) ZSM-20 0.5 (371°C) Mordenite 0.5 (316°C) Dealuminized Y (Deal Y) 0.5 (510°C) Zeolite Beta 0.6-2 (316°-399°C)
  • Constraint Index seems to vary somewhat with severity of operation (conversion) and the presence or absence of binders. Likewise, other variables, such as crystal size of the zeolite, the presence of occluded contaminants, etc., may affect the Constraint Index. Therefore, it will be appreciated that it may be possible to so select test conditions, e.g., temperatures, as to establish more than one value for the Constraint Index of a particular zeolite. This explains the range of Constraint Indices for Zeolite Beta.
  • zeolites for use in the present process are Zeolite ZSM-4 (described in U. S. Patent No. 3,923,639), Zeolite ZSM-20 (described in U. S. Patent No. 3,972,983), Zeolite Beta (described in U. S. Patent No. 3,308,069 and Re. 28,341), Zeolite Y (described in U. S. Patent No. 3,130,007) and modified forms of zeolite Y such as Ultrastable Y zeolite (described in U. S. Patent Nos. 3,293,192 and 3,449,070), dealuminized Y zeolite (U. S. Patent No. 3,442,795), and Zeolite UHP-Y (described in U. S. Patent No. 4,401,556).
  • the most preferred zeolite is a zeolite Y which may be treated by known methods, by steaming and/or acid dealumination, to raise its silica/alumina ratio to at least 50:1.
  • crystalline zeolites In practicing the process of the present invention, it may be useful to incorporate the above-described crystalline zeolites with a matrix comprising another material resistant to the temperature and other conditions employed in the process. Such matrix material is useful as a binder.
  • Useful matrix materials include both synthetic and naturally-occurring substances, as well as inorganic materials such as clay, silica and/or metal oxides.
  • the latter may be either naturally-occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides.
  • Naturally-occurring clays which can be composited with the zeolite include those of the montmorillonite and kaolin families, which families include the sub-bentonites and the kaolins commonly known as Dixie, McNamee-Georgia and Florida clays or others in which the main mineral constituent is haloysite, kaolinite, dickite, nacrite or anauxite.
  • Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification.
  • the zeolites employed herein may be composited with a porous matrix material, such as alumina, silica, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, and silica-titania, as well as ternary compositions, such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia.
  • the matrix may be in the form of a cogel.
  • the relative proportions of zeolite component and inorganic oxide gel matrix, on an anhydrous basis, may vary widely with the zeolite content ranging from between 1 to 99 wt %, and more usually in the range of 5 to 80 wt % of the dry composite.
  • the original cations associated with each of the crystalline zeolites utilized herein may be replaced by a wide variety of other cations, according to techniques well known in the art. Typical replacing cations including hydrogen, ammonium, alkyl ammonium and metal cations, including mixtures of the same.
  • the crystalline zeolite utilized in the process of this invention is employed in intimate combination with a noble metal, such as platinum or platinum in combination with other Group VIII metals, e.g., platinum-rhenium or platinum-iridium, in an amount between 0.1 to 5 wt %, and preferably 0.3 to 3 wt %.
  • a noble metal such as platinum or platinum in combination with other Group VIII metals, e.g., platinum-rhenium or platinum-iridium
  • Such component can be exchanged into the composition, impregnated thereon, or physical intimately admized therewith.
  • Such component can be impregnated into or onto the zeolite, such as, for example, in the case of platinum, by treating the zeolite with a platinum metal-containing ion.
  • suitable platinum compounds include chloroplatinic acid, platinous chloride and various compounds containing the platinum amine complex.
  • the present process is essentially a reforming process, in that the reactions which take place are reforming reactions.
  • the process cannot be called a reforming process per se since it passes an olefinic-containing feed at a high temperature over the catalyst and directly cyclizes the olefins to aromatics. Automatically, the process increases the octane value and reduces the sulfur content of the olefinic-containing feedstock.
  • the process of the present invention (1) accepts olefinic-containing feedstocks, (2) accepts surful-containing feedstocks, and (3) accepts feedstocks with a high boiling point, i.e., in excess of 350°F (177°C).
  • the feedstock is contacted with the catalyst in the presence of hydrogen under conditions of temperature, pressure, space velocity and hydrogen ratio similar to those used in conventional reforming processes.
  • the conditions include temperatures of 700° to 1000°F (370°-540°C), pressures from 100 to 500 psig (790 to 3550 kPa), space velocities from 2-16 LHSV, and hydrogen circulation rate of 1125 to 5620 SCF/bbl (200 to 1000 Nm3/m3).
  • the process may be conveniently operated in conventional equipment, i.e., in a series of reactors with inter-stage heating to maintain the desired reactions and heat balance.
  • a particular advantage of the use of the high siliceous zeolite supports is that the need for acidity maintenance by chlorination, use of water co-feed and the like is substantially reduced and may, in favorable circumstances, be eliminated. Nonetheless, if experience demonstrates that the use of these conventional expedients is necessary or desirable, resort may be made to them.
  • water may be fed in with the feedstock in conventional amounts, typically of 1 to 100 ppm, or halogenation may be used to maintain activity, for example, by incorporation of the halogen in the form of an acid or a salt or by addition of the halogen or halide compound during the reforming process itself, in a conventional manner.
  • Chlorine is the preferred halogen. Details of the halogen activity maintenance methods may be found in U. S. Patent Nos. 4,261,810; 4,049,539; 3,835,063; 6,661,768; and 3,649,524.
  • the catalyst used was prepared by steaming and acid dealumination of a Linde Ultrastable Y, followed by impregnation with platinum as the tetraamine.
  • the resultant dealuminized Y zeolite was analyzed and found to have a bulk SiO2/Al2O3 ratio of 45, with an approximate framework, i.e., tetrahedral alumina, SiO2/Al2O3 of 2600 by MAS NMR.
  • the activity represented by the alpha value of this material was determined to be 1.5, in good agreement with the appropriate framework aluminum content.
  • the platinum loading was determined to be 0.48% and had a substantially uniform dispersion of 96%, as determined by hydrogen chemisorption.
  • the intermediate boiling range fraction (180°-300°F) was used as the feed for the process of this Example. Additional analyses indicated that this fraction was composed of 17% paraffins, 44% olefins, and 27% aromatics by weight. Process conditions of 900°F (482°C), 250 psig (1825kPa), 4.0 LHSV and about 4000 SCF/bbl (712Nm3/m3) hydrogen flow were used to simultaneously desulfurize and increase the octaine rating of the olefinic FCC gasoline. For eighteen days prior to charging the FCC gasoline fraction, the dealuminized Y zeolite catalyst of the invention was used for reforming a number of conventional feeds.
  • Example 2 The catalyst utilized in Example 2 was the same catalyst as in Example 1.
  • the feedstock for Example 2 was FCC gasoline which was distilled and cut at 180°F (82°C) and 300°F (149°C).
  • a complete analysis of the full range FCC gasoline and of the cuts is given in Table 3.
  • cut 2 and cut 3 contain significant amounts of olefins (16% and 8%, respectively) and aromatics (37% and 61%, respectively). As a result, their octane is already high (88 and 90 RON+0). However, upon hydrotreating to remove the sulfur and nitrogen, the octane would drop considerably. Thus, the purpose of the present example is to find a way to maintain or even increase the level of octaine while removing the sulfur and nitrogen.
  • the catalyst was heated to 300°F (149°C) under hydrogen atmosphere, kept at that temperature for 2 hours, and then slowly heated to 660°F (349°C) at a rate of 90°F (50°C) per hour.
  • the feed was started after the catalyst had been at 660°F (349°C) for 2 hours.
  • the temperature was then increased to the desired reaction temperature.
  • the FCC gasoline heart cut (cut 2) was then added and maintained on-stream for 3 weeks at a temperature of 900°F (482°C).
  • the feed was then changed to the heavy FCC gasoline fraction (cut 3) for a period of 2 weeks. Although the fractions were processed separately, it is believed that the fractions may be co processed.
  • the light olefinic fraction which already had a high octane rating (92.5 RON) and a relatively low sulfur content (0.04 wt %), did not appear to need further upgrading, although it may be treated by conventional means to reduce mercaptans.
  • the runs were compared with runs using a standard chlorided platinum on alumina reforming catalyst.
  • the heavy FCC gasoline fraction is presently hydrotreated in a number of refineries to remove sulfur. Both the high sulfur level of about 8000 ppm and high end point of about 450°F (232°C) preclude conventional hydrotreating/reforming. The results here indicate that net gasoline yields on this fraction, approaching 97 vol %, could be achieved with an octane gain of about 13 RON and a reduction of sulfur in the product to less than 10 ppm.
  • the present process offers the potential for both increasing the overall FCC gasoline pool octane and reducing the level of sulfur.
  • Direct processing of the intermediate and heavy FCC gasoline fractions using a process of this type could be an attractive alternative to conventional hydrotreating/reforming or hydrodesulfurization of FCC feeds.
  • the catalyst can operate in the presence of a higher level of sulfur without any significant aging of the catalyst.
  • the conventional reforming processes can tolerate olefins in the feed which generally tend to coke very rapidly over conventional catalysts at reforming conditions.
  • the net result of this process is a high octane gasoline that is low in sulfur with a minimal loss of yield.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (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 (7)

  1. Einstufiges Verfahren zur Verringerung des Schwefelgehaltes und zur Erhöhung der Oktanzahl eines olefinischen Benzins, das vom katalytischen Wirbelschicht- oder Thermoforcracken von Gasölen abgeleitet ist, das den Kontakt von olefinhaltigem Ausgangsmaterial und Wasserstoffgas mit einem Katalysator umfaßt, der einen kristallinen Zeolith mit großen Poren umfaßt, der eng mit 0,1 bis 5 Gew.-% eines Edelmetalls verbunden ist, wobei dieser Zeolith einen Zwangsindex von weniger als 2 und ein Siliciumdioxid/Aluminiumoxid-Molverhältnis des Gitters von nicht weniger als 50:1 aufweist, wobei dieser Kontakt bei Kombination wirksamer Bedingungen durchgeführt wird, um ein Produkt mit höherer Oktanzahl als die Zufuhr zu bilden, wobei diese Bedingungen eine Temperatur von 370 bis 540°C (700 bis 1000°F), einen Druck von 790 bis 3350 kPa (100 bis 500 psig), eine LHSV von 2 bis 16 und eine Wasserstoffzirkulationsmenge von 200 bis 1000 Nm³/m³ (1125 bis 5260 SCF/bbl) umfassen.
  2. Verfahren nach Anspruch 1, dadurch gekenzeichnet, daß der Schwefel mit einer Konzentration von mehr als 100 ppm im Ausgangsmaterial vorhanden ist.
  3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das olefinhaltige Ausgangsmaterial vom katalytischen Crackverfahren abgeleitet ist.
  4. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß der Zeolith ein SiO₂/Al₂O₃-Verhältnis des Gitters von mehr als 500:1 aufweist.
  5. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß der kristalline Zeolith aus Zeolith Beta, Zeolith L, Zeolith Y, Mordenit, ZSM-3, ZSM-4, ZSM-18, ZSM-20 abgeleitet ist.
  6. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß der Zeolith Zeolith Y ist.
  7. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das Edelmetall Platin oder Platin in Kombination mit einem anderen Metall der Gruppe VIII ist.
EP87310493A 1986-12-04 1987-11-27 Verfahren zur Oktanzahlsteigerung und zur Verringerung des Schwefelgehaltes von olefinischen Benzinen Expired - Lifetime EP0271264B1 (de)

Applications Claiming Priority (2)

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US93784486A 1986-12-04 1986-12-04
US937844 1997-08-25

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EP0271264A1 EP0271264A1 (de) 1988-06-15
EP0271264B1 true EP0271264B1 (de) 1992-09-02

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EP (1) EP0271264B1 (de)
JP (1) JP2598051B2 (de)
CN (1) CN1015639B (de)
AU (1) AU596245B2 (de)
CA (1) CA1295275C (de)
DE (1) DE3781528T2 (de)
ES (1) ES2033881T3 (de)
FI (1) FI94394C (de)
PH (1) PH24485A (de)
PT (1) PT86294B (de)
TR (1) TR25245A (de)
ZA (1) ZA879144B (de)

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US7563358B2 (en) 2006-08-24 2009-07-21 Exxonmobil Chemical Patents Inc. Process for the production of benzene, toluene, and xylenes

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GB8926555D0 (en) * 1989-11-24 1990-01-17 Shell Int Research Process for upgrading a sulphur-containing feedstock
GB2249554A (en) * 1990-11-09 1992-05-13 Shell Int Research Upgrading sulphur-containing feedstock
AU658937B2 (en) * 1991-11-19 1995-05-04 Mobil Oil Corporation Hydrocarbon upgrading process
US5290534A (en) * 1992-11-09 1994-03-01 Mobil Oil Corporation Method for removing organic residue from as-synthesized ZSM-18
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US5576256A (en) * 1994-05-23 1996-11-19 Intevep, S.A. Hydroprocessing scheme for production of premium isomerized light gasoline
DE69508601T2 (de) * 1994-10-03 1999-12-09 Sanyo Petrochemical Co Ltd Verfahren zur herstellung von aromatischen kohlenwasserstoffen
WO2000029509A1 (en) * 1998-11-16 2000-05-25 Mobil Oil Corporation Desulfurization of olefinic gasoline with a dual functional catalyst at low pressure
ES2179753B1 (es) * 2000-10-11 2005-02-16 Universidad Politecnica De Valencia Proceso y catalizadores para la eliminacion de compuestos de azufre de la fraccion gasolina.
US20020148758A1 (en) * 2001-02-08 2002-10-17 Yun-Feng Chang Gasoline hydrodesulfurization
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JP4931052B2 (ja) * 2006-08-30 2012-05-16 Ｊｘ日鉱日石エネルギー株式会社 ガソリン基材の製造方法
JP5196391B2 (ja) * 2006-11-29 2013-05-15 石油コンビナート高度統合運営技術研究組合 低硫黄炭化水素油の製造方法
JP5328585B2 (ja) * 2009-07-10 2013-10-30 Ｊｘ日鉱日石エネルギー株式会社 ガソリン組成物
KR20190031440A (ko) * 2016-05-16 2019-03-26 메그 에너지 코오퍼레이션 열분해된 탄화수소 스트림의 직접 올레핀 저감

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US4097367A (en) * 1977-07-25 1978-06-27 Mobil Oil Corporation Conversion of olefinic naphtha
US4377468A (en) * 1979-01-22 1983-03-22 Mobil Oil Corporation Sulfur- and nitrogen-containing hydrocarbon feed hydrocracking over ZSM-20
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US4604189A (en) * 1984-12-24 1986-08-05 Mobil Oil Corporation Hydrocracking of heavy feeds with dispersed dual function catalyst
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7563358B2 (en) 2006-08-24 2009-07-21 Exxonmobil Chemical Patents Inc. Process for the production of benzene, toluene, and xylenes

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JP2598051B2 (ja) 1997-04-09
AU596245B2 (en) 1990-04-26
FI875343A (fi) 1988-06-05
CN1015639B (zh) 1992-02-26
JPS63159494A (ja) 1988-07-02
PH24485A (en) 1990-07-18
PT86294B (pt) 1990-11-07
DE3781528T2 (de) 1993-04-15
CA1295275C (en) 1992-02-04
ZA879144B (en) 1989-07-26
TR25245A (tr) 1992-12-01
PT86294A (en) 1988-01-01
CN87107315A (zh) 1988-06-15
DE3781528D1 (de) 1992-10-08
EP0271264A1 (de) 1988-06-15
FI94394C (fi) 1995-09-11
ES2033881T3 (es) 1993-04-01
FI94394B (fi) 1995-05-31
FI875343A0 (fi) 1987-12-03
AU8168087A (en) 1988-06-09

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