EP0203228B1 - Procédé d'hydrotraitement en une étape - Google Patents
Procédé d'hydrotraitement en une étape Download PDFInfo
- Publication number
- EP0203228B1 EP0203228B1 EP85201248A EP85201248A EP0203228B1 EP 0203228 B1 EP0203228 B1 EP 0203228B1 EP 85201248 A EP85201248 A EP 85201248A EP 85201248 A EP85201248 A EP 85201248A EP 0203228 B1 EP0203228 B1 EP 0203228B1
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- EP
- European Patent Office
- Prior art keywords
- catalyst
- stacked
- bed
- hydrotreating
- zone
- Prior art date
- 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
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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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
Definitions
- the present invention relates to a single-stage hydrorefining process for treating heavy oils using catalysts arranged in a particular manner, referenced to herein as "stacked bed". It particularly relates to a single-stage hydrorefining process for treating oils having a tendency to deactivate hydrotreating catalysts by coke formation, these being oils with high boiling components and/or oils with a low asphaltene content and very high boiling components, with a particular stacked bed catalyst arrangement. It has been found that the use of a stacked bed increases the catalyst life or allows increased conversions relative to the more traditional catalysts used for the treating of these oils.
- the invention is particularly useful for meeting the demands of increasing hydrotreatment severity, such as sulphur removal, for poorer quality heavy oil fractions both directly distilled or extracted from crude or crude fraction and oil fractions from thermal, steam, or catalytic cracking processes including mixtures of any of these materials.
- oils with high boiling components about 343°C-538°C and/or oils with a low asphaltene content and with very high boiling components (above 538°C) can be treated in a single stage hydrotreating process with improved catalyst-system life and/or increased hydrotreating conversions for a given feedstock.
- the process according to the present invention allows easy conversion of existing catalytic hydrotreating reactors to a stacked bed of specified catalysts.
- the present process operates well at hydrogen pressures below 75 bar (7500 kPa), so that no additional high pressure reactors need be constructed.
- the particular stacked bed combination of catalysts in accordance with the invention results in longer runs between replacements or regenerations for a given oil than would be experienced with either catalyst used alone.
- poorer quality oils can be processed at equivalent conversions or higher conversions for a given oil can be maintained with the same time between replacement or regeneration with the use of the single-stage stacked bed catalyst system according to the present invention.
- the invention can be applied most usefully in situations where rapid catalyst deactivation is occurring.
- the present invention thus relates to a process for catalytically hydrotreating hydrocarbon oils at elevated temperature and pressure in the presence of hydrogen by passing:
- the process according to the present invention is particularly suitable for systems where catalyst deactivation due to coking is a constraint.
- the bottom bed catalyst is preferably Ni-promoted when nitrogen removal is the predominant concern and is preferably Co-promoted when sulphur removal is the predominant concern.
- oils having a) final boiling point above 538°C whilst having a heptane asphaltenes content less than about 2% by weight, b) final boiling points in the range between 343°C and 538°C, or c) mixtures thereof are contacted with hydrogen or a hydrogen-containing gas and passed downwardly under hydrodesulphurization conditions over a stacked-bed catalyst.
- the boiling points referred to in the present description are as defined by the American Society for Testing and Materials (ASTM) method D 2887-83 ("Boiling Range Distribution of Petroleum Fractions by Gas Chromatography") and is commonly known as TBP-GLC (true boiling point by gas liquid chromatography).
- ASTM American Society for Testing and Materials
- TBP-GLC true boiling point by gas liquid chromatography
- oils to be used as feedstock in the process according to the present invention will be oils having a tendency to deactivate hydrotreating catalysts by coke formation, under hydrotreating conditions and particularly under hydrodesulphurization conditions.
- feedstocks to be applied in the process in accordance with this invention may be taken from straight run oils (non-cracked) or thermally-, steam-, or catalytically cracked hydrocarbonaceous materials.
- Suitable feeds include petroleum derived gas oils distilled from crude or crude fractions at atmospheric or at reduced pressure; solvent extracted oils such as extracted oils commonly referred to as Deasphalted Oils; thermally or steamed cracked oils or fractions thereof such as coker gas oils; gas oils or cycle oils from catalytic cracking and mixtures of two or more of the above materials.
- feedstocks after initial treating in accordance with the process according to the present invention are also possible.
- suitable uses may include feed and additions to feed to units for significant molecular weight reduction such as catalytic cracking units or hydrocracking units; direct use or by blending with other oils or additives for sale as transportation fuels such as diesel oils; or for refinery fuel.
- the stacked-bed catalyst system to be used in the process according to the present invention comprises firstly a normally Ni- and P-containing conventional hydrotreating catalyst.
- the second catalyst to be contacted by the oil normally comprises a low- or no-phosphorus content conventional catalyst.
- the second catalyst contains no phosphorus.
- the second catalyst is also a conventional catalyst and contains Ni and/or Co in the formulation.
- the second catalyst contains Co in preference to Ni; when denitrogenation is the primary objective, the second catalyst preferably contains Ni in preference to Co.
- the catalysts herein can be prepared by techniques well known in the art. The advantages of this invention primarily accrue from the particular combination of operable hydrotreating catalysts in a stacked-bed rather than from any particular method or manner of fabricating the catalyst.
- the first main hydrotreating zone catalyst used in the process according to the present invention suitably comprises a Ni- and P-containing conventional hydrotreating catalyst.
- Conventional hydrotreating catalysts which are suitable for the first catalyst zone generally comprise a phosphorus oxide and/or sulphide component and a component, selected from group VIB of the Periodic Table and a group VIII metal or metal oxide, or metal sulphide and/or mixtures thereof composited with a support. These catalysts will contain up to 10%w, usually 1 to about 5%w of the group VIII metal compound calculated on the base of the metal content, from 3 to about 15%w of the group VIB metal compound calculated on the base of the metal content, and from 0.1 to 10%w phosphorus compounds calculated on the base of phosphorus content.
- the catalyst comprises a nickel component and a molybdenum and/or tungsten component with an alumina support which may additionally contain silica.
- a more preferred catalyst comprises a nickel component, a molybdenum component, and a phosphorus component with an alumina support which may also contain small amounts of silica.
- Preferred amounts of components range from 2 to 4%w of a nickel component calculated on the base of metal content 8-15%w of a molybdenum component calculated on the base of metal content, and 1 to 4%w, more preferably 2 to 4%w, of a phosphorus component calculated on the base of the phosphorus content.
- the catalyst can be used in any of a variety of shapes such as spheres and extrudates. The preferred shape is a trilobal extrudate.
- the catalyst is suphided prior to use, as is well known to the art.
- Low-phosphorus content catalysts having high surface areas (greater than about 200 m 2 /g) and high compacted bulk densities (0.6-0.85 g/cm 3 ) are preferably used for the second zone as they appear to be highly active.
- the high surface area increases reaction rates due to generally increased dispersion of the active components.
- Higher density catalysts allow one to load a larger amount of active metals and promoter per reactor volume, a factor which is commercially important.
- the metal content specified above provides high activity per reactor volume. Lower metal contents normally result in catalysts exerting two low activities for proper use in the process according to the present invention. Higher metal loadings than specified above do not contribute significantly to the performance and thus lead to an inefficient use of the metals resulting in high catalyst cost with little advantage.
- the second zone catalyst can be used like the first zone catalyst in a variety of shapes.
- the catalyst is sulphided prior to use as is well known to the art.
- the Ni-containing catalyst used for the first zone is preferably a high activity conventional catalyst suitable for high levels of hydrogenation.
- Such catalysts have high surface areas (greater than 140 m 2 /g) and high compacted bulk densities (0.65-0.95 g/cm 3 , more narrowly 0.7-0.95 g/cm 3 ).
- the high surface area increases reaction rates due to generally increased dispersion of the active components.
- Higher density catalysts allow one to load a larger amount of active metals and promoter per reactor volume, a factor which is commercially important.
- the metal and phosphorus content specified above provides the high activity per reactor volume. Lower metal contents result in catalysts exerting too low activities for proper use in the process according to the present invention.
- a low-phosphorus or no-phosphorus conventional hydrotreating catalyst is used in the second zone of the catalyst system.
- Co and/or Ni containing conventional catalysts can be suitably applied.
- the second zone catalyst differs from the first zone catalyst primarily in its low-phosphorus content (less than 0.5%w).
- the preferred catalyst contains less than about 0.5%w phosphorus and comprises a component from group VIB and a group VIII metal or metal oxide, or metal sulphide and/or mixtures thereof composited with a support.
- the catalyst comprises a nickel and/or cobalt component and a molybdenum and/or tungsten component with an alumina support which may additionally contain silica.
- Preferred metal contents are up to 10%w, usually 1 to 5%w of group VIII metal component(s) calculated on the base of the metal content, and from 3 to 30%w of group VIB metal component(s) in the base of the metal content.
- a more preferred catalyst comprises a cobalt or nickel component and a molybdenum component with an alumina support.
- the present invention preferably relates to a process for hydrotreating oils having a tendency to deactivate hydrotreating catalysts by coke formation, by passing a) oils having a final boiling point above 538°C and having less than 2%w of heptane asphaltenes, b) oils having a final boiling point from 343°C to 538°C, or c) mixtures thereof downwardly with hydrogen or a hydrogen-containing gas (mixture) into a hydrotreating zone over a stacked-bed of two hydrotreating catalysts under conditions suitable to convert more than 25% of the sulphur compounds present to H 2 S, wherein said stacked-bed comprises an upper zone containing of from 15-85%v, based on total catalyst, of a high-activity hydrotreating catalyst which comprises from 2-4%w nickel, from 8-15%w molybdenum and from 1-4%w phosphorus supported on a carrier consisting mostly of alumina, and a lower zone containing of from 15-85%v, basis total catalyst, of a high-activity,
- the physical characterizations of the catalysts referred to herein are common to those skilled in the catalyst development art.
- Surface areas refer to nitrogen adsorption surface areas preferably determined by at least three points.
- Pore size distributions are determined by mercury intrusion and calculated with a 130 degree contact angle.
- Pore volumes stated are water pore volumes and indicate the volume of water per weight of catalyst necessary to fill the catalyst pores to an incipient wetness of the catalyst.
- the volume of the first catalyst zone in the present invention is from 15 to 85%v of the main catalyst charge.
- the remaining fraction of the main catalyst charge is composed of the second catalyst.
- the division of the catalyst volumes over the zones in the bed depends upon the requirement for nitrogen conversion versus the requirements for stability and other hydrotreating reactions such as sulphur and metals removal. Stacked-beds can be used to tailor the amount of nitrogen removal, sulphur and metals removal, and system stability.
- An increase in the first catalyst will increase the nitrogen removal but will effect the hydrodesulphurization (HDS) activity and stability of the system. Below a catalyst ratio of 15:85 or above a catalyst ratio of 85:15 (upper:lower) the benefits for the stacked-bed system are not large enough to be of practical significance. There is no physical limit on using a smaller percentage of one or the other beds.
- the catalyst zones referred to herein may be in the same or different reactors. For existing units with one reactor the catalysts are layered one on top of the other. Many hydrotreating reactors consist of two or more reactors in series. The catalyst zones are not restricted to the particular volume of one vessel and can extend into the next (prior) vessel. The zones discussed herein refer to the main catalyst bed. Small layers of catalysts which are different sizes are frequently used in reactor loading as is known to those skilled in the art. lntervessel heat exchange and/or hydrogen addition may also be used in the process according to the present invention.
- the pore size of the catalyst does not play a critical role in the process according to the present invention.
- the catalysts in the two zones may be based upon the same carrier. Normally, the finished catalysts will have small differences in their average pore sizes due to the differences in the respective metal and phosphorus loadings.
- Hydrogen partial pressure is very important in determining the rate of catalyst coking and deactivation. At pressures below 6.8 bar, the catalyst system cokes too rapidly even with better quality oil containing high boiling components. At pressures above 75 bar, the deactivation mechanism of the catalyst system appears to be predominantly that of metals deposition, if present, which results in pore-mouth plugging. Catalysts of varying porosity can be used to address deactivation by metals deposition, as is known by those skilled in the art.
- the hydrogen to feed ratio to be applied in the process according to the present invention is required to be above 17 NI/kg feed since the reactions occurring during hydrotreating consume hydrogen, resulting in a deficiency of hydrogen at the bottom of the reactor. This deficiency may cause rapid coking of the catalyst and leads to impractical operation. At hydrogen to feed ratios in excess of 890 NI/kg feed, no substantial benefit is obtained; thus the expense of compression beyond this rate is not warranted.
- Nitrogen removal is an important factor in hydrotreating heavy oils. Catalysts without phosphorus can be more stable with heavy oils under the conditions noted above; however, nitrogen removal activity is low for no-phosphorus catalysts relative to their phosphorus promoted counterparts. Additionally, Co promoted catalysts are less active for nitrogen removal than are Ni promoted catalysts. Stacked catalyst beds can be used to tailor the amount of nitrogen removal, sulphur and metals removal, and system stability. It has been found that a stacked-bed system also improves activities (other than nitrogen removal) as well as the stability of the overall catalyst system relative to either catalyst used individually. The stacked-bed catalyst system is applicable when processing feeds under conditions where a heavy feed is causing deactivation primarily by coking.
- the process according to the present invention should be operated at conditions suitable to remove at least 25% and generally conditions will be applied to remove 30-80%, more preferably 45-75%, of the sulphur in the feed.
- metals such as Ni and V are present in the feed and demetallization is the primary focus the process can be operated at the lower levels of desulphurization.
- there is little metal in the feed and demetallization is not the primary goal, one can operate the process at higher sulphur removal rates.
- a catalyst A containing nickel, molybdenum and phosphorus supported on a gamma alumina carrier was prepared from commercially available alumina powders. This carrier was extruded into 1.6 mm pellets having a trilobal cross section. The pellets were dried and calcined before being impregnated with the appropriate catalytically active metals by a dry pore volume method i.e., by adding only enough solution to fill the alumina pore volume. Carriers containing in addition to alumina, a few per cent of other components like silica or magnesia can also be applied.
- a catalyst B containing cobalt and molybdenum supported on a similar alumina carrier as used to prepare catalyst A was prepared.
- this carrier was also extruded into 1.6 mm pellets having a trilobal cross-section. The pellets were dried before being impregnated with the appropriate catalytically active metals by a dry pore volume method.
- An appropriate aqueous solution of cobalt carbonate, ammonium dimolybdate and ammonia was used to impregnate the carrier.
- the metal loadings and properties of the dried, calcined catalyst (B) are also given in Table II.
- Fig. 1 the reactor inlet temperature (RIT in °C) necessary to maintain 0.3% weight sulphur in the product is graphically represented as a function of time (days), which is a convenient measure of general catalyst activity.
- the Ni-Mo-P catalyst data are represented as circles (upper line), the Co-Mo catalyst data as triangles (middle line) and the stacked catalyst data as diamonds (lower line).
- the stacked-bed system has good activity and stability for sulphur removal as well as denitrification advantages.
- the average feed properties and average unit conditions are given in Table III.
- the feed applied was a heavy vacuum gas oil having a final boiling point above 538°C and containing less than 2%w of heptane asphaltenes. Feed to the unit and unit conditions were remarkably constant during the runs considering the unit is a commercial unit.
- the Ni-Mo-P catalyst formed about 33% of the main catalyst load while the Co-Mo catalyst made up the remainder of the main catalyst load. Oil and gas flowed in a single-stage and serially over first the Ni-Mo-P catalyst and then over the Co-Mo catalyst.
- the main advantages of the stacked-bed system shown by this Example comprises a) a significant increase in catalyst stability as can be seen in Fig. 1 where the increase in RIT with time is significantly less for the stacked-bed system (3.1°C/month versus 12.5°C/month) relative to the single catalyst system; b) an increase in catalyst activity as represented by about a 8.1°C lower initial RIT for the same level of sulphur in the product; c) a resulting greatly improved estimated catalyst life of about 400% for the stacked-bed relative to the single bed due to the improvements in activity and stability. An end of run temperature of 416°C and a continued linear decline rate was used to estimate the catalyst life of the stacked-bed system.
- a second set of two commercial runs with a Ni-Mo-P/alumina catalyst and a stacked-bed of a Ni-Mo-P/alumina catalyst over a Co-Mo/alumina catalyst was also carried out.
- a Ni-Mo-P/alumina catalyst would be one that one skilled in the art would traditionally have chosen for this feedstock when considering hydrogenation, denitrification, and desulphurization catalyst activity rather than a Co-Mo catalyst.
- Table IV summarizes approximate average unit conditions and feedstock.
- the oil is a blend of straight run vacuum gas oil (distilled from non-cracked oil) and a coker heavy gas oil.
- Table V the approximate average performance for the two runs at two catalyst ages is summarized and in Figure 2 the reactor outlet temperature necessary to maintain 0.75% weight and 0.60% weight sulphur in the product for the single catalyst and the stacked bed system is depicted as a function of time (days).
- the main advantage of the stacked-bed system relative to the single bed system shown by this Example comprise a) higher sulphur conversion, even at lower operating temperatures, b) greater catalyst stability when processing the same type feed-about first 60 days-, c) processing a heavier feed at comparable stabilities-about after 60 days-, and d) greater hydrogen addition even at lower operating temperatures.
- the single bed system has a lower start of run temperature in the first one or two weeks but this temperature relates to 0.75%w sulphur in the product where the temperature for the stacked-bed system relates to 0.60%w sulphur in the product.
- a third set of two commercial runs with a Ni-Mo-P/alumina catalyst and a stacked-bed of a Ni-Mo-P/alumina catalyst and a Co-Mo/alumina catalyst was also made.
- the feed used has a final boiling point between 343°C and 538°C and contained straight run light gas oil, coker naphtha, coker light gas oil and light cycle oil.
- Table VI the approximate average unit conditions and feed stock properties are summarized. Analysis of the data for these two runs showed that the stacked-bed used in accordance with the present instant invention showed the following advantages when compared to the single catalyst:
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Claims (12)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US735620 | 1985-05-21 | ||
US06/735,620 US4776945A (en) | 1984-11-30 | 1985-05-21 | Single-stage hydrotreating process |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0203228A1 EP0203228A1 (fr) | 1986-12-03 |
EP0203228B1 true EP0203228B1 (fr) | 1989-05-10 |
EP0203228B2 EP0203228B2 (fr) | 1996-10-23 |
Family
ID=24956534
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP85201248A Expired - Lifetime EP0203228B2 (fr) | 1985-05-21 | 1985-07-29 | Procédé d'hydrotraitement en une étape |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0203228B2 (fr) |
JP (1) | JPH0633364B2 (fr) |
CN (1) | CN1006230B (fr) |
BR (1) | BR8503786A (fr) |
CA (1) | CA1272153A (fr) |
DE (1) | DE3570088D1 (fr) |
ES (1) | ES8604292A1 (fr) |
PT (1) | PT80934B (fr) |
ZA (1) | ZA855849B (fr) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5116484A (en) * | 1990-10-31 | 1992-05-26 | Shell Oil Company | Hydrodenitrification process |
US5227353A (en) * | 1991-07-24 | 1993-07-13 | Mobil Oil Corporation | Hydroprocessing catalyst composition |
JP2000515198A (ja) * | 1996-08-01 | 2000-11-14 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | 水素処理法 |
EP0870817A1 (fr) | 1997-04-11 | 1998-10-14 | Akzo Nobel N.V. | Procédé pour l'hydrodésulphuration poussé de charges hydrocarbonées |
US7513989B1 (en) | 1997-07-15 | 2009-04-07 | Exxonmobil Research And Engineering Company | Hydrocracking process using bulk group VIII/Group VIB catalysts |
US7232515B1 (en) | 1997-07-15 | 2007-06-19 | Exxonmobil Research And Engineering Company | Hydrofining process using bulk group VIII/Group VIB catalysts |
US7229548B2 (en) | 1997-07-15 | 2007-06-12 | Exxonmobil Research And Engineering Company | Process for upgrading naphtha |
US7288182B1 (en) * | 1997-07-15 | 2007-10-30 | Exxonmobil Research And Engineering Company | Hydroprocessing using bulk Group VIII/Group VIB catalysts |
AU2004279081A1 (en) * | 2003-10-02 | 2005-04-14 | Exxonmobil Research And Engineering Company | Process for upgrading naphtha |
CA2455011C (fr) | 2004-01-09 | 2011-04-05 | Suncor Energy Inc. | Traitement de mousse bitumineuse par injection de vapeur en ligne |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2300038C2 (de) * | 1973-01-02 | 1987-05-07 | Basf Ag, 6700 Ludwigshafen | Verwendung eines geschwefelten Katalysators für die Herstellung von technischen Weißölen |
US4016067A (en) * | 1975-02-21 | 1977-04-05 | Mobil Oil Corporation | Process for demetalation and desulfurization of petroleum oils |
DE2837018A1 (de) * | 1978-08-24 | 1980-03-06 | Basf Ag | Verwendung von kobalt- und/oder nickelmolybdaenoxid-katalysatoren zur hydrierenden raffination von erdoel- kohlenwasserstoffen |
AU530497B2 (en) * | 1978-09-28 | 1983-07-21 | Amoco Corporation | Catalyst comprising hydrogenation component on support containing alumina and phosphorus oxides |
US4406779A (en) * | 1981-11-13 | 1983-09-27 | Standard Oil Company (Indiana) | Multiple catalyst system for hydrodenitrogenation of high nitrogen feeds |
AU571189B2 (en) * | 1982-12-06 | 1988-04-14 | Amoco Corporation | Hydrotreating catalyst |
US4500424A (en) * | 1983-04-07 | 1985-02-19 | Union Oil Company Of California | Desulfurization catalyst and process |
-
1985
- 1985-07-29 EP EP85201248A patent/EP0203228B2/fr not_active Expired - Lifetime
- 1985-07-29 DE DE8585201248T patent/DE3570088D1/de not_active Expired
- 1985-08-02 ZA ZA855849A patent/ZA855849B/xx unknown
- 1985-08-06 CA CA000488159A patent/CA1272153A/fr not_active Expired - Fee Related
- 1985-08-09 ES ES546041A patent/ES8604292A1/es not_active Expired
- 1985-08-09 PT PT80934A patent/PT80934B/pt not_active IP Right Cessation
- 1985-08-09 BR BR8503786A patent/BR8503786A/pt not_active IP Right Cessation
- 1985-08-09 JP JP60174439A patent/JPH0633364B2/ja not_active Expired - Fee Related
- 1985-08-09 CN CN85106942.8A patent/CN1006230B/zh not_active Expired
Also Published As
Publication number | Publication date |
---|---|
CA1272153A (fr) | 1990-07-31 |
DE3570088D1 (en) | 1989-06-15 |
BR8503786A (pt) | 1986-12-09 |
JPH0633364B2 (ja) | 1994-05-02 |
ZA855849B (en) | 1986-03-26 |
CN85106942A (zh) | 1987-02-04 |
ES8604292A1 (es) | 1986-01-16 |
EP0203228B2 (fr) | 1996-10-23 |
PT80934A (en) | 1985-09-01 |
JPS61266490A (ja) | 1986-11-26 |
CN1006230B (zh) | 1989-12-27 |
ES546041A0 (es) | 1986-01-16 |
PT80934B (pt) | 1987-09-30 |
EP0203228A1 (fr) | 1986-12-03 |
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