EP0778332B1 - Procédés et dispositifs de viscoréduction de charges lourdes d'hydrocarbures - Google Patents
Procédés et dispositifs de viscoréduction de charges lourdes d'hydrocarbures Download PDFInfo
- Publication number
- EP0778332B1 EP0778332B1 EP96402489A EP96402489A EP0778332B1 EP 0778332 B1 EP0778332 B1 EP 0778332B1 EP 96402489 A EP96402489 A EP 96402489A EP 96402489 A EP96402489 A EP 96402489A EP 0778332 B1 EP0778332 B1 EP 0778332B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- charge
- annular discs
- discs
- soaking vessel
- visbreaking
- 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 - Lifetime
Links
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 19
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 5
- 238000005336 cracking Methods 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 7
- 230000004323 axial length Effects 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims 12
- 230000001939 inductive effect Effects 0.000 claims 2
- 238000000605 extraction Methods 0.000 abstract 1
- 238000011946 reduction process Methods 0.000 abstract 1
- 238000005292 vacuum distillation Methods 0.000 description 7
- 238000004821 distillation Methods 0.000 description 6
- 238000005194 fractionation Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Images
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
- C10G51/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only
- C10G51/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only
- C10G51/023—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only only thermal cracking steps
-
- 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
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/007—Visbreaking
Definitions
- the present invention relates to improvements brought to visbreaking processes and devices heavy loads of hydrocarbons.
- the ripener is usually in the form of a cylindrical enclosure, which does not have any means of additional heating of the load and, the cracking being endothermic, the temperature of the load drops by a few tens of degrees between its entry into the ripener and its release.
- the temperature there is generally of the order of 400 to 500 ° C and the pressure of about 2 to 30 10 5 Pascals.
- the residence time in the ripener is approximately 10 to 30 minutes.
- the severity, which depends on the residence time and the temperature of the ripener, is of the order of 20 minutes.
- the treated charge is injected at the base of the ripener, while cracked products, including products gaseous possibly formed, are evacuated to the part upper towards a split assembly by atmospheric distillation, then by vacuum distillation.
- the feedstock can be heavy crude oil, a residue from atmospheric distillation, which is little frequent, because there are other types of recovery, a vacuum distillation residue or a pitch of deasphalting.
- the products resulting from visbreaking are, after fractionation, gaseous hydrocarbons and gas liquefied petroleum, petrol, diesel, distillate and the visbreaking vacuum residue.
- the visbreaking vacuum residue is the last recoverable product and it must meet requirements severe stability and compatibility with others petroleum cuts to be able to be used as a base for fuel oil, which causes the operator to adjust the conditions of implementation of visbreaking, in particular the temperature, so as to comply with the imposed criteria.
- a major problem encountered in the units of visbreaking resides in a non-homogeneous progression of the charge inside the ripener, effects of back mixing (in English, "back mixing") and vortices encountered in particular in the vicinity of the side walls of the ripener, in particular at the bottom thereof.
- back mixing in English, "back mixing”
- vortices encountered in particular in the vicinity of the side walls of the ripener, in particular at the bottom thereof.
- Each tray thus produces, at the orifices that he understands and borrows the bubbles of the gases present, a charge mixing effect, and the patent application aforementioned European recommends the use of 1 to 20 trays of this type in the ripener.
- the present invention aims to avoid these drawbacks by proposing means suitable for ensuring a residence time more homogeneous charge in the ripener allowing to obtain better stability of the visbreaked residue and an increase in the conversion rate for products obtained from visbreaking.
- the invention also aims to limit the phenomena of retromix associated with the treatment of a load of heavy hydrocarbons in the ripener of a set of visbreaking.
- the invention finally aims to reduce the formation of coke in visbreaking processes and devices.
- the Applicant has, in fact, established that by having in the ripener, transverse to the direction of displacement of the treated load, of the annular discs spaced from each other, whose edges are joined or not with the internal faces of the side walls of the maturer, we obtain simultaneously a more significant load, and therefore a reduction significant coke formed, and better stability of the visbreaking vacuum residue.
- the invention therefore relates to a method of visbreaking of a heavy load of hydrocarbons in the state liquid, in which this charge is brought to a temperature likely to cause cracking of at least one part of the hydrocarbons present, then is introduced to the lower part of a ripener in which it is moves from bottom to top, to be evacuated to the part superior of this ripener towards a unit of fractionation, this process being characterized in that, at inside the ripener, transverse to the direction displacement of the load to be treated, is arranged a plurality of annular discs spaced from each other, each having a substantially circular central passage coaxial with the ripener, the treated charge flowing from bottom to high in the ripener using the central passages different annular discs.
- the annular discs By forcing the load to move from bottom to top along the axis of the ripener, the annular discs have for main effect of limiting a radial dispersion of this charge.
- edges of the annular discs are contiguous with the adjoining internal faces of the walls side of the soaker.
- a cylindrical ripener having a axial length from 8 meters to 14 meters, and a diameter between 1.5 and 2.5 meters, from 3 to 10 discs regularly spaced annulars will be arranged between the bottom and upper part of the ripener.
- each disc annular will represent at least 30% of the surface of the disc and preferably between 30 and 65% of this surface.
- these discs are preferably perforated, the orifices thus formed in the discs being distributed substantially evenly on their surface and occupying between about 5 and 30% of this surface.
- the orifices will have a diameter large enough to to prevent possible coking which would risk them shut off. In particular, they will have a diameter of at least 30 millimeters and preferably between 30 and 100 millimeters.
- the orifices of the annular discs contiguous perforated will be offset laterally by relation to others, in order to avoid the phenomena of foxing that could occur if the orifices of consecutive discs were arranged opposite.
- the invention naturally also relates to a heavy load visbreaking device of hydrocarbons in the liquid state, of the type comprising a means of heating the load to a temperature likely to cause cracking of at least some of the hydrocarbons, and a ripener comprising, in its part lower, at least one load supply line preheated and, at the top, at least one line evacuation of the treated load to a fractionation of this charge, this device being characterized in that inside the ripener, transverse to the direction of movement of the load to be treated, is arranged a plurality of annular discs spaced from each other, whose edges are preferably contiguous with the contiguous internal faces of the side walls of the soaker which each have a circular central passage substantially coaxial at ripener.
- the single figure in this drawing is a schematic view visbreaking equipment in accordance with this invention.
- annular discs 5, having a central circular passage 6, are arranged at the interior of the ripener 3, perpendicular to its axis.
- These discs 5, 8 in number, for example, for a 12 meter high ripener, are spaced so substantially regular to each other, from the bottom of the ripener 3 to the top of it. Their edges are in contact with the inside of the walls side of the soaker and the circular passages 6 represent at least 35% of the surface of the disc.
- Each disc 5 is crossed by perforations 7 forming regularly spaced orifices on its surface. These ports allow passage to the treated charge, including the gases formed and / or injected, transversely to the disc, thus avoiding the formation of dead zones between the contiguous discs.
- the openings 7 of the contiguous discs do not are not arranged opposite, but are offset angularly with respect to each other, in view avoid foxing phenomena. They occupy approximately 30% of the surface of the discs, on which they are regularly distributed.
- the discs annulars according to the invention allow to obtain a visually reduced stability vacuum residue greatly improved, as will emerge from the examples below.
- a visbreaking unit is controlled using stability as a benchmark of the visbreaking vacuum residue, for its use as fuel oil, because if the stability is not greater at a certain threshold, fuel oil can present problems of use, due to the formation of sediments by precipitation of asphaltenes.
- a central rod removable by the top of the ripener, penetrates into it through the central passages of the annular discs.
- This rod also supports “internals” additional spaced apart, whose surface transverse is such that these "interns” can pass to the through central passages of the discs, so that be removed, but is greater than 5% of the surface transverse of the ripener.
- Additional “interns” are for example solid discs, possibly perforated.
- the different “internal” can be arranged to form a alternation between solid discs and annular discs.
- Each full disc is for example positioned at a distance between one third and two thirds of the distance separating two consecutive annular discs, and preferably halfway between these.
- This vacuum residue is heated to a temperature of around 440 ° C in a visbreaking unit oven, then is introduced into a visbreaking ripener not modified in accordance with the present invention.
- This ripener has a diameter of 2.5 meters and a height of 14 meters.
- the load flow rate is 100 t / h and its average residence time is 18 minutes.
- the visbreaking effluent is fractionated in a distillation column atmospheric and then in a distillation column under empty.
- Example 2 The same vacuum distillation residue as in Example 1 is again subjected to a visbreaking treatment under conditions of identical severity.
- the load is heated in the oven to a temperature of the order of 440 ° C and one operates in the ripener at a temperature of 425 ° C under a pressure of 8.10 5 Pascals.
- the charge rate remains the same as before.
- the ripener was modified in accordance with the invention and it has six annular discs, separated from each other others at a distance of 2 meters, the lowest disc being located 2.5 meters from the bottom. These discs are made of steel and have a thickness of 3 millimeters. They are willing coaxially with the ripener and they each have a circular central passage with a diameter of 1.5 meters and holes of 90 millimeters in diameter are distributed regularly on their surface.
- the six discs are identical and angularly offset by 20 °, so that the holes of two contiguous discs are not arranged opposite.
- the visbreaking effluent is fractionated in a column atmospheric distillation then in a column of vacuum distillation.
- Example 2 With the same vacuum distillation residue as in Example 1, a visbreaking treatment is carried out under conditions of increased severity compared to Examples 1 and 2.
- the residue is heated in the oven to 448 ° C, then is introduced into the ripener equipped with six discs annulars identical to that of Example 2.
- the ripener is maintained at a temperature of 434 ° C.
- the conditions of pressure as well as the flow rate of the charge and its time average stay in the ripener are the same as in the Examples 1 and 2.
- the effluent from the ripener is fractionated in an atmospheric distillation column, then in a vacuum distillation column.
- Example 2 It can be seen that the quantities of gas and residue under vacuum obtained with the ripener according to the invention of Example 2 are lower than those obtained with the standard technique (Example 1) and that the higher amounts of petrol and distillate. Above all, there is a very marked increase in the amount of diesel.
- the viscosity of the visbreaking vacuum residue (R.S.V.R.) of Example 2 is higher than that of the vacuum residue obtained according to the prior art method.
- stability is better for the residue from treatment with ripener according to the invention.
- the conversion is further improved and results in an increase in the quantities of gasoline, distillate and diesel.
- the viscosity of the vacuum residue significantly increases compared to Examples 1 and 2 and its stability is identical to that of Example 1, despite the more severe conditions of visbreaking.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Thermal Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Carbon And Carbon Compounds (AREA)
- Steroid Compounds (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Description
- une ligne 1 d'amenée de la charge lourde, à l'état liquide, d'hydrocarbures à traiter ;
- un four 2, que traverse la ligne 1 et qui préchauffe la charge lourde à une température propre à assurer le craquage d'au moins une partie des hydrocarbures qu'elle contient ;
- un maturateur 3, se présentant sous la forme d'une enceinte cylindrique fermée, disposée verticalement, qui est alimentée à sa base par la ligne 1 et qui est équipée à sa partie supérieure d'une ligne 4 d'évacuation des produits de craquage de la charge vers une unité de fractionnement.
- densité : 1,0375 ,
- viscosité
(10-6 m2/s à 100°C): 3500 , - teneur en souffre
(% en poids): 3,86 , - teneur en carbone
Conradson (% en poids): 19,6 , - teneur en asphaltènes
(% en poids) : 12,1 , - point de coupe
(°C) : 520°C.
| Produits obtenus après fractionnement (% en poids) | Exemple 1 | Exemple 2 | Exemple 3 |
| Gaz | 0,64 | 0,50 | 0,55 |
| Essence + LPG | 5,00 | 5,50 | 5,80 |
| Gazole | 12,30 | 13,70 | 14,70 |
| Distillat | 10,90 | 11,10 | 11,75 |
| R.S.V.R. (résidu sous vide) | 71,20 | 69,20 | 67,20 |
| Stabilité du R.S.V.R. | |||
| - stabilité () | + | ++ | + |
| - sédiments () (ppm) | 850 | 500 | 800 |
| Viscosité du R.S.V.R. (cst à 100°C) | 40 000 | 63 000 | 102 000 |
Claims (12)
- Procédé de viscoréduction d'une charge lourde d'hydrocarbures à l'état liquide, dans lequel cette charge est amenée à une température propre à provoquer le craquage d'au moins une partie des hydrocarbures présents, puis est introduite à la partie inférieure d'un maturateur (3) dans lequel elle se déplace de bas en haut, pour être évacuée à la partie supérieure de ce maturateur en direction d'une unité de fractionnement, ce procédé étant caractérisé en ce que, à l'intérieur du maturateur (3), transversalement à la direction de déplacement de la charge à traiter, est disposée une pluralité de disques annulaires (5) espacés les uns des autres et comportant chacun un passage central circulaire (6) sensiblement coaxial au maturateur, la charge traitée circulant de bas en haut dans le maturateur en empruntant les passages centraux des différents disques annulaires (6).
- Procédé selon la revendication 1, caractérisé en ce que les bords des disques annulaires sont jointifs avec les faces internes contiguës des parois latérales du maturateur.
- Procédé selon l'une des revendications 1 et 2, caractérisé en ce que les volumes du maturateur (3) séparés par les disques annulaires (5) communiquent également entre eux par l'intermédiaire d'orifices (7) de ces disques qu'emprunte la charge traitée, y compris les gaz formés.
- Dispositif de viscoréduction d'une charge lourde d'hydrocarbures à l'état liquide, du type comprenant un moyen (2) de chauffage de la charge jusqu'à une température propre à provoquer le craquage d'au moins une partie des hydrocarbures, et un maturateur (3) comprenant, à sa partie inférieure, au moins une ligne (1) d'alimentation en charge préchauffée et, à sa partie supérieure, au moins une ligne (4) d'évacuation de la charge traitée vers une unité de fractionnement de cette charge, ce dispositif étant caractérisé en ce qu'à l'intérieur du maturateur (3), transversalement à la direction de déplacement de la charge à traiter, est disposée une pluralité de disques annulaires (5) espacés les uns des autres, dont les bords sont de préférence jointifs avec les faces internes contiguës des parois latérales du maturateur et qui comportent chacun un passage central circulaire (6) sensiblement coaxial au maturateur (3).
- Dispositif selon la revendication 4, caractérisé en ce que les disques annulaires (5) sont régulièrement espacés les uns des autres.
- Dispositif selon l'une des revendications 4 et 5, caractérisé en ce que le passage circulaire (6) des disques annulaires (5) représente au moins 30 % de la surface du disque et, de préférence, entre 30 et 65 % de cette surface.
- Dispositif selon l'une des revendications 4 à 6, caractérisé en ce que les disques annulaires (5) sont perforés d'orifices (7).
- Dispositif selon la revendication 7, caractérisé en ce que les orifices (7) sont régulièrement répartis à la surface de chaque disque annulaire (5).
- Dispositif selon l'une des revendications 7 et 8, caractérisé en ce que les orifices (7) occupent entre environ 5 et 30 % de la surface des disques annulaires (7).
- Dispositif selon l'une des revendications 7 à 9, caractérisé en ce que les orifices (7) ont un diamètre d'au moins 30 mm et, de préférence, compris entre 30 et 100 mm.
- Dispositif selon l'une des revendications 6 à 9, caractérisé en ce que les orifices (7) correspondants des disques contigus sont décalés latéralement les uns par rapport aux autres.
- Dispositif selon l'une des revendications 4 à 10, dans lequel le maturateur (3) a une longueur axiale comprise entre 8 et 14 mètres et un diamètre compris entre 1,5 et 2,5 mètres, caractérisé en ce qu'il comprend entre 3 et 10 disques annulaires (5).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9514313A FR2741888B1 (fr) | 1995-12-04 | 1995-12-04 | Perfectionnements apportes aux procedes et aux dispositifs de viscoreduction de charges lourdes d'hydrocarbures |
| FR9514313 | 1995-12-04 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0778332A1 EP0778332A1 (fr) | 1997-06-11 |
| EP0778332B1 true EP0778332B1 (fr) | 1999-09-22 |
Family
ID=9485124
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP96402489A Expired - Lifetime EP0778332B1 (fr) | 1995-12-04 | 1996-11-20 | Procédés et dispositifs de viscoréduction de charges lourdes d'hydrocarbures |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US5853567A (fr) |
| EP (1) | EP0778332B1 (fr) |
| JP (1) | JPH09183982A (fr) |
| CN (1) | CN1086409C (fr) |
| AT (1) | ATE184909T1 (fr) |
| CA (1) | CA2191912C (fr) |
| DE (1) | DE69604368T2 (fr) |
| DK (1) | DK0778332T3 (fr) |
| ES (1) | ES2136957T3 (fr) |
| FR (1) | FR2741888B1 (fr) |
| ZA (1) | ZA9610148B (fr) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040230029A1 (en) * | 2002-11-25 | 2004-11-18 | Joseph Mathias | Reactor and process for making amide plastics and super plastics |
| JP2009531530A (ja) * | 2006-03-29 | 2009-09-03 | シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー | 低級オレフィンの製造方法 |
| US7718839B2 (en) * | 2006-03-29 | 2010-05-18 | Shell Oil Company | Process for producing lower olefins from heavy hydrocarbon feedstock utilizing two vapor/liquid separators |
| WO2015000061A1 (fr) * | 2013-07-04 | 2015-01-08 | Nexen Energy Ulc | Réduction d'oléfines d'une charge d'hydrocarbures par alkylation d'oléfines-composés aromatiques |
| FR3164472A1 (fr) | 2024-07-15 | 2026-01-16 | Totalenergies Onetech | Procede de craquage thermique d’hydrocarbures d’origine fossile en presence d’huile de pneus |
| FR3164468A3 (fr) | 2024-07-15 | 2026-01-16 | Totalenergies Onetech | Procede de conversion d’hydrocarbures d’origine fossile suivi d’un fractionnement en presence d’huile de pneus |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1137434A (fr) * | 1978-07-11 | 1982-12-14 | Mohammed Akbar | Methode fractionnement en continu des petroles |
| US4443328A (en) * | 1982-06-01 | 1984-04-17 | Toyo Engineering Corporation | Method for continuous thermal cracking of heavy petroleum oil |
| GB8323635D0 (en) * | 1983-09-02 | 1983-10-05 | Shell Int Research | Continuous thermal cracking of hydrocarbon oils |
-
1995
- 1995-12-04 FR FR9514313A patent/FR2741888B1/fr not_active Expired - Fee Related
-
1996
- 1996-11-20 EP EP96402489A patent/EP0778332B1/fr not_active Expired - Lifetime
- 1996-11-20 DK DK96402489T patent/DK0778332T3/da active
- 1996-11-20 AT AT96402489T patent/ATE184909T1/de not_active IP Right Cessation
- 1996-11-20 ES ES96402489T patent/ES2136957T3/es not_active Expired - Lifetime
- 1996-11-20 DE DE69604368T patent/DE69604368T2/de not_active Expired - Lifetime
- 1996-12-03 ZA ZA9610148A patent/ZA9610148B/xx unknown
- 1996-12-03 CA CA002191912A patent/CA2191912C/fr not_active Expired - Fee Related
- 1996-12-03 CN CN96121515.1A patent/CN1086409C/zh not_active Expired - Fee Related
- 1996-12-04 US US08/759,520 patent/US5853567A/en not_active Expired - Lifetime
- 1996-12-04 JP JP8323716A patent/JPH09183982A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CN1086409C (zh) | 2002-06-19 |
| FR2741888A1 (fr) | 1997-06-06 |
| JPH09183982A (ja) | 1997-07-15 |
| DK0778332T3 (da) | 2000-02-21 |
| ES2136957T3 (es) | 1999-12-01 |
| CA2191912A1 (fr) | 1997-06-05 |
| CN1156169A (zh) | 1997-08-06 |
| CA2191912C (fr) | 2007-04-24 |
| DE69604368T2 (de) | 2000-02-17 |
| US5853567A (en) | 1998-12-29 |
| EP0778332A1 (fr) | 1997-06-11 |
| ATE184909T1 (de) | 1999-10-15 |
| DE69604368D1 (de) | 1999-10-28 |
| ZA9610148B (en) | 1997-06-18 |
| FR2741888B1 (fr) | 1998-02-20 |
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