CN1086247A - The separation stripping tower that contains the dissipation plate that is used for fluid catalytic cracking process - Google Patents
The separation stripping tower that contains the dissipation plate that is used for fluid catalytic cracking process Download PDFInfo
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- CN1086247A CN1086247A CN92112441.4A CN92112441A CN1086247A CN 1086247 A CN1086247 A CN 1086247A CN 92112441 A CN92112441 A CN 92112441A CN 1086247 A CN1086247 A CN 1086247A
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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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
Abstract
The method and apparatus that is used for FCC technology, it uses the dissipation plate with the stripping gas that fast catalyzer separated with product steam (gas) and prevent to enter separator entrained catalyst again at separator outlet.This method and apparatus uses the riser of conversion FCC raw material and the effluent of riser is directly sent into separator with separating catalyst from product steam (gas).Catalyzer leaves separator outlet and the dissipation plate by a series of elimination tangential velocities (also will cause carrying secretly again of catalyzer otherwise eddy current will produce tangential velocity) downwards.The dissipation plate is arranged in when stripping tower near separator outlet below leaves separator with convenient catalyzer accepts it.
Description
The present invention relates to the method and apparatus of fluid catalytic cracking (FCC).More particularly, the present invention relates to the method for separating catalyst from the gaseous product of FCC reaction zone.
The fluid catalytic cracking of hydrocarbon is to use heavy hydrocarbon always, as vacuum gas oil, produces the main method of gasoline and light hydrocarbon products.By with the big hydrocarbon molecule cracking in the heavy hydrocarbon feedstocks, long chain hydrocarbon is broken, obtain light hydrocarbon.These light hydrocarbons reclaim as product, and can directly use or further processing, to improve the octane productive rate with respect to heavy hydrocarbon feedstocks.
From this century the forties early stage, the basic equipment and the device of hydrocarbon stream fluidized catalytic cracking have just been arranged.The basic equipment of FCC method comprises a reactor, a revivifier and a catalyst vapor stripper.The zone of action is arranged in the reactor, and hydrocarbon feed contacts with granules of catalyst therein; And the disengaging zone, gaseous product and catalyzer that cracking reaction therein obtains are separated.Further separated product in the catalyst vapor stripper.In stripping tower, by contacting with water vapor or other stripping medium counter flow, the catalyzer in the self-separation of collecting district also therefrom removes the hydrocarbon of deentrainment.By being contacted with catalyzer trickle or that the particulate solid material is formed, raw material (vacuum gas oil, reduced oil or the higher hydrocarbon of other boiling point) implements the FCC method.By feeding gas or steam, catalyzer is transmitted as fluid with the speed that produces enough required fluid transmission.Oil plays katalysis with contacting of fluidizing storeroom to cracking reaction.In the cracking reaction process, sedimentation of coke is on catalyzer.
Coke contains hydrogen and carbon, also can contain other composition of trace, as sulphur and the metal of being brought into by raw material.Coke can block the active site (on these active sites cracking reaction taking place just) of catalyst surface, thereby influences the catalytic activity of catalyzer.Catalyzer is transferred to revivifier from stripping tower, with by removing coke with the oxygen-containing gas oxidation.The less preparing catalyst of coke content (after this being called regenerated catalyst) is compared in collection with the catalyzer in the stripping tower, use to return in the reaction zone again.The oxidation of coke discharges a large amount of heats on the catalyst surface.Part heat is discharged from revivifier with the gaseous product (generally being referred to as stack gas) of coke oxidation, and all the other heats are discharged from revivifier with regenerated catalyst.Fluidized catalyst autoreaction district continuously is recycled to the breeding blanket, and then to reaction zone.Except that having katalysis, fluidized catalyst is also as the carrier of heat being transferred to another district from a district.The catalyzer that leaves reaction zone can be referred to as used catalyst, the catalyzer of the coke part deactivation that promptly is deposited.Various zone of action, breeding blanket and stripping zone and in the detail of the arrangement of each interval transmission catalyzer to those skilled in the art all are known.
Control the interior conversion of raw material of reaction zone the duration of contact of the amount of the temperature by regulating catalyzer, activity of such catalysts, catalyzer (being catalyzer and the ratio of oil) and catalyzer and raw material.The most popular method of conditioned reaction temperature be regulate catalyzer from the breeding blanket to the cycle rate of reaction zone, this ratio that makes catalyzer and oil simultaneously changes with the variation of temperature of reaction.That is to say, improve transformation efficiency, should improve fluidized catalyst from the cycle rate of revivifier to reactor as hope.Because the catalyst temperature in the breeding blanket is generally a fixed value, and than high many of reaction zone temperature, increase can improve the temperature of reaction zone to the catalyst recirculation amount of reaction zone from the high temperature regeneration district.
The hydrocarbon product of FCC reaction reclaims with gas form, and transfers in the product recvery facility.The product recvery facility generally comprises a king-tower, and this tower is used to cool off the hydrocarbon gas of autoreactor, reclaims a series of heavy crackates that generally include bottoms material, turning oil and heavy gasoline.Send into enriching section further to be separated into other product stream from the light material of king-tower.
The surface-area of used granules of catalyst is bigger in the FCC method, and this is owing to a large amount of holes is arranged in the particle.As a result, retain in the catalyst pores and on the outside surface hydrocarbon is arranged.Although the amount of the hydrocarbon of retaining in each catalyst pores is very little, because normal a large amount of catalyzer and the high catalyst circulation rate used in the modern FCC method, the hydrocarbon of significant quantity is taken out of reaction zone by catalyzer.
Therefore, common way is, will be with crossing before catalyzer send into the breeding blanket, therefrom removes or stripping goes out hydrocarbon.From technology and economic angle, the hydrocarbon of removing retention from used catalyzer is very important.At first, the hydrocarbon that enters revivifier can increase the load of making charcoal of this revivifier, and causes regenerator temperature too high.Strip, hydrocarbons also can reclaim hydrocarbon as product from catalyzer.When handling heavy (molecular weight is bigger) raw material, avoid unwanted hydrocarbon burning particularly important, because when handling these raw materials, be deposited on coke on the catalyzer in the reaction process and can increase (the carbon deposit rate when handling than lightweight material is compared), and increase the burning load of breeding blanket.Burning load is big more, and temperature is also high more.When the temperature height arrives to a certain degree, can damage catalyzer, or surpass the metallurgy design limit of regenerating unit.
The method of the most frequently used stripping catalyst is to make stripping gas, is generally water vapor, and adverse current is by the mobile catalyst stream.The operation of this water vapor stripping is removed the hydrocarbon gas of catalyst entrainment with different efficient and is adsorbed on hydrocarbon on the catalyzer.
By keeping at a certain distance away in vertical direction some baffle plates are set, make catalyzer in stripping tower, form cascading when the lastblock baffle plate flows to flowing downward of next piece baffle plate and contact, just can improve the steam stripping efficiency of catalyzer with the stripping medium counter flow.The tangential movement of catalyzer has increased contacting between catalyzer and stripping medium, thereby removes more hydrocarbon from catalyzer.Under this arrangement, a series of baffle plates that are positioned at different heights make catalyzer tortuous mobile.By this arrangement, increased contacting between catalyzer and gas, do not have the bigger vertical channel freely of sectional area in the stripping tower.Typical stripping tower comprises the stripping tower shell, and a series of cross sections are the conical baffle plate of frustum, and these baffle plates make catalyzer turn to again, outwards flow to outer baffle.The stripping medium enters from the bottom of the lower baffle plate of a series of baffle plates, and the bottom from a baffle plate upwards continues up in the bottom of a baffle plate again.
Along with the development of FCC Technology, the temperature in the reaction zone progressively improves.The general now temperature that adopts is about 975 °F (525 ℃).At high temperature, generally can lose some gasoline components, because under katalysis and strict hot mechanism effect, gasoline component can cracking be light-weight hydrocarbon more.At 525 ℃, generally have 1% potential gasoline component hot tearing and turn to more light-weight hydrocarbon gas.Along with the raising of temperature, as 1025 °F (550 ℃), the thermally splitting meeting makes most of significant loss 6% or more gasoline component.But the loss meeting of gasoline is offseted by producing more required light olefin.
By adopting the riser cracking to improve FCC technology, can reduce the product loss that thermally splitting produces.In the riser cracking, the regenerated catalyzer enters tubular reactor with raw material.The vaporization of the fluidizing medium of hydrocarbon and other existence makes gas expansion owing to contacting with thermocatalyst, and above-mentioned regenerated catalyst is upwards carried with raw material.The riser cracking has improved contacting of live catalyst and oil, and can change turbulent flow and the back-mixing of catalyzer residence time by elimination and make catalyzer more easy to control with the duration of contact of oil.Now, in the common riser zone of cracking, catalyzer is 1-5 second with the duration of contact of oil.At some riser reaction zones, carry gas in the employing so that catalyst stream is evenly distributed.In first district of riser, before raw material enters, use and carry the gas accelerator activator, thereby reduce the turbulent flow that can change the duration of contact of catalyzer and hydrocarbon.
In most of reactors, catalyzer and converted product are sent into a big chamber again with initial gross separation catalyzer and hydrocarbon.The open large space of separator makes hydrocarbon gas turbulization and back-mixing, thereby continues the different time of contact with catalyzer, and makes hydrocarbon gas continue to keep high temperature in the regular hour.Therefore, in separator, can produce the problem of thermally splitting.Use cyclonic separator, will separate with granules of catalyst from the light hydrocarbon that reaction zone is discharged by centripetal force, thereby hydrocarbon gas and catalyzer are separated.
For making the thermally splitting in the separator reduce to minimum degree, proposed some in the prior art and made riser reactor outlet and the direct-connected device of cyclonic separator import.In reaction zone, make a large amount of in reaction zone, being separated with contacted hydrocarbon gas of catalyzer and catalyst solid particle with impact and/or centrifugal separation method.With the outlet of the import of first cyclonic separator and first cyclonic separator and the import of second cyclonic separator directly link to each other (being referred to as " directly being connected cyclone system ") can reduce the thermally splitting of hydrocarbon to a great extent.Regrettably, in most of the cases, cyclonic separator directly linked to each other can make FCC technology more complicated.If cyclonic separator directly links to each other with riser, the pressure fluctuating that regular meeting occurs in the FCC technological operation can make cyclonic separator break down, and will cause catalyzer to be admitted in the separating device of king-tower and recovery product.The arrangement that some different riseies and cyclonic separator are arranged in the prior art is to improve the operational reliability of the cyclonic separator that directly links to each other with riser.
A kind of method that overcomes pressure fluctuating and catalyzer branch problem is to connect a large vol separating device in the riser outlet.US-A-4,689,206 accompanying drawing 8 has been drawn this separating device.This separating device makes gaseous product mixture enter the less common cyclonic separator of volume and is separated with catalyzer before.Because volume is bigger, this separating device is difficult for overload, and the fluctuating of general pressure can not influence its operation.But the separation efficiency of this large volume separating device is lower, the granules of catalyst load of downstream cyclonic separator is increased, or need the two stage cyclone separator, or need long length to improve separation efficiency.Low separation efficiency owing to from this separating device effluent air again entrained catalyst particles cause.Therefore, the invention provides a kind of directly link to each other solution of the problem that causes of this and cyclonic separator that overcomes.
An object of the present invention is to provide a kind of interior catalyst separating system of reactor of the FCC of being used for technology, this separation system is separating catalyst and gaseous product rapidly, and is easy and simple to handle, good reliability.
Second purpose of the present invention provides a kind of separation system that is used for the reactor product and the catalyzer of separating FCC technology, and this separation system is not subject to because the influence of the caused overload of pressure surge and compact.
The 3rd purpose of the present invention provides a kind of whirlwind type separator, and this separator receives all materials from FCC reactor riser, and the separation efficiency height is not subject to because the influence of the caused overload of pressure surge.
The 4th purpose of the present invention provides a kind of FCC method, and this method is divided gas flow product and catalyzer rapidly, makes overcracking reduce to minimum, and the influence of the caused overload of variation of be difficult for being stressed fluctuation or reactor assembly operational condition.
By providing a kind of separation system that above-mentioned purpose of the present invention is achieved.This separation system directly links to each other with the outlet of riser in the FCC technology, in separator, carry out basic whirlwind operation, and at separator positioned beneath breaker plate or dissipation plate with the separating effect that improves catalyzer and prevent carrying secretly again of catalyzer, thereby this separation system can provide high efficiency separation.Above-mentioned breaker plate or dissipation plate are positioned at the below near outer eddy current, and the operation of most of whirlwind can form outer eddy current.In general, eddy current has tangential velocity, as not with its dispersion, will form turbulent flow, and turbulent flow can be carried the granules of catalyst that has separated again secretly.Contact with breaker plate, just can disperse tangential velocity, and reduce the turbulence that abuts against the eddy current below.When breaker plate being inserted in the eddy current to reduce particle speed and when preventing to carry secretly, breaker plate also can be used to the capture catalyst particle again.
Therefore, in one embodiment of the invention, the invention provides a cover fluidized catalyst cracking unit, comprise a reactor and a tubular type riser.This tubular type riser has entrance end and the exit end that receives raw material and catalyzer.The separator that a lengthening is arranged in reactor, this separator has top and bottom.There is a tangential entry that directly links to each other with the outlet of riser the upper end of this separator, and a center gas outlet is arranged at the top, and an opening end is arranged in its lower end, and the most external of this opening end is sealing not, flows not hinder fluid and particulate.In the positive lower end of separator, a stripping tower is arranged.This stripping tower has an import that directly links to each other with the opening end of separator, also has an outlet of discharging catalyzer from this stripping tower.The device that adds stripping gas is arranged on stripping tower.An isolated area is arranged in stripping tower, and this isolated area comprises at least two vertical breaker plates or dissipation plate, and is positioned at the below of the opening end of separator.
In a narrower embodiment of the present invention, the invention provides a cover fluidized catalytic cracker, comprise a reactor and a tubular type riser.This tubular type riser has entrance end and the exit end that receives raw material and catalyzer.The separator that a lengthening is arranged in reactor, this separator has top and bottom.There is a tangential entry that directly links to each other with the outlet of riser the upper end of this separator, and a center gas outlet is arranged at the top.There is vertically extending sidewall its lower end, opening end, and at the bottom of vertically extending sidewall some openings along the circumferential direction.Below near separator a stripping tower is arranged, the upper end of this stripping tower is positioned at reactor, and the upper end of this stripping tower is inserted in the lower end of separator.In this stripping tower, have two dissipation plates at least.This dissipation plate extends internally from the stripping tower wall, and the centerline of each dissipation plate and stripping tower is in same plane.And each dissipation plate level and vertical direction extend and under near the open bottom of separator square frame go out a free zone.The dissipation plate has a central section, and the top of this central section is positioned at the below of separator lower end.There is a catalyst outlet lower end of this stripping tower, between the top and catalyst outlet of dissipation plate central section, has an interior stripping baffles and at least one outer stripping baffles at least.This stripping tower also has the device of the stripping fluid being introduced stripping tower.A vortex stabiliser extends into the lower end of separator.In an embodiment preferred, described vortex stabiliser diameter does not seal except described vortex stabiliser less than 20% and described open bottom of the diameter of separator open bottom.Also has the device that gas is discharged from the open space of reactor.
In a narrower embodiment of the present invention, the invention provides a cover fluidized catalytic cracker, comprise a reactor and a tubular type riser.This tubular type riser has entrance end and the exit end that receives raw material and catalyzer.The separator that a lengthening is arranged in reactor, this separator has top and bottom.There is a tangential entry that directly links to each other with the outlet of riser the upper end of this separator, and a center gas outlet is arranged at the top.There is vertically extending sidewall its lower end, opening end, and at the bottom of vertically extending sidewall some openings along the circumferential direction.At least a portion with stripping tower of upper end areas and following petiolarea is positioned at reactor.The upper end areas of stripping tower is fixed on the lower end of separator, and the following petiolarea of stripping tower is fixed on the lower end of reactor.In the upper end areas of stripper and the slip joint in interval, lower end two petiolareas are linked together.The device that on the stripping tower stripping tower inside is linked to each other with inside reactor.The diameter of the upper end areas of stripping tower is greater than the diameter of separator lower end.The upper end areas of stripping tower has two dissipation plates at least,, this dissipation plate extends internally from the stripping tower wall, and the centerline of each dissipation plate and stripping tower is in same plane.The dissipation plate has a central section, and this central location is in the below of separator lower end.The dissipation plate also has an outside area, and this outside area extends upwardly to the opening end that is higher than separator from the top, central section.In dissipation plate bottom, has a stripping baffles at least.The following petiolarea of stripping tower has the upper end and the lower end that is positioned at outside the reactor that are positioned at reactor.There are a catalyst outlet and a divider from stripping gas to stripping tower that introduce in the lower end of petiolarea under the stripping tower.The upper end of petiolarea has at least one to be positioned at wherein stripping baffles under the stripping tower.A vortex stabiliser extends into the lower end of separator.The device of introducing fluidizing agent is arranged in the bottom of reactor.Cyclonic separator receives gaseous product and the catalyzer from the pneumatic outlet of separator.This cyclonic separator has a drop-pipe of catalyzer being sent back to reactor.First conduit is directly sent into cyclonic separator with gaseous product from pneumatic outlet.Second conduit is sent into the product recovery system with gaseous product from cyclonic separator.This fluidisation catalytic unit also comprises the device of fluidizing agent being discharged reactor.
According to another embodiment of the invention, the invention provides a kind of method of utilizing the described FCC apparatus of above-mentioned any embodiment with FCC feedstream fluidized catalytic cracking.This method comprises the steps: FCC catalyzer and FCC raw material are sent into the riser reaction zone, and the FCC raw material is contacted with the FCC catalyzer at the riser reaction zone, being product steam (gas) with feedstock conversion; Gaseous product mixture and exhausted FCC catalyzer are directly sent into the import of separator from riser, and said mixture are tangentially introduced separator from above-mentioned import, with the interior eddy current that in separator, forms product steam (gas) and outside eddy current; With the stable interior eddy current of the vortex stabiliser in the separator; Granules of catalyst is directly sent into the top of the stripper that is positioned at the separator below from the separator bottom.This method comprises stripping gas sent in the stripping tower and with granules of catalyst and contacts, with desorb hydrocarbon from granules of catalyst; The hydrocarbon gas that makes desorb with stripping gas in stripper on flow, by some vertical spacer plates of placing, by the open space of the stripper on the central section that is positioned at spacer plate, under the separator, leave the top of stripper, enter the bottom of separator; Keep in the stripping tower under dissipation plate central section than dense bed; Extract product steam (gas) and gaseous stream out from the separator top through central outlet; Product steam (gas) and gaseous stream are sent into separator to reclaim extra granules of catalyst from central outlet; From separator, reclaim product stream; Granules of catalyst is sent into the stripping tower bottom from reactor; Remove used catalyst and it is delivered to the breeding blanket from the stripping tower lower end; By the oxidation decoking, at breeding blanket regeneration FCC catalyzer; The FCC catalyzer that will come out from the breeding blanket is sent into the riser reaction zone.
Accompanying drawing 3 is that the disengaging zone of amplification of accompanying drawing 2 is in the sectional view at 3/3 place;
The raw material of FCC technology is generally gas oil, and as lightweight gas oil or vacuum gas oil, other the FCC raw materials technology that comes from oil can comprise the hydrocarbon mixture with diesel boiling range or the hydrocarbon of heavy more, as reduced oil.Feedstream preferably is higher than about 230 ℃ hydrocarbon mixture by boiling point and forms, and particularly is higher than about 290 ℃.Above-mentioned boiling point is measured by corresponding ASTM measuring method, will process heavy feed stock usually, is called slag oil cracking technology as the FCC technology of normal pressure reduced oil, or residue cracking technology.Method and apparatus of the present invention can be used for FCC technology or slag oil cracking operation.For simplicity, the other parts of this specification sheets are only put forward FCC technology.
The chemical constitution of the raw material of FCC technology and structure are deposited on influence the amount of the coke on the catalyzer in the reaction zone.Usually the molecular weight of raw material is high more, the Kang Laxun carbon residue is many more, heptane insolubles is many more and carbon/hydrogen is higher than more, and then sedimentary coke is many more on used catalyst.In addition, compound nitrogen many more (as in the shale derived oils, finding), then sedimentary coke is also many more on used catalyst.The original normal pressure tower bottom distillate (being commonly referred to reduced oil) as the deasphalted oil fractionation operation of refining heavy will cause some or all increase in the above-mentioned factor, thereby cause the coke content on used catalyst to increase.The term " used catalyst " that is used for herein is meant that at the reaction zone used catalyst it will be transported to the breeding blanket to remove sedimentary coke.This term means that never granules of catalyst all loses catalytic activity
Reaction zone (owing to being extensive use of vertical tube, so be referred to as " riser " usually) maintains under the hot conditions, generally includes to be higher than 427 ℃.The preferred reaction district maintains under the cracking conditions, this condition comprise temperature from 480 ℃ to 590 ℃ and pressure from 65 to 601KPa, but preferably less than 376KPa.Based on the catalyzer that enters riser bottom and the weight of hydrocarbon, the catalyst/oil ratio can be up to 20: 1, but preferably between 4: 1 to 10: 1.Usually hydrogen is not added in the riser, is known in the art although add hydrogen.Sometimes, water vapor can lead in the riser.The mean residence time of catalyzer in riser is preferably less than 5 seconds.The catalyst type that is used for this technology can be selected from various commercially available catalyzer.The catalyzer that contains the zeolite base-material is preferred, but if desired, old-fashioned amorphous catalyst also can use.The further information of FCC reaction zone operation can be by U.S-A-4, obtains in 541,922 and U.S-A-4,541,923.
The FCC technique unit comprises reaction zone and catalyst regeneration zones.The present invention is applicable to any combination of reactor and breeding blanket.Anyway make up, all should contact in riser with medium direct draught at high temperature with the fluidized catalyst particle by raw material, its conversion.In the present invention, catalyzer and raw material contact and the conversion of raw material occurs in the riser.This riser comprises that the effluent of a vertical substantially pipe and this pipe flows in the separator.One or more additional solid vapour separating devices (almost always cyclonic separator) are usually located at the top in the big separator.Separator and cyclonic separator are separated reactor product and the catalyzer that is carried by air-flow.One or more pipes are discharged gas from cyclonic separator and disengaging zone.After initial gross separation, used catalyst is sent to the stripping zone that is positioned under the separator.For the present invention, stripping tower should be positioned under the disengaging zone, and the equipment that is used for disperseing at separator outlet turbulence should be equipped with in stripping tower top.Catalyzer is through behind the stripping zone, and it can be sent to reactor or the one or more additional stripping steps of process.
Catalyzer is behind stripping, and it can enter the breeding blanket, and catalyzer carries out from the reaction zone to the breeding blanket circulation to reaction zone continuously again in FCC technology.Therefore catalyzer can play the carrier function that conducts heat district by district and the catalytic activity of institute's palpus is provided.The catalyzer of extracting out from the breeding blanket is called " regenerated catalyzer ".The catalyzer that is added to the breeding blanket and oxygen-containing gas such as air or oxygen-rich air contact under the coke incendiary condition promoting.This will cause the rising of catalyst temperature and produce a large amount of hot gass of discharging and be referred to as flue gas stream from the breeding blanket.Breeding blanket operation between 600 ℃ to 800 ℃ usually.The further information of FCC reaction zone and regeneration zone operation can be from U.S-A-4, and 431,749; U.S-A-4,419,221 and U.S-A4,220,623 obtain.
Catalyst regeneration zones is preferably in 136 to the operation down of 601KPa pressure.The used catalyst that is added to the breeding blanket can contain 0.2% to 5%(weight) coke.This coke mainly is made up of carbon and can be contained 3% to 15%(weight) hydrogen, and sulphur and other element.The oxidation of coke will produce the ordinary combustion product: carbonic acid gas, carbon monoxide and water.By a step or a multistep regenerative operation, several combinations can be taked in the breeding blanket.The further variation of regeneration zone operation can realize by regeneration fluidized catalyst in dilute phase or concentrated phase.Term " dilute phase " is meant that density is less than 320kg/m
3Catalyst/gas mixture.Term " concentrated phase " is meant that density is equal to or greater than 320kg/m similarly
3Catalyst/gas mixture.Representational dilute phase operational condition often comprises that density is 15 to 150kg/m
3Catalyst/gas mixture.
Fig. 1 shows the layout of the traditional FCC reactor/regenerator that is modified to incorporate into separation system of the present invention.In its elementary operation, raw material enters the lower end of riser 10 through nozzle, and it contacts with fresh regenerated catalyzer from regenerated catalyst pipeline 14 at this.Valve 16 controls are added to the catalyzer speed of riser 10.Water vapor also can add to reach desirable feed rate and to help raw material to disperse in stream of catalyst particles with raw material through nozzle 12.Raw material hydrocarbon contacts and cracking with catalyzer in riser, and used catalyst and product steam (gas) are discharged from riser 10 tops through horizontal pipeline section 18.The catalyzer and product steam (gas) mixture of discharging from pipeline section 18 directly enter the separator 20.Comprise stripping gas in the reactor 19, used catalyst and product steam (gas).In separator 20, enter downwards in the stripping tower 22 with catalyzer after product steam (gas) separates with stripping gas.The water vapor that enters stripping tower 22 through nozzle 24 contacts with stripping from catalyzer with the granules of catalyst adverse current and goes out unnecessary hydrocarbon.Catalyzer escapes and enter the second catalyst vapor stripper 28 through nozzle 26 from stripping tower 22.The water vapor that enters stripping tower 28 through nozzle 30 contacts to remove wherein unnecessary hydrocarbon with the granules of catalyst adverse current again.Stripping gas with separate after hydrocarbon rise through stripping tower 28 and 22 and below the mode of describing in detail is extracted out through separator 20 and center gas outlet 32.Collector 34 imports cyclonic separator 36 with stripping fluid and product steam (gas), further granules of catalyst is separated with product steam (gas) with the stripping fluid at this.Collector 38 is collected stripping fluid and product steam (gas) and is discharged from reactor through managing 40 from cyclonic separator 36.Enter from the product steam (gas) of collector 38 and stripping fluid and to be generally used for reclaiming in the FCC product separation equipment.
All are directly delivered in the revivifier from the used catalyst of reactor region.The used catalyst of collecting by cyclonic separator 36 through drop-pipe 42 fall and between the outer wall of the wall of reactor 19 and stripping tower 22 aggregation become fine and close bed 44.Many aperture 46(below will describe in detail) catalyzer is transported to stripping tower 22 inside from bed 44.After the strip, hydrocarbons, used catalyst is extracted out from container 28 bottoms with the speed of being controlled by valve 50 through used catalyst pipeline 48.
In revivifier 52, the coke on oxidation catalyst particles surface, and generation contains H
2O, CO and CO
2As the stack gas of combustion prod, thus with catalyst regeneration.Catalyzer enters revivifier 52 and contacts with the air that enters in the revivifier through nozzle 56 through nozzle 54.The present invention does not need the regeneration system rapidly of specific type.Revivifier 52 is fine and close bed 58 in its underpart of operation usually.The distribution apparatus of some crosscut regenerator bottoms with air distribution on the whole transverse section of this revivifier.Various these type of distribution apparatus are known those skilled in the art.In addition, the present invention can implement by having multistage coke incendiary breeding blanket.In addition, CO perfect combustion or partial combustion can be finished in the breeding blanket.In fine and close bed operation as shown in Figure 1, stack gas and the granules of catalyst of carrying secretly rise from bed 58.First step cyclonic separator 60 collecting flue gas also carry out initial gross separation to granules of catalyst and stack gas, and granules of catalyst turns back to bed 58 through drop-pipe 62, and stack gas is transported in the secondary cyclone 66 through pipeline 64.Further being separated in the cyclonic separator 66 of granules of catalyst and stack gas carried out, and granules of catalyst turns back to bed 58 through drop-pipe 68, and stack gas is left cyclonic separator 66 upper ends and revivifier through collecting chamber 70 and flue gas line 72.
Operation and understanding more completely of layout to separator 20 and stripping tower 22 can be with reference to Fig. 2.Fig. 2 shows the separator 20 that is arranged in reactor 19 fully.Separator is handled and is tangentially entered the used catalyst of separator 20 upper ends and the mixture of product steam (gas) through horizontal pipeline 18.Gas and solid tangentially enter separator 20, have formed the well-known duplex flow pattern of finding in traditional cyclonic separator usually in separator.Catalyzer and gas are rotated down in the deuterostrophies near separator 20 outer walls, and form internal screw and begin upwards to return, and make helical flow be full of the center of separator 20, and discharge from the separator top through center gas outlet 32.The screw action of gas and catalyst mixture makes solid particulate at close separator 20 wall place aggregations.Action of gravity make particle along the wall of separator 20 to dirty and discharge through outlet at bottom 74.The efficient of separator is improved by the position that the vortex stabiliser 76 control duplexs that are positioned at separator 20 centers flow.Solid 95% through pipeline 18 is removed by separator 20, makes the air-flow through pipeline 32 discharges only contain the granules of catalyst of underload.The shape of eddy current also can be a bit larger tham the truncate taper shape of lower diameter and improve by making separator 20 have upper diameter.It also is preferred finishing near the bottom of opening 74 or its that separator 20 is designed to outer vortex.This design is different with traditional cyclonic separator, and the latter's length is more much longer than the length of outer vortex.The space that separator requires can reach or only be lower than outlet 74 slightly and reduce by it being designed to the outer vortex bottom.For specific spirane structure requirement, separator length will depend on its size and gas flow rate.For the separator of stock size, from 5 to 10 feet of its diameter ranges (1.5 to 3m), the length from gas and catalyzer bottom inlet to outlet 74 is 2 to 3 times of separator maximum diameter.
When solid through exporting 74 when leaving separator 20, its may be carried secretly near opening 74 round-robin gases or through the gas that opening 74 enters into separator 20 again.Outlet 74 is fixed on bottoms near the outer vortex of separator can produce and will carry the turbulence of additional catalyst again secretly.Upwards flow into also entrained catalyst particles again of stripping gas the separator and the hydrocarbon behind the stripping from stripping tower.In one embodiment of the invention, radially discharge from exporting 74 in a series of apertures 78 of part granules of catalyst through exporting 74 bottoms and along the circumferential direction distributing.Usually this outlet has 8 to 24 apertures that distribute along its space outerpace.These apertures have the length of 12 to 24 inches (305 to 600mm) and the width of about 3 to 6 inches (76 to 152mm) usually.These apertures are by improving separation efficiency and make simultaneously and outwards be sprayed onto stripping tower 22 outsides under the influence of granules of catalyst at eddy current containing eddy current near outlet 74 places, whereby outlet 74 centre portionss that compile of purge gas.
The opening of separator 20 directly reaches the top of stripping tower 22.The spiral air flow that produces by the whirlwind eddy current and from stripping tower 22 upwards the counter-current flow of mobile gas below outlet 74, produce a long turbulent area usually.The influence of any turbulence can reduce by a cover column plate 80, and these column plates play any turbulence of dispersion by the screw action generation of spiral air flow.These column plates are positioned at the below of the bottom of opening 74, disperse or the top, central section 82 of distribution plate 80 and outlet 74 bottoms between formation open space 84.This spatial length represents and preferably equals to export half of 74 diameters with A.Arrange that this space makes logistics can not directly enter opening 74 bottoms from the top 82 of column plate 80, so as descending eddy current with disperse column plate contact before its speed of reduction.
When catalyzer flows downward, it and the stripping gas counter current contact that enters through nozzle 24.For improving steam stripping efficiency, conical baffle is installed to improve contacting at stripping tower middle part or bottom solid particulate and stripping gas.These stripping baffles have taper shape common in the FCC stripping tower to arrange.In a specific layout, uppermost inner conical baffle plate 88 is received on the breaker plate 80, and bottom outer cone 90 is received on the wall of stripping tower 22.These baffle plates can be any common design well known by persons skilled in the art and be usually used in baffle plate in the FCC stripping tower.Best, stripping baffles has the overskirt that is suspended in down tapered segment at the bottom of the baffle plate.These overskirts can be perforated to improve the contact efficiency between stripping fluid and the granules of catalyst.
Fig. 2 has provided the layout of stripping tower.The top 22 of this stripping tower ' be arranged in reactor 19, bottom 22 " to reach under reactor 19 inside.Be furnished with like this and be beneficial to the nozzle 26 that is fixed for from stripping tower, extracting out used catalyst.
Stripping tower and separator can be supported on the reactor 19 in any mode that thermal expansion allows between separator 20 and reactor 19.A kind of support arrangement be the solid stripping tower is fixed on reactor 19 shells at the bottom of, the separator rigidity joins thereon, with such layout, knockout tower and stripping tower top 22 ' thermal expansion can expand to connect by pipeline 18 and central outlet 32 or the collector on it and provide.
Fig. 2 shows a kind of like this layout, knockout tower 20 bottoms, its middle and upper part 22 ' be fixed to and with stripping tower top 22 ' and bottom 22 " be slidingly connected.
Except the catalyst channels aperture, being slidingly connected of Fig. 2 arrange show stripping tower lower section 22 ' the additional aperture on top.When separator and cross section, stripping tower top 22 with respect to knockout tower lower section 22 ' when moving down, these additional apertures provide breach for breaker plate.
The size in these apertures is advisable to keep consistent dense catalyst bed at reactor bottom.This bed has prevented that stripped vapor (gas) from entering the reactor open space.Fig. 3 has drawn dissipation plate, stripping tower upper guard-plate, has been slidingly connected the vertical view in part and aperture.Referring to Fig. 3, show four dissipation plates that are mutually an angle of 90 degrees on the space, they from cross section, stripping tower top 22 ' outer wall extend to the outside of vortex stabiliser 76.Vortex stabiliser 76 is supported on the dissipation plate between two parties.Near the aperture 22 ' upper end, cross section 92 be positioned at dissipation plate 80 under interfere with each other with prevent to dissipate plate bottom and 22 ' top, cross section.Aperture 46 is circumferential regular arrangement along 22 ' bottom, cross section.Such aperture 46 has 4 to 16 usually.The open space that the size in aperture is enough to keep a certain amount of catalyzer in bed 44 and prevents to enter from the stripping tower escaping gas reactor 19.For typical a layout, the length in aperture 46 is 500 to 1000mm, and width is 300 to 400mm.The size in aperture 92 to be to provide suitable breach to be advisable to the dissipation plate, and for a common arrangement, the have an appointment size of 250mm * 250mm of this aperture will provide suitable breach.
The catalyzer that leaves stripping tower through nozzle 26 enters second stripping tower 28.The stripping tower 28 that is shown in greater detail among Fig. 4 is operated in a usual manner.Catalyzer is downwards through stripping tower and side/side graded a series of Internal baffles 100 of process and outer baffle 102.Catalyzer is extracted out through the aperture 104 in the support tube bottom, and stripping Internal baffle 100 is received on the supporting tube 106.Pipeline 48 is delivered to catalyzer in aperture 104, carries this catalyzer more in the above described manner in revivifier 52. Stripping baffles 100 and 102 can have attached overskirt and aperture again to increase catalyzer and to enter contact between the water vapor in the stripping tower through nozzle 30.The water vapor that contacts with used catalyst or other stripping fluid rise with respect to the catalyzer adverse current and flow out stripping tower 28 through nozzle 26.
The all water stripping steam and the hydrocarbon of discharge upwards flow and enter separator through the top stripping tower, and they are extracted out in center tracheae 32 with the form of product steam (gas) at this.Fig. 5 shows the top of reactor 19.The top of separator 20 reaches the top of reactor 19.Separator is supported by the supporting leg (not shown) that is linked on reactor 19 walls.Central gas nozzle 32 extends upward and branches in the collector, and this collector provides the transfer tube 32 of arm 110.Each arm 110 is connected in the import 112 of cyclonic separator 36.The top of collector arm and cyclonic separator is supported on the gas outlet tube 40.Providing the connection of expanding to adapt to the different heat expansion between flue and support arm and reactor 19 shells on the support arm.
All product steam (gas), strip, hydrocarbons, stripping gas and fluidizing gas enter center gas outlet 32 in aforesaid mode from separator.Pressure equilibrium aperture 116 open in the side of center gas pipe 32 and make the reactor open space and the inner UNICOM of flue to discharge fluidizing gas from the reactor open space.The size in aperture 116 is fallen (usually less than 0.7KPa) and is advisable to keep between reactor open space and the center gas pipe 32 suitable pressure.Certainly, even also can realize in reactor 19 inside or another outside cyclonic separator by venting port, a cyclonic separator import 112 that is arranged in support arm 110 from reactor open space discharge gas.In addition, the present invention can use the secondary cyclone 36 of any number, and this it will be apparent to those skilled in the art that.
Claims (7)
1, a kind of fluidized catalytic cracker, it comprises:
(a) reactor (19);
(b) the tubular type riser of a raw material and catalyst inlet end and an exit end is arranged;
(c) the lengthening separator (20) that is arranged in described reactor (19) of a top and bottom is arranged, described top has a tangential entry and the center gas at described separator (20) top with the direct UNICOM of outlet of described riser to export (32), there is an open bottom (74) described bottom, and the outermost layer of wherein said open bottom partly is untight so that fluid and particle flow unobstructedly;
(d) stripping tower (22) that is positioned under the described separator (20), described stripping tower have a described open bottom (74) with described separator (20) to open wide import and an outlet (26) that is used for extracting out from this stripping tower (22) catalyzer of UNICOM;
(e) be used for stripping gas is added to equipment (24) and (30) of described stripping tower (22); With
(f) be arranged in the isolated area of described stripping tower (22), this district comprises at least two vertical dissipation plates (80) that are positioned at the below, described open bottom (74) space of described separator (20).
2, the device of claim 1, wherein a swirl stabilization organ pipe (76) reaches the described separator (20) from described open bottom (74).
3, the device of claim 2, the diameter of wherein said vortex stabiliser (76) does not seal except described swirl stabilization organ pipe less than 20% and described open bottom of the diameter of open bottom (74).
4, claim 1,2 or 3 device, wherein said vertical dissipation plate (80) level and vertical direction is extended and near the described open bottom (74) of described separator (20) down square frame going out a free zone.
5, each device of claim 1 to 4, wherein said stripping tower (22) diameter is greater than the base diameter of described separator (20), described vertical panel extends internally to limit the chamber of two circumferential extensions from the wall of described stripping tower (22) at least, and this chamber is positioned at outer side-lower and close this outside of the described open bottom (74) of described separator.
6, each device of claim 1 to 5, wherein said center gas outlet (32) and at least one cyclonic separator (36) UNICOM, described cyclonic separator has the drop-pipe and the vapour outlet that is used for the exhaust vapour product flow that are used for catalyzer is turned back to reactor (19).
7, the method for a kind of fluid catalytic cracking of FCC feedstream (FCC), described method comprises:
(a) send FCC catalyzer and described FCC raw material to flow to riser reaction zone (10) and described feedstream is contacted with described FCC catalyzer described feedstream is converted into product steam (gas) at this;
(b) the described product steam (gas) that will from described riser, discharge and exhausted FCC mixture of catalysts directly enter the import of separator (20) and directly from described import tangentially described mixture is added to the described separator (20) with in forming and outside eddy current;
(c) eddy current in usefulness vortex stabiliser (76) is stablized in described separator (20);
(d) granules of catalyst is with the top of enclosed UNICOM mode adjacent stripping tower (22) below the bottom of described separator (20) flows directly to;
(f) annotate stripping gas in described stripping tower (22) and described granules of catalyst is contacted with described stripping gas with desorb hydrocarbon from described granules of catalyst;
(g) air-flow of the hydrocarbon of desorb and the stripping gas that makes progress is discharged from described stripping tower (22) through a plurality of vertical dissipation plate (80) in described stripping tower (22), the open space (84) of the described stripping tower (22) of below, the top of the central section (82) through being positioned at described dissipation plate (80) and described separator (20) bottom (74) leaves the top of described stripping tower (22) and enters the bottom of described separator (20);
(h) in the stripping tower (22) of the below, described central section (84) that is lower than described dissipation plate (80), keep fine and close relatively catalytic bed;
(i) extract described product steam (gas) and described air-flow through central outlet (32) out from the top of described separator (20);
(j) carry described product steam (gas) and described gas to flow to the separator (36) from described central outlet to reclaim extra granules of catalyst;
(k) from described separator (36), reclaim product flow;
(l) from described separator (36), carry the bottom of granules of catalyst to described stripping tower (22);
(m) remove exhausted FCC catalyzer and be transported to breeding blanket (52) from the lower end of described stripping tower (22);
(n) remove coke with the described FCC catalyzer of regenerating in described breeding blanket (52) by oxidation; With
(o) the FCC catalyzer is transported to described riser reaction zone (10) from described breeding blanket (52).
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002080974A CA2080974C (en) | 1990-11-15 | 1992-10-20 | Disengager stripper containing dissipation plates for use in an fcc process |
| AU27278/92A AU649889B1 (en) | 1990-11-15 | 1992-10-21 | Disengager stripper containing dissipation plates for use in an FCC process |
| AT92309716T ATE142247T1 (en) | 1990-11-15 | 1992-10-23 | DRAIN EXTRACTION DEVICE CONTAINING DISSIPATION PLATES FOR FCC PROCESSES |
| EP92309716A EP0593827B1 (en) | 1990-11-15 | 1992-10-23 | Disengager stripper containing dissipation plates for use in an FCC process |
| DE69213458T DE69213458T2 (en) | 1990-11-15 | 1992-10-23 | Drainage stripping device for FCC processes containing dissipation plates |
| ES92309716T ES2093798T3 (en) | 1990-11-15 | 1992-10-23 | REMOVAL DRAG SEPARATOR CONTAINING DISSIPATION PLATES FOR USE IN A FLUIDIZED CATALYTIC CRACKING PROCEDURE (FCC). |
| CN92112441A CN1035773C (en) | 1990-11-15 | 1992-10-26 | Disengager stripper containing dissipation plates for use in an FCC process |
| GR960403018T GR3021647T3 (en) | 1990-11-15 | 1996-11-14 | Disengager stripper containing dissipation plates for use in an FCC process |
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/613,037 US5158669A (en) | 1990-11-15 | 1990-11-15 | Disengager stripper |
| CA002080974A CA2080974C (en) | 1990-11-15 | 1992-10-20 | Disengager stripper containing dissipation plates for use in an fcc process |
| AU27278/92A AU649889B1 (en) | 1990-11-15 | 1992-10-21 | Disengager stripper containing dissipation plates for use in an FCC process |
| EP92309716A EP0593827B1 (en) | 1990-11-15 | 1992-10-23 | Disengager stripper containing dissipation plates for use in an FCC process |
| CN92112441A CN1035773C (en) | 1990-11-15 | 1992-10-26 | Disengager stripper containing dissipation plates for use in an FCC process |
| US07/966,777 US5316662A (en) | 1990-11-15 | 1992-10-27 | Integrated disengager stripper and its use in fluidized catalytic cracking process |
| US07/966,776 US5314611A (en) | 1990-11-15 | 1992-10-27 | External integrated disengager stripper and its use in fluidized catalytic cracking process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1086247A true CN1086247A (en) | 1994-05-04 |
| CN1035773C CN1035773C (en) | 1997-09-03 |
Family
ID=36791815
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92112441A Expired - Fee Related CN1035773C (en) | 1990-11-15 | 1992-10-26 | Disengager stripper containing dissipation plates for use in an FCC process |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0593827B1 (en) |
| CN (1) | CN1035773C (en) |
| AT (1) | ATE142247T1 (en) |
| AU (1) | AU649889B1 (en) |
| CA (1) | CA2080974C (en) |
| DE (1) | DE69213458T2 (en) |
| ES (1) | ES2093798T3 (en) |
| GR (1) | GR3021647T3 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055492C (en) * | 1996-03-22 | 2000-08-16 | 中国石油化工集团公司 | Fast gas-solid separation and gas lead-out method and equipment for hoisting-pipe catalytic-cracking reaction system |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5869008A (en) * | 1996-05-08 | 1999-02-09 | Shell Oil Company | Apparatus and method for the separation and stripping of fluid catalyst cracking particles from gaseous hydrocarbons |
| FR2894842B1 (en) * | 2005-12-21 | 2008-02-01 | Inst Francais Du Petrole | NEW SOLID GAS SEPARATION AND STRIPING SYSTEM FOR FLUIDIZED BED CATALYTIC CRACKING UNITS |
| US11261143B2 (en) * | 2019-04-12 | 2022-03-01 | Uop Llc | Apparatus and process for separating gases from catalyst |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4500423A (en) * | 1981-02-26 | 1985-02-19 | Chevron Research Company | Separation of reacted hydrocarbons and catalyst in fluidized catalytic cracking |
| US4414100A (en) * | 1981-12-29 | 1983-11-08 | Chevron Research Company | Fluidized catalytic cracking |
| US4749471A (en) * | 1983-09-06 | 1988-06-07 | Mobil Oil Corporation | Closed FCC cyclone process |
| CA1277276C (en) * | 1984-07-18 | 1990-12-04 | James H. Haddad | Fcc catalyst stripping method and apparatus |
| US4927527A (en) * | 1984-07-18 | 1990-05-22 | Mobil Oil Corporation | Method for reducing overcracking during FCC catalyst separation |
| US4572780A (en) * | 1984-10-22 | 1986-02-25 | Mobil Oil Corporation | Multistage stripper for FCC unit with catalyst separation by spinning |
| CN1009659B (en) * | 1985-06-24 | 1990-09-19 | 法国石油公司 | Process and equipment for fluidized bed catalytic cracking |
| US5043145A (en) * | 1986-08-21 | 1991-08-27 | Exxon Research & Engineering Company | Minimal holdup reactor grid |
| GB8904409D0 (en) * | 1989-02-27 | 1989-04-12 | Shell Int Research | Process for the conversion of a hydrocarbonaceous feedstock |
| US5062945A (en) * | 1988-09-23 | 1991-11-05 | Mobil Oil Corporation | Method of FCC spent catalyst stripping for improved efficiency and reduced hydrocarbon flow to regenerator |
| US5059302A (en) * | 1989-05-16 | 1991-10-22 | Engelhard Corporation | Method and apparatus for the fluid catalytic cracking of hydrocarbon feed employing a separable mixture of catalyst and sorbent particles |
| US4988430A (en) * | 1989-12-27 | 1991-01-29 | Uop | Supplying FCC lift gas directly from product vapors |
| US5158669A (en) * | 1990-11-15 | 1992-10-27 | Uop | Disengager stripper |
-
1992
- 1992-10-20 CA CA002080974A patent/CA2080974C/en not_active Expired - Fee Related
- 1992-10-21 AU AU27278/92A patent/AU649889B1/en not_active Ceased
- 1992-10-23 EP EP92309716A patent/EP0593827B1/en not_active Expired - Lifetime
- 1992-10-23 AT AT92309716T patent/ATE142247T1/en not_active IP Right Cessation
- 1992-10-23 ES ES92309716T patent/ES2093798T3/en not_active Expired - Lifetime
- 1992-10-23 DE DE69213458T patent/DE69213458T2/en not_active Expired - Fee Related
- 1992-10-26 CN CN92112441A patent/CN1035773C/en not_active Expired - Fee Related
-
1996
- 1996-11-14 GR GR960403018T patent/GR3021647T3/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055492C (en) * | 1996-03-22 | 2000-08-16 | 中国石油化工集团公司 | Fast gas-solid separation and gas lead-out method and equipment for hoisting-pipe catalytic-cracking reaction system |
Also Published As
| Publication number | Publication date |
|---|---|
| GR3021647T3 (en) | 1997-02-28 |
| DE69213458D1 (en) | 1996-10-10 |
| CN1035773C (en) | 1997-09-03 |
| ATE142247T1 (en) | 1996-09-15 |
| EP0593827A1 (en) | 1994-04-27 |
| AU649889B1 (en) | 1994-06-02 |
| EP0593827B1 (en) | 1996-09-04 |
| DE69213458T2 (en) | 1997-01-02 |
| CA2080974C (en) | 2004-02-17 |
| CA2080974A1 (en) | 1994-04-21 |
| ES2093798T3 (en) | 1997-01-01 |
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| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
| OR01 | Other related matters | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |