CA2222597C - Reduced chaos cyclone separation - Google Patents
Reduced chaos cyclone separation Download PDFInfo
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- CA2222597C CA2222597C CA002222597A CA2222597A CA2222597C CA 2222597 C CA2222597 C CA 2222597C CA 002222597 A CA002222597 A CA 002222597A CA 2222597 A CA2222597 A CA 2222597A CA 2222597 C CA2222597 C CA 2222597C
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- Prior art keywords
- gas
- cyclone
- solids
- cyclone body
- inlet
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/005—Separating solid material from the gas/liquid stream
- B01J8/0055—Separating solid material from the gas/liquid stream using cyclones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B04—CENTRIFUGAL APPARATUS OR MACHINES FOR CARRYING-OUT PHYSICAL OR CHEMICAL PROCESSES
- B04C—APPARATUS USING FREE VORTEX FLOW, e.g. CYCLONES
- B04C5/00—Apparatus in which the axial direction of the vortex is reversed
- B04C5/08—Vortex chamber constructions
- B04C5/081—Shapes or dimensions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B04—CENTRIFUGAL APPARATUS OR MACHINES FOR CARRYING-OUT PHYSICAL OR CHEMICAL PROCESSES
- B04C—APPARATUS USING FREE VORTEX FLOW, e.g. CYCLONES
- B04C5/00—Apparatus in which the axial direction of the vortex is reversed
- B04C5/24—Multiple arrangement thereof
- B04C5/28—Multiple arrangement thereof for parallel flow
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B04—CENTRIFUGAL APPARATUS OR MACHINES FOR CARRYING-OUT PHYSICAL OR CHEMICAL PROCESSES
- B04C—APPARATUS USING FREE VORTEX FLOW, e.g. CYCLONES
- B04C5/00—Apparatus in which the axial direction of the vortex is reversed
- B04C5/24—Multiple arrangement thereof
- B04C5/30—Recirculation constructions in or with cyclones which accomplish a partial recirculation of the medium, e.g. by means of conduits
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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
A cyclone (500) suitable for use in a third stage separator in a fluid catalytic cracking unit or to improve other gas/solid separations. The cyclo ne has an inlet for gas and entrained solids (515) and a clean gas outlet tube (520) at one end of a cyclone body. Solids and some gas are withdrawn through a solid s outlet (545) and discharged into a catch chamber. Some of the gas discharged with the solids into the catch chamber is returned to the interior of the cyclone body through a gas reflux opening in the cyclone (555). Chaotic reflux of ga s back into the cyclone through the solids outlet is eliminated.
Description
REDUCED CHAOS CYCLONE SEPARATION
This invention relates to cyclone separators and their use in fluidized catalytic cracking (FCC) of heavy hydrocarbon feeds.
Cyclones are used extensively to separate solid particles from gases in many industrial applications. One area of use is in fluid catalytic cracking (FCC) of hydrocarbons to form lighter products. In FCC units, the cyclones are found in two main locations, in the reactor (a term used alternatively with "disengager" since the desired cracking reactions take place in a riser upstream of the reactor) and in the regenerator where the fine particles of the cracking catalyst need to be separated from the regenerator gases.
Reactor Cyclones In the FCC reactor vessel a riser discharges cracked product vapor and spent catalyst into the "reactor" or disengaing vessel. Primary cyclones separate most of the cracked product from the spent catalyst, but large amounts of product vapor remain with the recovered spent catalyst.
The product vapors must be present to keep the recovered catalyst in a fluidized state as the spent catalyst passes down the primary cyclone diplegs. The product vapors are eventually removed from the catalyst in the stripping section which is generally in the same vessel containing the cyclone(s). Stripping vapor returns or refluxes into the cyclone through an opening on the inlet to the cyclone, or the gas outlet from the cyclone, or in some instances into an inlet associated with the cyclone itself.
There is a large volume of product entrained with or absorbed by the catalyst, as the catalyst:oil weight ratio is usually 3:1 to 6:1. There is a large volume of stripping steam used to displace or recover the product gas from the spent catalyst. The stripper vapor is a large stream which represents a significant amount of product and a significant amount of gas traffic. Stripper vapor may pass through the primary cyclones used to generate the spent catalyst solids rich stream.
There are two types of cyclone systems which operate in the FCC reactor environment. The two types in widespread use today are open and closed cyclones (in contrast to open-bottom and closed-bottom cyclones previously discussed, which can be quite different).
In an open cyclone system the vessel receiving material discharged from a riser reactor is relatively open. Gas can have a 10 to 30 second or even longer residence time in this vessel. The riser reactor discharges into a large vessel containing a stripper in a lower portion of the vessel and cyclones in an upper portion. Gas recycle is relatively straightforward.
Stripping steam and stripped cracked product gas all enter the inlet horn of primary cyclone(s). In a closed cyclone system product gas is generally isolated from the reactor vessel and leave the vessel within a few seconds of residence time. The shortened gas residence time greatly reduces undesired thermal cracking which would otherwise occur in the reactor vessel.
Gas recycle in a closed or relatively closed bottom cyclone system is more complicated than gas recycle in an open system. This is because the product gas is removed in a system which is "closed" to the reactor freeboard. The riser discharges into a cyclone, the gas outlet of which is closely coupled to or connected directly with a secondary cyclone. The gas exiting through the cyclone gas outlets is efficiently dealt with in such systems, but the gas discharged with the recovered solids phase also has to be removed. Most systems remove this gas,:and accompanying stripping steam, through an annular opening around either the primary cyclone inlet or primary cyclone gas outlet transfer line to accommodate stripper vapor.
US 5,362,379 discloses the use of an annular opening around the gas outlet of the primary cyclone outlet to permit stripping vapor to flow from the reactor vessel into the primary cyclone. The device is an improvement over similar open bottom cyclones (US 4,478,708) where stripping gas flows up into the open bottom at the same time that separated catalyst exits the bottom of the chamber. The incoming gas entrains some separated catalyst and carries it back into the chamber, reducing cyclone efficiency.
In both closed and open bottom cyclone systems the gas streams involved are large. The gas feed to the cyclone is large, and the gas stream associated with gas from the stripper is large. There is always a minor amount of gas entrained with catalyst discharged from the cyclones.
While this gas is essential to maintain the discharged solids in a fluidized state the amount of gas involved is so much less than the feed gas and stripping vapor streams that most designers ignore the gas associated with entrained solids.
Regenerator Cyclones FCC regenerator cyclones usually include primary and secondary cyclones. Gas and entrained catalyst enter the inlet horns of the primary cyclones. Recovered catalyst is discharged down primary cyclone diplegs into the fluidized bed in the regenerator vessel. Fluidizing gas discharged from the diplegs with the recovered catalyst simply reemerges from the catalyst bed to reenter the inlet horn of the primary cyclone. The gas discharged from each primary cyclone usually is charged to the inlet of a coupled secondary cyclone, and again some fluidizing gas is discharged down the diplegs of the secondary cyclone into the catalyst bed within the regenerator vessel. This WO 96/40840 PCTlUS96/07229 secondary cyclone dipleg gas stream also reemerges from the catalyst bed to reenter the inlet horn of the primary =
cyclones.
The cyclone dipleg gas, from both the primary and secondary cyclones, simply mixes with gas rising from the fluidized bed of regenerated catalyst and reenters the primary cyclone inlet horn. The gas streams discharged with the recovered solids streams are thus easily recycled through the large freeboard volume within the regenerator vessel.
Gas Recycle - Third Stage Separator Third stage separator (TSS) cyclones used to remove residual fine partiles from the regenerator effluent gases are different from primary and secondary cyclones. The difference is not just gas/solids makeup, which is similar to the gas/solids feed to the secondary cyclones. Solids are generally discharged in a different way than occurs in primary cyclone, and handling of gas discharged with solids is different.
TSS cyclones have generally not satisfactorily addressed the problem of how to deal with gas discharged with the solids. In some TSS cyclones there is no dipleg and no place for deaeration of solids. The solids are discharged at a relatively high velocity and may aspirate a significant amount of gas. Rather than gas fluidizing the solids the solids are carrying out excessive amounts of gas. At the solids outlet of TSS cyclones, the considerable kinetic energy in the solids carries gas from the cyclone body. Large amounts of gas exit the cyclone, and re-enter the cyclone in some way. Pulses of catalyst and gas discharge form the cyclone, alternating with reverse flow of gas back into the barrel. This is the only way for gas discharged with the solids rich phase to return to the cyclones from the catch chamber, as there is not enough gas removed with the solids phase from the bottom of the device to mass balance the cyclones. Tests with helium (He) tracer and two cyclones confirmed there is significant gas traffic from the interior of the cyclone out with the 5 solids and back to the interior of the cyclone. This circulation had to occur through the solids outlet. In a multiple cyclone third stage separator we speculated that all cyclones discharge solids and gas, and some or all unintentionally recycle or reflux gas back through the solids outlet into the cyclone body. Refluxing gas entrains solids back into the inner vortex of the cyclone and out the gas outlet tube. Multiple cyclones may interact with each other to continuously and chaotically discharge and reentrain dust. Reverse flow, chaotic or randomly fluctuating in space and time, refluxes this gas through the solids outlet in countercurrent to flow out of the solids discharge.
While such chaotic operation is most troublesome in a multiple cyclone installation it may occur in a single cyclone. The effect of chaotic reflux through the solids outlet is to disrupt gas streamlines of the tangential flow within the cyclone body.
The present invention provides a simple and effective way to improve cyclone efficiency by providing a separate gas reentry means to the cyclone to re-introduce the refluxed gas. Gas refluxed in this way has little adverse effect on tangential velocity of the outer cyclone vortex, and might even increase it. It is in this outer vortex region where fines separation occurs.
Cyclone operation may be stabilized and the amount of fines discharged from the gas outlet tube may be reduced by one half, by providing a separate gas reflux, preferably in the bottom of the cyclone body.
This invention relates to cyclone separators and their use in fluidized catalytic cracking (FCC) of heavy hydrocarbon feeds.
Cyclones are used extensively to separate solid particles from gases in many industrial applications. One area of use is in fluid catalytic cracking (FCC) of hydrocarbons to form lighter products. In FCC units, the cyclones are found in two main locations, in the reactor (a term used alternatively with "disengager" since the desired cracking reactions take place in a riser upstream of the reactor) and in the regenerator where the fine particles of the cracking catalyst need to be separated from the regenerator gases.
Reactor Cyclones In the FCC reactor vessel a riser discharges cracked product vapor and spent catalyst into the "reactor" or disengaing vessel. Primary cyclones separate most of the cracked product from the spent catalyst, but large amounts of product vapor remain with the recovered spent catalyst.
The product vapors must be present to keep the recovered catalyst in a fluidized state as the spent catalyst passes down the primary cyclone diplegs. The product vapors are eventually removed from the catalyst in the stripping section which is generally in the same vessel containing the cyclone(s). Stripping vapor returns or refluxes into the cyclone through an opening on the inlet to the cyclone, or the gas outlet from the cyclone, or in some instances into an inlet associated with the cyclone itself.
There is a large volume of product entrained with or absorbed by the catalyst, as the catalyst:oil weight ratio is usually 3:1 to 6:1. There is a large volume of stripping steam used to displace or recover the product gas from the spent catalyst. The stripper vapor is a large stream which represents a significant amount of product and a significant amount of gas traffic. Stripper vapor may pass through the primary cyclones used to generate the spent catalyst solids rich stream.
There are two types of cyclone systems which operate in the FCC reactor environment. The two types in widespread use today are open and closed cyclones (in contrast to open-bottom and closed-bottom cyclones previously discussed, which can be quite different).
In an open cyclone system the vessel receiving material discharged from a riser reactor is relatively open. Gas can have a 10 to 30 second or even longer residence time in this vessel. The riser reactor discharges into a large vessel containing a stripper in a lower portion of the vessel and cyclones in an upper portion. Gas recycle is relatively straightforward.
Stripping steam and stripped cracked product gas all enter the inlet horn of primary cyclone(s). In a closed cyclone system product gas is generally isolated from the reactor vessel and leave the vessel within a few seconds of residence time. The shortened gas residence time greatly reduces undesired thermal cracking which would otherwise occur in the reactor vessel.
Gas recycle in a closed or relatively closed bottom cyclone system is more complicated than gas recycle in an open system. This is because the product gas is removed in a system which is "closed" to the reactor freeboard. The riser discharges into a cyclone, the gas outlet of which is closely coupled to or connected directly with a secondary cyclone. The gas exiting through the cyclone gas outlets is efficiently dealt with in such systems, but the gas discharged with the recovered solids phase also has to be removed. Most systems remove this gas,:and accompanying stripping steam, through an annular opening around either the primary cyclone inlet or primary cyclone gas outlet transfer line to accommodate stripper vapor.
US 5,362,379 discloses the use of an annular opening around the gas outlet of the primary cyclone outlet to permit stripping vapor to flow from the reactor vessel into the primary cyclone. The device is an improvement over similar open bottom cyclones (US 4,478,708) where stripping gas flows up into the open bottom at the same time that separated catalyst exits the bottom of the chamber. The incoming gas entrains some separated catalyst and carries it back into the chamber, reducing cyclone efficiency.
In both closed and open bottom cyclone systems the gas streams involved are large. The gas feed to the cyclone is large, and the gas stream associated with gas from the stripper is large. There is always a minor amount of gas entrained with catalyst discharged from the cyclones.
While this gas is essential to maintain the discharged solids in a fluidized state the amount of gas involved is so much less than the feed gas and stripping vapor streams that most designers ignore the gas associated with entrained solids.
Regenerator Cyclones FCC regenerator cyclones usually include primary and secondary cyclones. Gas and entrained catalyst enter the inlet horns of the primary cyclones. Recovered catalyst is discharged down primary cyclone diplegs into the fluidized bed in the regenerator vessel. Fluidizing gas discharged from the diplegs with the recovered catalyst simply reemerges from the catalyst bed to reenter the inlet horn of the primary cyclone. The gas discharged from each primary cyclone usually is charged to the inlet of a coupled secondary cyclone, and again some fluidizing gas is discharged down the diplegs of the secondary cyclone into the catalyst bed within the regenerator vessel. This WO 96/40840 PCTlUS96/07229 secondary cyclone dipleg gas stream also reemerges from the catalyst bed to reenter the inlet horn of the primary =
cyclones.
The cyclone dipleg gas, from both the primary and secondary cyclones, simply mixes with gas rising from the fluidized bed of regenerated catalyst and reenters the primary cyclone inlet horn. The gas streams discharged with the recovered solids streams are thus easily recycled through the large freeboard volume within the regenerator vessel.
Gas Recycle - Third Stage Separator Third stage separator (TSS) cyclones used to remove residual fine partiles from the regenerator effluent gases are different from primary and secondary cyclones. The difference is not just gas/solids makeup, which is similar to the gas/solids feed to the secondary cyclones. Solids are generally discharged in a different way than occurs in primary cyclone, and handling of gas discharged with solids is different.
TSS cyclones have generally not satisfactorily addressed the problem of how to deal with gas discharged with the solids. In some TSS cyclones there is no dipleg and no place for deaeration of solids. The solids are discharged at a relatively high velocity and may aspirate a significant amount of gas. Rather than gas fluidizing the solids the solids are carrying out excessive amounts of gas. At the solids outlet of TSS cyclones, the considerable kinetic energy in the solids carries gas from the cyclone body. Large amounts of gas exit the cyclone, and re-enter the cyclone in some way. Pulses of catalyst and gas discharge form the cyclone, alternating with reverse flow of gas back into the barrel. This is the only way for gas discharged with the solids rich phase to return to the cyclones from the catch chamber, as there is not enough gas removed with the solids phase from the bottom of the device to mass balance the cyclones. Tests with helium (He) tracer and two cyclones confirmed there is significant gas traffic from the interior of the cyclone out with the 5 solids and back to the interior of the cyclone. This circulation had to occur through the solids outlet. In a multiple cyclone third stage separator we speculated that all cyclones discharge solids and gas, and some or all unintentionally recycle or reflux gas back through the solids outlet into the cyclone body. Refluxing gas entrains solids back into the inner vortex of the cyclone and out the gas outlet tube. Multiple cyclones may interact with each other to continuously and chaotically discharge and reentrain dust. Reverse flow, chaotic or randomly fluctuating in space and time, refluxes this gas through the solids outlet in countercurrent to flow out of the solids discharge.
While such chaotic operation is most troublesome in a multiple cyclone installation it may occur in a single cyclone. The effect of chaotic reflux through the solids outlet is to disrupt gas streamlines of the tangential flow within the cyclone body.
The present invention provides a simple and effective way to improve cyclone efficiency by providing a separate gas reentry means to the cyclone to re-introduce the refluxed gas. Gas refluxed in this way has little adverse effect on tangential velocity of the outer cyclone vortex, and might even increase it. It is in this outer vortex region where fines separation occurs.
Cyclone operation may be stabilized and the amount of fines discharged from the gas outlet tube may be reduced by one half, by providing a separate gas reflux, preferably in the bottom of the cyclone body.
According to the present invention the cyclone separator comprises:
(i) a closed-bottom cyclone body, (ii) a feed gas inlet at the inlet end of the cyclone body for the stream of gas and entrained solids, (iii) a gas outlet tube in the inlet end having a longitudinal axis aligned with the longitudinal axis of the cyclone body for withdrawing gas with a reduced entrained solids content (iv) one or more solids outlets in a sidewall of the cyclone body for tangential discharge of solids and a minor amount of gas from the closed-bottom cyclone into a catch chamber, and (v) at least one gas reflux opening fluidly isolated from the feed gas inlet for recycling gas from the catch chamber back into the cyclone body.
The gas reflux inlet suitably comprises a gas reflux tube at the closed end of cyclone body (usually at least partially cylindrical in shape); this reflux tube has a diameter smaller than the diameter of the cyclone body and terminates in a reflux inlet outside the cyclone body and a reflux exit inside the cyclone body. The gas reflux tube extends within the cyclone body from 0 to 1 cyclone body lengths and extends outside the cyclone body into a catch chamber from 0 to 1 cyclone body lengths. The cyclone body has the gas outlet tube at the opposite end from the closed end, and this gas outlet tube (which has a diameter smaller than the diameter of the cyclone body) has a longitudinal axis axially aligned with the cyclone body. The reflux exit inside the cyclone body is on a portion of the gas reflux tube which is axially aligned with the gas outlet tube. In addition, the inlet for the gas/solids stream is at the end of the cyclone body remote from the reflux inlet and is disposed tangentially to admit the incoming gas/solids mixture with a swirl motion.
The solids outlet discharges a concentrated solids stream with a minor portion of gas from the cyclone body through one or more openings in the sidewall of the cyclone body near the sealed end. The solids outlet and the gas reflux inlet are in fluid communication outside the cyclone body.
When used in a fluidized catalytic cracking process, the hydrocarbon feed is catalytically cracked by contact with a regenerated cracking catalyst in a cracking reactor to produce lighter products and spent catalyst and the spent catalyst is regenerated in a catalyst regenerator equipped with one or more separators for recovery of catalyst and fines from flue gas to produce the regenerated catalyst which is recycled to the cracking reactor. The regenerator flue gas containing catalyst fines is circulated to an external separator in an external separator which removes at least a portion of the fines from the regenerator flue gas stream. This external separator comprises a number of the cyclones described above. The solids outlets discharge fines and a minor amount of gas into a catch chamber in a lower portion of the external separator from which the gas reflux takes place to recycle at least a portion of the gas discharged with the solids from the catch chamber back into the cyclone body.
The multi-cyclone gas/solids separator preferably comprises a number of the cyclones each of which has a gas/solids inlet for admitting gas and entrained solids into the annular space defined by the sidewall of the cyclone body and the cylindrical gas outlet tube axially aligned with the cyclone body. The solids outlet at the opposite end of the cyclone body has a tangential outlet for solids and the entrained gas. The cyclones share both a common catch chamber for solids discharged from the solids outlet and a common manifold for gas and entrained solids.
The present cyclones are preferably used in a third stage separator removing catalyst and fines from regenerator flue gas. In many instances, existing equipment may be used by adding an extension to the prior art small diameter horizontal cyclones.
When used as a third stage separator in FCC there will be so little solids loading at this point in the FCC process so that refractory lining may not be needed.
The gas reflux open area should be large enough to handle anticipated return gas flow, but should be no larger than the conventional solids outlet. In many instances, good results will be achieved with an open area equal to 1 to 10%,and preferably 1.5 to 5%, and most preferably 2 to 4% of the cross sectional area available for fluid flow through the conventional solids outlet.
The gas reflux entry may be a simple hole in the bottom of the cyclone or, preferably, may comprise a gas reflux tube which has an interior portion within the cyclone body which terminates in an open end, with an exterior portion extending into the catch chamber having a closed end and at least one tangential inlet or slot in its sidewall to impart swirl to the recycled gas entering the interior of the cyclone body.
The reflux tube can extend on either side of the cyclone body by a distance equal to 0 to 100% of the length of the cyclone body.
Also, the gas reflux tube discharges tangentially into the cyclone body in the same direction as the tangential feed gas inlet.
Figure 1 (prior art) is a simplified schematic view of an FCC
unit of the prior art.
Figure 2 (prior art) is a simplified schematic view of a third stage separator of the prior art with vertical cyclones.
Figure 3 (prior art) is a simplified schematic view of a third stage separator of the prior art with horizontal cyclones.
Figure 4 (invention) is a simplified sectional view of a preferred cyclone with a gas reentry cyclone.
Figure 5 (invention) is a bottom view of the Fig. 4 cyclone.
Figure 6 (invention) a cyclone with a conical bottom and simple orifice hole for gas reentry.
(i) a closed-bottom cyclone body, (ii) a feed gas inlet at the inlet end of the cyclone body for the stream of gas and entrained solids, (iii) a gas outlet tube in the inlet end having a longitudinal axis aligned with the longitudinal axis of the cyclone body for withdrawing gas with a reduced entrained solids content (iv) one or more solids outlets in a sidewall of the cyclone body for tangential discharge of solids and a minor amount of gas from the closed-bottom cyclone into a catch chamber, and (v) at least one gas reflux opening fluidly isolated from the feed gas inlet for recycling gas from the catch chamber back into the cyclone body.
The gas reflux inlet suitably comprises a gas reflux tube at the closed end of cyclone body (usually at least partially cylindrical in shape); this reflux tube has a diameter smaller than the diameter of the cyclone body and terminates in a reflux inlet outside the cyclone body and a reflux exit inside the cyclone body. The gas reflux tube extends within the cyclone body from 0 to 1 cyclone body lengths and extends outside the cyclone body into a catch chamber from 0 to 1 cyclone body lengths. The cyclone body has the gas outlet tube at the opposite end from the closed end, and this gas outlet tube (which has a diameter smaller than the diameter of the cyclone body) has a longitudinal axis axially aligned with the cyclone body. The reflux exit inside the cyclone body is on a portion of the gas reflux tube which is axially aligned with the gas outlet tube. In addition, the inlet for the gas/solids stream is at the end of the cyclone body remote from the reflux inlet and is disposed tangentially to admit the incoming gas/solids mixture with a swirl motion.
The solids outlet discharges a concentrated solids stream with a minor portion of gas from the cyclone body through one or more openings in the sidewall of the cyclone body near the sealed end. The solids outlet and the gas reflux inlet are in fluid communication outside the cyclone body.
When used in a fluidized catalytic cracking process, the hydrocarbon feed is catalytically cracked by contact with a regenerated cracking catalyst in a cracking reactor to produce lighter products and spent catalyst and the spent catalyst is regenerated in a catalyst regenerator equipped with one or more separators for recovery of catalyst and fines from flue gas to produce the regenerated catalyst which is recycled to the cracking reactor. The regenerator flue gas containing catalyst fines is circulated to an external separator in an external separator which removes at least a portion of the fines from the regenerator flue gas stream. This external separator comprises a number of the cyclones described above. The solids outlets discharge fines and a minor amount of gas into a catch chamber in a lower portion of the external separator from which the gas reflux takes place to recycle at least a portion of the gas discharged with the solids from the catch chamber back into the cyclone body.
The multi-cyclone gas/solids separator preferably comprises a number of the cyclones each of which has a gas/solids inlet for admitting gas and entrained solids into the annular space defined by the sidewall of the cyclone body and the cylindrical gas outlet tube axially aligned with the cyclone body. The solids outlet at the opposite end of the cyclone body has a tangential outlet for solids and the entrained gas. The cyclones share both a common catch chamber for solids discharged from the solids outlet and a common manifold for gas and entrained solids.
The present cyclones are preferably used in a third stage separator removing catalyst and fines from regenerator flue gas. In many instances, existing equipment may be used by adding an extension to the prior art small diameter horizontal cyclones.
When used as a third stage separator in FCC there will be so little solids loading at this point in the FCC process so that refractory lining may not be needed.
The gas reflux open area should be large enough to handle anticipated return gas flow, but should be no larger than the conventional solids outlet. In many instances, good results will be achieved with an open area equal to 1 to 10%,and preferably 1.5 to 5%, and most preferably 2 to 4% of the cross sectional area available for fluid flow through the conventional solids outlet.
The gas reflux entry may be a simple hole in the bottom of the cyclone or, preferably, may comprise a gas reflux tube which has an interior portion within the cyclone body which terminates in an open end, with an exterior portion extending into the catch chamber having a closed end and at least one tangential inlet or slot in its sidewall to impart swirl to the recycled gas entering the interior of the cyclone body.
The reflux tube can extend on either side of the cyclone body by a distance equal to 0 to 100% of the length of the cyclone body.
Also, the gas reflux tube discharges tangentially into the cyclone body in the same direction as the tangential feed gas inlet.
Figure 1 (prior art) is a simplified schematic view of an FCC
unit of the prior art.
Figure 2 (prior art) is a simplified schematic view of a third stage separator of the prior art with vertical cyclones.
Figure 3 (prior art) is a simplified schematic view of a third stage separator of the prior art with horizontal cyclones.
Figure 4 (invention) is a simplified sectional view of a preferred cyclone with a gas reentry cyclone.
Figure 5 (invention) is a bottom view of the Fig. 4 cyclone.
Figure 6 (invention) a cyclone with a conical bottom and simple orifice hole for gas reentry.
Figure 7 (invention) shows a closed bottom cyclone with a tangential solids exit, and tube for gas reentry.
The present invention can be better understood by reviewing it in conjunction with a conventional riser cracking FCC unit. When used in an FCC process, the typical cracking conditions and catalysts may be used with the exception of the adoption of the present cyclones.
Figure 1 illustrates a fluid catalytic cracking system of the prior art, and is similar to the Kellogg Ultra Orthoflow converter Model F shown as Fig. 17 of Fluid Catalytic Cracking Report, in the January 8, 1990 edition of Oil & Gas Journal. The process of the present invention works well with this type of FCC unit.
A heavy feed such as a gas oil, vacuum gas oil is added to riser reactor 6 through feed injection nozzles 2.
The cracking reaction is almost completed in the riser reactor, which takes a 90 turn at the top of the reactor at elbow 10. Spent catalyst and cracked products discharged from the riser reactor pass through riser cyclones 12 which efficiently separate most of the spent catalyst from cracked product. Cracked product is discharged into disengager 14 and eventually is removed through upper cyclones 16 and conduit 18 to the fractionator.
Spent catalyst is discharged down from a dipleg of riser cyclones 12 into catalyst stripper 8 where one, or preferably 2 or more, stages of steam stripping occur, with stripping steam admitted by means 19 and 21. The stripped hydrocarbons, and stripping steam, pass into disengager 14 and are removed with cracked products after passage through upper cyclones 16.
Stripped catalyst is discharged down through spent catalyst standpipe 26 into catalyst regenerator 24. The flow of catalyst is controlled with spent catalyst plug valve 36.
Catalyst is regenerated in regenerator 24 by contact with air, added through air lines and an air grid 5 distributor not shown. A catalyst cooler 28 is provided so heat may be removed from the regenerator if desired.
Regenerated catalyst is withdrawn from the regenerator through re-generated catalyst plug valve assembly 30 and discharged through lateral 32 into the base of the riser 10 reactor 6 to contact and crack fresh feed injected through injectors 2 as previously discussed. Flue gas, and some entrained catalyst, is discharged into a dilute phase region in the upper portion of_regenerator 24. Entrained catalyst is separated from flue gas in multiple stages of cyclones 4 and discharged through outlets 38 into plenum 20 for discharge to the flue gas line through line 22.
The bubbling dense bed in such a regenerator exhibits excellent horizontal mixing, and the heat exchanger 28 allows full CO burn operation even with heavy feeds.
Figure 1 does not show a third stage separator. Line 22 in most refineries would go to some type of third stage separator (not shown), usually one involving 50 to 100 (or more) small diameter horizontal or vertical cyclones.
Purified flue gas would then pass through an optional power recovery turbine (not shown) then go to a stack for discharge to the atmosphere, optionally through a flue gas clean up device, such as an SOX scrubber, or the like, not shown.
Figure 2 (Prior Art) is similar to Fig. 1 of Improved hot-gas expanders for cat cracker flue gas, Hydrocarbon ~
Processing, March 1976, p. 141.
M
Third stage separator 200 receives a fines containing FCC flue gas through inlet 210. Gas is distributed through plenum 220 to the inlets of a plurality of small diameter ceramic tubes 235 containing swirl vanes not shown. Fines collect on the walls of tubes 235 and are discharged from the base of the tubes as an annular stream of solids 230. A clean gas stream is withdrawn through outlet tubes 239 to be removed from the vessel through outlet 290. Solids are removed through solids outlet 265.
Figure 3 (Prior Art) shows another type of commercially available TSS unit, with cyclones mounted horizontally, as shown in Fig. 1 of US 5,178,648. Separator 10 comprises gas inlet 12, housing 14, clean gas discharge outlet 16, a main solids outlet 18 and an auxiliary solids outlet 20.
The wall of housing 14 may be insulated, or a heat exchanger, not shown, may be used to cool the gas. The interior of housing 14 is divided into a clean gas chamber 22 bounded on the outside by housing 14 and on the interior by subhousing 24 which also forms the boundary of chamber 26.
The interior of chamber 26 is defined by discharge chamber housing structure 28 concentrically enclosing a particle discharge chamber 30.
Subhousing 24 is supported centrally by refractory insulated member 32 which is supported by top cover 36.
Discharge chamber 28 is supported from conical section 38 of subhousing 24 by cylindrical skirt 40. Adjacent skirt 40, the lower section of structure 28 may be formed as cone structure 42 joined at its apex to conduit 44 having at its lower end the main solids outlet 18. Housing 14 is supported by cleats 60.
Particulate laden gas enters the device and passes through the inlets 82 of a plurality of small diameter, horizontally mounted cyclones 80. Clean gas is discharged through outlet tube 84, while solids are discharged through orifice 86 into the particle discharge chamber 30 and descend for withdrawal through solids outlet 18. The cyclones 80 are connected laterally between the wall of subhousing 24 and the wall of structure 28.
The present invention can be better understood by reviewing it in conjunction with a conventional riser cracking FCC unit. When used in an FCC process, the typical cracking conditions and catalysts may be used with the exception of the adoption of the present cyclones.
Figure 1 illustrates a fluid catalytic cracking system of the prior art, and is similar to the Kellogg Ultra Orthoflow converter Model F shown as Fig. 17 of Fluid Catalytic Cracking Report, in the January 8, 1990 edition of Oil & Gas Journal. The process of the present invention works well with this type of FCC unit.
A heavy feed such as a gas oil, vacuum gas oil is added to riser reactor 6 through feed injection nozzles 2.
The cracking reaction is almost completed in the riser reactor, which takes a 90 turn at the top of the reactor at elbow 10. Spent catalyst and cracked products discharged from the riser reactor pass through riser cyclones 12 which efficiently separate most of the spent catalyst from cracked product. Cracked product is discharged into disengager 14 and eventually is removed through upper cyclones 16 and conduit 18 to the fractionator.
Spent catalyst is discharged down from a dipleg of riser cyclones 12 into catalyst stripper 8 where one, or preferably 2 or more, stages of steam stripping occur, with stripping steam admitted by means 19 and 21. The stripped hydrocarbons, and stripping steam, pass into disengager 14 and are removed with cracked products after passage through upper cyclones 16.
Stripped catalyst is discharged down through spent catalyst standpipe 26 into catalyst regenerator 24. The flow of catalyst is controlled with spent catalyst plug valve 36.
Catalyst is regenerated in regenerator 24 by contact with air, added through air lines and an air grid 5 distributor not shown. A catalyst cooler 28 is provided so heat may be removed from the regenerator if desired.
Regenerated catalyst is withdrawn from the regenerator through re-generated catalyst plug valve assembly 30 and discharged through lateral 32 into the base of the riser 10 reactor 6 to contact and crack fresh feed injected through injectors 2 as previously discussed. Flue gas, and some entrained catalyst, is discharged into a dilute phase region in the upper portion of_regenerator 24. Entrained catalyst is separated from flue gas in multiple stages of cyclones 4 and discharged through outlets 38 into plenum 20 for discharge to the flue gas line through line 22.
The bubbling dense bed in such a regenerator exhibits excellent horizontal mixing, and the heat exchanger 28 allows full CO burn operation even with heavy feeds.
Figure 1 does not show a third stage separator. Line 22 in most refineries would go to some type of third stage separator (not shown), usually one involving 50 to 100 (or more) small diameter horizontal or vertical cyclones.
Purified flue gas would then pass through an optional power recovery turbine (not shown) then go to a stack for discharge to the atmosphere, optionally through a flue gas clean up device, such as an SOX scrubber, or the like, not shown.
Figure 2 (Prior Art) is similar to Fig. 1 of Improved hot-gas expanders for cat cracker flue gas, Hydrocarbon ~
Processing, March 1976, p. 141.
M
Third stage separator 200 receives a fines containing FCC flue gas through inlet 210. Gas is distributed through plenum 220 to the inlets of a plurality of small diameter ceramic tubes 235 containing swirl vanes not shown. Fines collect on the walls of tubes 235 and are discharged from the base of the tubes as an annular stream of solids 230. A clean gas stream is withdrawn through outlet tubes 239 to be removed from the vessel through outlet 290. Solids are removed through solids outlet 265.
Figure 3 (Prior Art) shows another type of commercially available TSS unit, with cyclones mounted horizontally, as shown in Fig. 1 of US 5,178,648. Separator 10 comprises gas inlet 12, housing 14, clean gas discharge outlet 16, a main solids outlet 18 and an auxiliary solids outlet 20.
The wall of housing 14 may be insulated, or a heat exchanger, not shown, may be used to cool the gas. The interior of housing 14 is divided into a clean gas chamber 22 bounded on the outside by housing 14 and on the interior by subhousing 24 which also forms the boundary of chamber 26.
The interior of chamber 26 is defined by discharge chamber housing structure 28 concentrically enclosing a particle discharge chamber 30.
Subhousing 24 is supported centrally by refractory insulated member 32 which is supported by top cover 36.
Discharge chamber 28 is supported from conical section 38 of subhousing 24 by cylindrical skirt 40. Adjacent skirt 40, the lower section of structure 28 may be formed as cone structure 42 joined at its apex to conduit 44 having at its lower end the main solids outlet 18. Housing 14 is supported by cleats 60.
Particulate laden gas enters the device and passes through the inlets 82 of a plurality of small diameter, horizontally mounted cyclones 80. Clean gas is discharged through outlet tube 84, while solids are discharged through orifice 86 into the particle discharge chamber 30 and descend for withdrawal through solids outlet 18. The cyclones 80 are connected laterally between the wall of subhousing 24 and the wall of structure 28.
In the device shown, solids collection is split between solids discharged through the solids outlets of the horizontal cyclones and some solids which naturally settle down around the cyclones and are removed through solids outlet 20. Most commercial devices have only a single solids withdrawal, with all solids discharged through outlets 86. Clean gas is removed from the device through gas outlet 16.
Figure 4 shows a simplified sectional view of a preferred cyclone of the invention, while Figure 5 shows a bottom view of the same cyclone. Gas and entrained solids flow through tangential inlet duct 510 through inlet 515. Gas flow passes around outlet tube 520 into region 524, where centrifugal force throws particulates to the wall 514 of the cyclone 500.
Solids collect as a relatively thin, circulating layer of particles which are discharged through one or more tangential dust outlets 545. The cyclone has a closed bottom. Gas reentry is provided through a reentry cyclone 400 having a tangential inlet 410 and inlet opening 415.
The gross flow of gas through the device is in a classical double helix. Gas passes down the outside roughly as shown in helix 575 and up the inside of the interior volume of the cyclone as helix 580. If the gas passes down in a clockwise direction then gas flow reverses axial direction for the return trip, maintaining a clockwise spin. The mini-cyclone, or gas reentry cyclone 400 is configured to impart a swirl to the reentry gas which is in the same direction as that of the vortex 575 (outer helix) and vortex 580 (inner helix).
Figure 6 shows another embodiment which is simpler to fabricate and is self draining. A feed gas is charged through opening 615 in tangential inlet 610 into region 624 of cyclone 600. Incoming gas flows around clean gas outlet tube 620, with dust collecting on the walls 614. Dust may be tangentially discharged through outlet 645, or the lower portion of the cyclone body may comprise a truncated cone 630 with perforations or tangential outlet 646. The gas reflux opening 635 functions to reflux gas back into the cyclone from the dust catcher, and also functions as a drain during shutdowns.
Figure 4 shows a simplified sectional view of a preferred cyclone of the invention, while Figure 5 shows a bottom view of the same cyclone. Gas and entrained solids flow through tangential inlet duct 510 through inlet 515. Gas flow passes around outlet tube 520 into region 524, where centrifugal force throws particulates to the wall 514 of the cyclone 500.
Solids collect as a relatively thin, circulating layer of particles which are discharged through one or more tangential dust outlets 545. The cyclone has a closed bottom. Gas reentry is provided through a reentry cyclone 400 having a tangential inlet 410 and inlet opening 415.
The gross flow of gas through the device is in a classical double helix. Gas passes down the outside roughly as shown in helix 575 and up the inside of the interior volume of the cyclone as helix 580. If the gas passes down in a clockwise direction then gas flow reverses axial direction for the return trip, maintaining a clockwise spin. The mini-cyclone, or gas reentry cyclone 400 is configured to impart a swirl to the reentry gas which is in the same direction as that of the vortex 575 (outer helix) and vortex 580 (inner helix).
Figure 6 shows another embodiment which is simpler to fabricate and is self draining. A feed gas is charged through opening 615 in tangential inlet 610 into region 624 of cyclone 600. Incoming gas flows around clean gas outlet tube 620, with dust collecting on the walls 614. Dust may be tangentially discharged through outlet 645, or the lower portion of the cyclone body may comprise a truncated cone 630 with perforations or tangential outlet 646. The gas reflux opening 635 functions to reflux gas back into the cyclone from the dust catcher, and also functions as a drain during shutdowns.
Figure 7 shows a closed bottom cyclone 700 with a flat bottom and tangential exit. Gas and dust are charged through inlet opening 715 in tangential inlet 710 to swirl around clean gas outlet tube 720. Dust collects on wall 714 and is discharged through outlet 745 into the dust catcher, not shown. Excess gas discharged with solids is returned to the interior of the cyclone through orifice 785 in tube 735. In the embodiment shown, the tube extends into the interior of the cyclone body through tubular extension 737. The bottom of the cyclone is closed by seal plate 740.
The gas/solids inlet may comprise an axial discharge inlet.
The new cyclone is easy to fabricate using conventional techniques and materials. The cyclone bottom can be conical to the outside or the inside of the cyclone. The reflux port may be a round hole but preferably is a small upside down cyclone provided to induce swirl into the reflux gases entering the body of the main cyclone. Alternatively, swirl vanes may be provided in the reflux port for this purpose.
The body of the cyclones may be fully or partially lined with concrete or other refractory lining, or may be unlined.
The edges of outlets may be hard faced.
The gas/solids inlet may comprise an axial discharge inlet.
The new cyclone is easy to fabricate using conventional techniques and materials. The cyclone bottom can be conical to the outside or the inside of the cyclone. The reflux port may be a round hole but preferably is a small upside down cyclone provided to induce swirl into the reflux gases entering the body of the main cyclone. Alternatively, swirl vanes may be provided in the reflux port for this purpose.
The body of the cyclones may be fully or partially lined with concrete or other refractory lining, or may be unlined.
The edges of outlets may be hard faced.
The new cyclone may be used in revamps, especially of pre-existing TSS units with either multiple horizontal or multiple vertical cyclones. The cyclone significantly improves removal of fines, that is, 0 - 5 micron particles.
The new cyclone design will reduce erosion on power recovery turbine blades and substantially reduce particulate emissions.
In many FCC units the use of our cyclone in a third stage separator will eliminate the need for an electrostatic precipitator to reduce opacity and achieve particulate emissions of less than 50 mg/Nm3.
The new cyclone design will reduce erosion on power recovery turbine blades and substantially reduce particulate emissions.
In many FCC units the use of our cyclone in a third stage separator will eliminate the need for an electrostatic precipitator to reduce opacity and achieve particulate emissions of less than 50 mg/Nm3.
Claims (20)
1. A cyclone separator comprising:
a cyclone body having a closed end;
a gas/solids inlet at the inlet end of the cyclone body for a stream of gas and entrained solids;
a gas outlet tube at the inlet end having its longitudinal axis aligned with the longitudinal axis of the cyclone body for withdrawing gas with a reduced content of entrained solids;
at least one solids outlet in a sidewall of the cyclone body for tangential discharge of solids and a minor amount of gas from the cyclone into a catch chamber, and at least one gas reflux isolated from the gas/solids inlet for recycling gas from the catch chamber back into the cyclone body.
a cyclone body having a closed end;
a gas/solids inlet at the inlet end of the cyclone body for a stream of gas and entrained solids;
a gas outlet tube at the inlet end having its longitudinal axis aligned with the longitudinal axis of the cyclone body for withdrawing gas with a reduced content of entrained solids;
at least one solids outlet in a sidewall of the cyclone body for tangential discharge of solids and a minor amount of gas from the cyclone into a catch chamber, and at least one gas reflux isolated from the gas/solids inlet for recycling gas from the catch chamber back into the cyclone body.
2. A cyclone according to claim 1 in which the cyclone has a cylindrical cyclone body with a sealed end remote from the gas/solids inlet.
3. A cyclone according to claim 1 or 2 in which the gas reflux comprises a gas reflux tube extending within the cyclone body from 0 to 1 cyclone body lengths and extending outside the cyclone body into the catch chamber from 0 to 1 cyclone body lengths.
4. A cyclone according to claim 3 in which the gas outlet tube has a diameter smaller than the diameter of the cyclone body and a longitudinal axis axially aligned with the cyclone body, the gas reflux tube being axially aligned with the gas outlet tube.
5. A cyclone according to any one of claims 1 to 4 which includes a tangential gas/solids inlet at one end of the cyclone body and a solids outlet for discharging a concentrated solids stream with a minor portion of gas from the cyclone body through at least one opening in the cyclone body near the sealed end.
6. A cyclone according to claim 5 in which the solids outlet is disposed intermediate the gas/solid inlet and the closed end of the cyclone body.
7. A cyclone according to claim 6 in which the cyclone body has a cylindrical portion adjacent the inlet end and a conical portion adjacent the closed end, the tangential solids outlet being located at the juncture of the cylindrical portion and the conical portion.
8. A cyclone according to claim 4 in which the gas reflux inlet comprises a gas reflux tube at the closed end of the cyclone body which is at least partially cylindrical, the reflux tube having a diameter smaller than the diameter of the cyclone body.
9. A cyclone according to any one of claims 1 to 8 in which the gas/solids inlet comprises a tangential discharge inlet.
10. A cyclone according to any one of claims 1 to 8 in which the gas/solids inlet comprises an axial discharge inlet.
11. A cyclone according to any one of claims 1 to 10 in which the reflux tube extends on either side of the cyclone body by a distance equal to 0 to 100% of the length of the cyclone body.
12. A cyclone according to any one of claims 1 to 11 in which the gas reflux tube discharges tangentially into the cyclone body in the same direction as the tangential feed gas inlet.
13. A cyclone according to any one of claims 1 to 12 in which the gas reflux includes means for imparting swirl to the gas.
14. A cyclone according to claim 13 in which the means for imparting swirl comprises swirl vanes.
15. A cyclone according to claim 13 in which the means for imparting swirl comprises a tangential gas reflux entry into the gas reflux tube.
16. A multi-cyclone gas/solids separator comprising a plurality of cyclones as claimed in any one of claims 1 to 10 in which the plurality of cyclones share both a common catch chamber for solids discharged from the solids outlets of the cyclones and a common manifold for gas and entrained solids connected to the gas/solids inlets of the cyclones.
17. A separator according to claim 16 in which the gas reflux comprises a gas reflux tube which has an interior portion within the cyclone body and an exterior portion extending into the catch chamber, and in which the interior portion is a cylinder with an open end, and the exterior portion is a cylindrical tube closed at the end extending into the catch chamber and having at least one tangential inlet or slot in a sidewall for recycle of gas from the catch chamber into the interior of the cyclone body.
18. A fluidized catalytic cracking process in which a hydrocarbon feed is catalytically cracked by contact with a regenerated cracking catalyst in a cracking reactor to produce lighter products and spent catalyst, spent catalyst is regenerated in a catalyst regenerator having one or more separators for recovery of catalyst and fines from flue gas to produce regenerated catalyst which is recycled to the cracking reactor and regenerator flue gas containing catalyst fines, is subjected to separation in an external separator in an external separator to remove at least a portion of the fines from the regenerator flue gas stream, the external separator vessel comprising a plurality of cyclones as claimed in any one of claims 1 to 15, each cyclone having its solids outlet in communication with a catch chamber for discharge of fines and a minor amount of gas into the catch chamber in a lower portion of the separator vessel and its gas reflux to the catch chamber for recycling at least a portion of the gas discharged with the solids through the solids outlet from the catch chamber back into the cyclone body.
19. A process according to claim 18 in which the separator comprises a separator as claimed in claim 16 or 17.
20. A process according to claim 18 or 19 in which the separator has the gas/solids inlets connected to a common manifold which is disposed concentrically around the catch chamber.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US480,724 | 1995-06-07 | ||
| US08/480,724 US5681450A (en) | 1995-06-07 | 1995-06-07 | Reduced chaos cyclone separation |
| PCT/US1996/007229 WO1996040840A1 (en) | 1995-06-07 | 1996-05-17 | Reduced chaos cyclone separation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2222597A1 CA2222597A1 (en) | 1996-12-19 |
| CA2222597C true CA2222597C (en) | 2007-07-03 |
Family
ID=38279211
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002222597A Expired - Lifetime CA2222597C (en) | 1995-06-07 | 1996-05-17 | Reduced chaos cyclone separation |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2222597C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220063373A1 (en) * | 2020-08-28 | 2022-03-03 | Hutchinson | Vortex separation device for a fluid transfer circuit |
-
1996
- 1996-05-17 CA CA002222597A patent/CA2222597C/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220063373A1 (en) * | 2020-08-28 | 2022-03-03 | Hutchinson | Vortex separation device for a fluid transfer circuit |
| US11691477B2 (en) * | 2020-08-28 | 2023-07-04 | Hutchinson | Vortex separation device for a fluid transfer circuit |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2222597A1 (en) | 1996-12-19 |
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