Device for burning a gaseous fuel/oxidant mixture

Information

  • Patent Grant
  • 6638055
  • Patent Number
    6,638,055
  • Date Filed
    Tuesday, April 30, 2002
    22 years ago
  • Date Issued
    Tuesday, October 28, 2003
    20 years ago
Abstract
A device for burning a gaseous fuel/oxidant mixture, in particular for a power plant installation, includes a catalyzer/swirl generator arrangement. Part of the fuel/oxidant mixture is burned in the catalyzer/swirl generator arrangement and the catalyzer/swirl generator arrangement generates a swirl flow. The catalyzer/swirl generator arrangement includes several flow channels, of which some are constructed catalytically active and others catalytically inactive. The flow channels can be arranged distributed around a longitudinal central axis of the catalyzer/swirl generator arrangement, and can be slanted relative to the axis.
Description




FIELD OF THE INVENTION




The invention relates to a device for burning a gaseous fuel/oxidant mixture, in particular for a power plant installation.




BACKGROUND OF THE INVENTION




EP 0 833 105 A2 discloses a premix burner, in which a conical inner body that converges in the flow direction is arranged in an inside chamber. An outer enclosure of the inside chamber is interrupted by tangentially positioned air engagement channels, through which a combustion air flow flows into the inside chamber. As a result, a swirl flow is able to form in the inside chamber, which swirl flow is then enriched by means of at least one fuel nozzle with a fuel. The mixture of both media is then formed in the following mixing pipe. The mixing pipe then changes, via a cross-section increase, into a combustion chamber, whereby a reflux zone that ensures the combustion stability then forms in the region of the plane of the cross-section increase. In order to construct such a mixing pipe, the known premix burner requires a relatively large installation space. In the absence of the mixing pipe, the stability and homogeneity of the flames in the combustion chamber is reduced. There is also a risk of pressure pulsations.




U.S. Pat. Nos. 5,202,303 and 5,328,359 disclose catalyzers constructed from corrugated or folded web material, whereby their folds or corrugations form a plurality of flow channels. A fuel/oxidant mixture is partially burned when flowing through such a catalyzer. In order to prevent overheating in such a catalyzer, the combustion must be limited to only part of the mixture flowing through the catalyzer. For this purpose, only some of the channels are constructed catalytically active, for example by way of an appropriate coating, while the other channels are catalytically inactive. When flowing through the catalyzer, combustion then takes place only inside the catalytically active channels, while the catalyzer is cooled by flowing through the catalytically inactive channels. In conventional catalyzers, the catalyzer outlet temperatures are too low, however, to sufficiently stabilize the flames in the combustion chamber.




SUMMARY OF THE INVENTION




In view of the above disadvantages of the prior art, the invention is directed to a device that provides a compact construction and stability and homogeneity of the flames in the combustion chamber.




The invention is based on the general idea of creating a swirl flow from the fuel/oxidant mixture and increasing the temperature of the mixture prior to its entrance into the combustion chamber by use of a catalyzer. For this purpose, the device according to the invention comprises a flow-enabling catalyzer/swirl generator arrangement, in which part of the fuel/oxidant mixture is burned and which generates a swirl flow. The invention makes it possible to increase the stability and homogeneity of the flames in the combustion chamber and to reduce the pulsation risk. In addition, such a catalyzer/swirl generator arrangement may have a relatively short construction in the flow direction, so that the device overall has a compact construction.




In principle, it is possible to construct the catalyzer/swirl generator arrangement in such a way that it has a catalyzer and, immediately following the catalyzer in a downstream direction, a swirl generator. However, an embodiment in which the catalyzer/swirl generator arrangement comprises a catalyzer constructed as a swirl generator is preferred. In other words, the catalyzer or catalyzer body is constructed in such a way that the flow exiting from it has the desired swirl. With this construction, two functions, i.e., the catalytic combustion and the swirl generation, can be integrated into a compact component.




It is useful that the catalyzer/swirl generator arrangement comprises several flow channels extending essentially parallel, i.e., in the same direction, to each other, of which some, in particular approximately half, are constructed catalytically active, and the others catalytically inactive. The channels may be arranged distributed around a longitudinal center axis of the catalyzer/swirl generator arrangement, whereby this longitudinal center axis extends in the main flow direction of the catalyzer/swirl generator arrangement. According to an advantageous embodiment, the channels can be slanted in relation to the longitudinal center axis in such a way that the longitudinal direction of the channels in each case extends slanted in relation to a straight line that extends parallel to the longitudinal center axis. This results in an arrangement for the channels that causes the desired swirl flow to exit on the outflow side of the catalyzer/swirl generator arrangement, i.e., at the outlet ends of the channels.




In order to reduce the pressure loss during the flow through the catalyzer/swirl generator arrangement, the slant of the channels in relation to the longitudinal center axis may increase in the flow direction, in particular steadily or in a stepped manner as well as continuously or progressively, whereby the slant of the channels may have the value zero at the inlet, i.e., the channels then extend parallel to the longitudinal center axis with their inlet.




According to a special further development, the catalyzer/swirl generator arrangement may comprise, radially to the longitudinal center axis, several layers of a corrugated or folded first web material whose corrugations or folds form the catalytically active or catalytically inactive channels. An intermediate layer of a flat or smooth second web material is arranged between two adjoining layers in a radial direction. This construction ensures that radially adjoining corrugations or folds are unable to project inside each other, so that the channels always have unchanging flow cross-sections.











BRIEF DESCRIPTION OF THE DRAWINGS




Preferred exemplary embodiments of the invention are shown in the drawings and are explained in more detail in the following description, wherein identical reference numbers refer to identical or functionally identical or similar components. The schematic drawings show in:





FIG. 1

is a greatly simplified principle view of a device according to the invention.





FIG. 2

is a perspective view onto a catalyzer/swirl generator arrangement in a preferred embodiment.





FIG. 3

is a partial section through the catalyzer/swirl generator arrangement according to FIG.


2


.





FIG. 4

is a partial section through the catalyzer/swirl generator according to a first alternative embodiment.





FIG. 5

is a partial section through the catalyzer/swirl generator according to a second alternative embodiment.





FIG. 6

is a partial section through the catalyzer/swirl generator according to a third alternative embodiment.





FIG. 7

is a perspective view of the outlet nozzle of the catalyzer/swirl generator arrangement according to FIG.


2


.











DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS




Referring initially to

FIG. 1

, a device


1


according to the invention comprises a flow-enabling catalyzer/swirl generator arrangement


2


to the inflow side


3


of which a gaseous fuel/oxidant mixture


4


is fed, symbolized in

FIG. 1

by arrows. The device


1


forms a burner with a feed line


30


, in which the catalyzer/swirl generator arrangement


2


is arranged. The catalyzer/swirl generator arrangement


2


according to the invention is constructed in such a way that part of the fuel/oxidant mixture


4


is burned in it, and that a swirl flow exits on an outflow side


5


, which is symbolized by an arrow


6


. The catalyzer/swirl generator arrangement


2


is arranged directly before an abrupt cross-section increase


7


formed at the inlet of a combustion chamber


8


. This allows the swirl flow to immediately burst open,




With a sufficiently high swirl value, a central recirculation zone


9


is therefore able to form in the combustion chamber


8


. Corresponding vortices


10


are suggested by closed lines with arrows. The recirculation zone


9


forms a kind of anchor for a homogeneous flame front


11


in the combustion chamber


8


. A stabilization of the flame front


11


is achieved in that the central vortices


10


support a mixing of the products of the homogeneous combustion in the combustion chamber


8


with the partially burned products of the catalytic combustion in the catalyzer/swirl generator arrangement


2


. This corresponds to an internal waste gas recycling that effects an intensive preheating of the total mixture and at the same time reduces the local velocities to values that correspond to the flame velocity. This process is also supported in a corresponding manner by a recirculation zone


12


that is generated by the abrupt cross-section increase


7


. Corresponding vortices


13


are also suggested here by closed lines with arrows. The flame stabilization achieved in this manner additionally supports the complete combustion and reduces the emission of noxious substances, such as, for example, CO and NOx, as a result of the improved mixing.




Such a device is used, for example, in power plant installations, and is used there to generate hot gases for operating a turbine, in particular a gas turbine.




As already explained above, part of the fuel/oxidant mixture


4


is burned while flowing through the catalyzer/swirl generator arrangement


2


, resulting in an increase in the temperature of the supplied fuel/oxidant mixture at the inlet of the combustion chamber


8


. These high temperatures additionally improve the flame stability and prevent the formation of pulsations.




The exact position of the flame front


11


in the combustion chamber


8


can be influenced by the geometry and/or arrangement and/or construction of the catalyzer/swirl generator arrangement


2


.




The catalyzer/swirl generator arrangement


2


preferably consists of a catalyzer


14


that is constructed as a swirl generator. Also possible is a construction of the swirl generator and catalyzer as separate components that are positioned consecutively in the flow direction. Such an embodiment is additionally suggested in

FIG. 1

with a broken line that symbolizes the boundary


15


between an upstream catalyzer


16


and a downstream swirl generator


17


directly following the catalyzer


16


downstream.




According to

FIGS. 2 and 3

, the catalyzer/swirl generator arrangement


2


comprises several flow channels


18


and


19


extending essentially parallel to each other. Some of the channels are constructed as catalytically active channels


18


, while the others are constructed as catalytically inactive channels


19


. It is useful that catalytically active channels


18


and catalytically inactive channels


19


alternate, thus improving the cooling effect for the catalyzer


14


or the catalyzer/swirl generator arrangement


2


. The channels


18


,


19


are arranged so as to be distributed radially and circumferentially around a longitudinal center axis


20


of the catalyzer/swirl generator arrangement


2


that is here constructed cylindrically, in particular circular-cylindrically. The longitudinal center axis


20


hereby extends parallel to the main flow direction of the catalyzer/swirl generator arrangement


2


.




In order to integrate the swirl generator into the catalyzer


14


, the channels


18


,


19


are slanted in relation to the longitudinal center axis


20


, i.e., the longitudinal directions of the channels


18


,


19


each extend slanted in relation to a straight line that extends parallel to the longitudinal center axis


20


. This relationship is illustrated as an example in

FIG. 2

using a single channel


18


, i.e., a longitudinal direction


21


(drawn with a broken line) of this channel


18


is angled in relation to a straight line


22


(also drawn with a broken line) that extends parallel to the longitudinal center axis


20


.




This angle of slant α must be selected large enough to ensure that the central recirculation zone


9


is able to form in the combustion chamber


8


. In addition, the angle of slant α may also not be selected too large in order to prevent a too high pressure loss at the cross-section increase


7


. At least in the case of channels


18


,


19


arranged radially further out, suitable values for the angle range, for example, between 30° and 60°, which may correspond to, for example, swirl values Ω of 0.4 to 1.2. If the outflow side


5


of the catalyzer/swirl generator arrangement


2


is positioned immediately before the cross-section increase


7


, the angle of slant α, and thus the pressure loss of the arrangement, can be reduced.




In the embodiment according to

FIG. 2

, all channels


18


,


19


have the same slant α in relation to the longitudinal center axis


20


along their entire length. In another embodiment, not shown here, the slant a of the channels


18


,


19


in relation to the longitudinal center axis


20


can increase in the flow direction of the catalyzer/swirl generator arrangement


2


. It is useful that this change in slant a takes place steadily and progressively. In particular, the slant may have the value α=0° at the inflow side of the catalyzer/swirl generator arrangement


2


. This design of the channels


18


,


19


makes it possible to optimize the flow resistance of the catalyzer/swirl generator arrangement


2


. In another embodiment, the slant α of the channels may increase radially from the inside to the outside. This means that for channels


18


,


19


that are located radially further inside, the slant a can be smaller than for channels


18


,


19


that are located radially further outside. These measures simplify the production of the catalyzer/swirl generator arrangement


2


.




For example, the catalyzer/swirl generator arrangement


2


may have a first longitudinal section


23


comprising the inflow section


3


as well as a second longitudinal section


24


comprising the outflow section


5


. These longitudinal sections


23


,


24


are designated in

FIG. 2

with brackets. The longitudinal sections


23


,


24


may be—as is the case here—of approximately identical size. In a preferred embodiment, the channels


18


and


19


in the first longitudinal section


23


may extend parallel to the longitudinal center axis


20


, while in the second longitudinal section


24


they have a slant in relation to the longitudinal center axis


20


that may optionally increase in the flow direction. This forms the swirl generator


17


in the rear longitudinal section


24


of the arrangement


2


. It is useful that the second longitudinal section


24


extends over approximately one fifth, one quarter, or one third of the total length of the arrangement


2


.




According to

FIGS. 2 and 3

, it is useful that the catalyzer/swirl generator arrangement


2


is constructed by placing a corrugated or folded first web material


25


onto a flat or smooth second web material


26


. As a result, a layering occurs radially in relation to the longitudinal center axis


20


, whereby the layers formed by the first web material


25


are separated radially from each other by intermediate layers formed from the second web material


26


. In this construction, the second web material


26


ensures that the corrugations and folds of the first web material


25


of one layer are unable to project into the corrugations and folds of the first web material


25


of a radially adjoining layer. Rather, the intermediate layers made from the second web material


26


ensure unchanging channel cross-sections. The individual channels


18


and


19


are hereby formed by the corrugations or folds of the first web material


25


. In order to construct the catalytically active channels


18


, it is useful that one side of the first web material


25


, in each case the top according to

FIG. 3

, can be coated with a catalytically active coating


27


. The opposite underside of the first web material


25


is then uncoated, thus creating the catalytically inactive channels


19


. Alternatively or additionally, the layers of the second web material


26


may also be coated on one side with the catalyzer coating


27


in order to form the catalytically active channels


18


. It is useful that the web materials


25


,


26


consist of a metal sheet that is appropriately preshaped and potentially coated.




The web materials


25


and


26


may be concentrically layered in relation to the longitudinal center axis


20


. However, an embodiment in which the web materials


25


and


26


are layered helically in relation to the longitudinal center axis


20


is preferred. This arrangement allows for an especially simple method of producing the catalyzer/swirl generator arrangement


2


:




The web materials


25


and


26


that were placed on top of each other are wound onto a spindle


28


, which, after the winding, forms the center of the catalyzer/swirl generator arrangement


2


and extends concentrically to the longitudinal center axis


20


. The spindle


28


is shown in FIG.


7


and includes an outlet nozzle.




The spindle


28


therefore carries the web material


25


,


26


, and its diameter size is selected so that the winding of the corrugated or folded first web material


25


can still be realized with justifiable expenditure. The complete winding can be secured, for example, with tension wires


29


that enclose the winding circumferentially and maintain its shape at least until the installation of the catalyzer/swirl generator arrangement


2


into a burner, etc.




It is useful that this spindle


28


is constructed so as to be able to influence the central recirculation zone


9


or the flame front


11


in the combustion chamber


11


(FIG.


1


), in particular with respect to shape and position. The spindle


28


, for example, is constructed as a flow pipe that enables a central flow through the catalyzer/swirl generator arrangement


2


by the fuel/oxidant mixture


4


. It is useful that the tubular spindle


28


then has at its outlet end an outlet nozzle or outlet aperture, whereby it may also be useful to construct the outlet end so that it converges in the flow direction. These measures make it possible to change the aerodynamic values of the flow entering the combustion chamber


8


, whereby said values influence the position and extension of the flame front


11


and/or central recirculation zone


9


.




It is also possible to integrate a lance for the fuel and/or oxidizer injection into the spindle


28


.




In order to be able to generate the desired swirl, the swirl-generating structure requires a minimum length L, obtained by dividing the channel diameter by the tangent of the angle of slant. The calculated length is relatively short, so that even the construction with separate catalyzer


16


and separate swirl generator


17


, explained above in reference to

FIG. 1

, still has a relatively short length in the flow direction. In the integrated construction, the axial length of the catalyzer


14


constructed as a swirl generator, i.e., the axial length of the catalyzer/swirl generator arrangement


2


, may depend on the requirements of the catalytic conversion of the system.




The integrated construction of the catalyzer/swirl generator arrangement


2


is also of special advantage if the arrangement


2


, as explained above in reference to

FIG. 1

, has two or more longitudinal sections


23


,


24


, in which the channels


18


,


19


differ from each other with respect to their slant. For example, the channels


18


,


19


in the upstream first longitudinal section


23


are not slanted in relationship to the longitudinal center axis


20


, so that they extend parallel to the main flow direction, while they are slanted in the downstream longitudinal section


24


, and in this way form the swirl generator. The one-piece construction of the catalyzer/swirl generator arrangement


2


hereby reduces pressure losses during the transition between the consecutive longitudinal sections


23


,


24


. While in a construction with separate longitudinal sections


23


,


24


a minimum distance between the consecutive longitudinal sections


23


,


24


must be maintained for the transition from one longitudinal section


23


to the other longitudinal section


24


in order to achieve sufficient mixing, such a transition and mixing area is not required in the one-piece construction of the longitudinal sections


23


,


24


, so that the arrangement


2


according to the invention can be constructed especially short.




With reference to

FIG. 4

, a first alternative embodiment of the invention shows an increasing slant (angles α


1





2


, and α


3


) of the channel


18


′ in the flow direction.





FIG. 5

illustrates a second alternative embodiment of the present invention, wherein the channel radially increases from the inside to the outside, wherein


18


designates the outside and


18


″ designates an inner channel of the catalyzer/swirl generator arrangement


2


. According to this embodiment, the inner angle As is smaller than the outer radial angle α.




With reference to

FIG. 6

, the channel


18


′″, which is arranged in parallel to the longitudinal center axis


20


in a first longitudinal section


23


of the catalyzer/swirl generator arrangement


2


, is only slanted in relation to the longitudinal center axis


20


in a second longitudinal section


24


of the catalyzer/swirl generator arrangement


2


(see angle α


5


).



Claims
  • 1. A device for burning a gaseous fuel/oxidant mixture, comprising:a flow-enabling catalyzer/swirl generator arrangement in which part of the fuel/oxidant mixture is burned and which generates a swirl flow, wherein the catalyzer/swirl generator arrangement comprises several flow channels which are continuous through the whole catalyzer/swirl generator arrangement, some of said flow channels being constructed catalytically active, and the others of said flow channels being constructed catalytically inactive, wherein the flow channels are arranged distributed around a longitudinal center axis of the catalyzer/swirl generator arrangement that extends in the main flow direction of the catalyzer/swirl generator arrangement, and the flow channels are slanted in relation to the longitudinal center axis of the catalyzer/swirl generator arrangement in such a way that the longitudinal directions of the flow channels each extend slanted in relation to a straight line that extends parallel to the longitudinal center axis of the catalyzer/swirl generator arrangement.
  • 2. The device according to claim 1, wherein the catalyzer/swirl generator arrangement comprises a catalyzer and a swirl generator, the swirl generator directly following the catalyzer in a downstream direction.
  • 3. The device according to claim 1, wherein the catalyzer/swirl generator arrangement comprises a catalyzer that is constructed as a swirl generator.
  • 4. The device according to one of claims 1 to 3, wherein the catalyzer/swirl generator arrangement is arranged directly upstream from an abrupt cross-section increase at the entrance of a combustion chamber.
  • 5. The device according to claim 1, wherein the slant of the flow channels in relation to the longitudinal center axis of the catalyzer/swirl generator arrangement increases in the flow direction.
  • 6. The device according to claim 1, wherein flow channels located further radially inward in relation to the longitudinal center axis of the catalyzer/swirl generator arrangement have a slant that is smaller than the slant of flow channels located further radially outward.
  • 7. The device according to claim 1, wherein the flow channels extend in a first longitudinal section comprising the inflow side of the catalyzer/swirl generator arrangement parallel to the longitudinal center axis of the catalyzer/swirl generator arrangement, and the flow channels are slanted in relation to the longitudinal center axis of the catalyzer/swirl generator arrangement in a second longitudinal section comprising the outflow side of the catalyzer/swirl generator arrangement.
  • 8. The device according to claim 1, wherein the catalyzer/swirl generator arrangement comprises layers of a corrugated or folded first web material whose corrugations or folds form the flow channels, the layers arranged in a radial direction relative to a longitudinal center axis that extends parallel to the main flow direction of the catalyzer/swirl generator arrangement, and an intermediate layer of a flat or smooth second web material is arranged between two adjoining layers in a radial direction.
  • 9. The device according to claim 8, wherein the web materials are layered in relation to the longitudinal center axis at least one of concentrically and helically.
  • 10. The device according to claim 8, wherein the catalyzer/swirl generator arrangement comprises a central spindle that extends concentrically to the longitudinal center axis and carries the web materials.
  • 11. The device according to claim 10, wherein the spindle is constructed so that it aerodynamically influences at least one of a recirculation zone and a flame front in a combustion chamber arranged downstream from the catalyzer/swirl generator arrangement.
  • 12. The device according to claim 10, wherein the spindle is constructed as a flow pipe through which part of the fuel/oxidant mixture centrally flows through the catalyzer/swirl generator arrangement.
  • 13. The device according to claim 12, wherein the spindle is constructed to have an outlet end that is configured to at least one of converge at the outlet end of the spindle, form an outlet aperture at the outlet end and form an outlet nozzle at the outlet end.
  • 14. A catalyzer/swirl generator arrangement for a device for burning a fuel/oxidant mixture in a power plant installation, wherein the catalyzer/swirl generator arrangement is constructed so that the fuel/oxidant mixture is able to flow through it, and the fuel/oxidant mixture is provided with a swirl when flowing through the catalyzer/swirl generator arrangement and is partially burned, wherein the catalyzer/swirl generator arrangement comprises several flow channels which are continuous through the whole catalyzer/swirl generator arrangement, some of said flow channels being constructed catalytically active, and the others of said flow channels being constructed catalytically inactive, wherein the flow channels are arranged distributed around a longitudinal center axis of the catalyzer/swirl generator arrangement that extends in the main flow direction of the catalyzer/swirl generator arrangement, and the flow channels are slanted in relation to the longitudinal center axis of the catalyzer/swirl generator arrangement in such a way that the longitudinal directions of the flow channels each extend slanted in relation to a straight line that extends parallel to the longitudinal center axis of the catalyzer/swirl generator arrangement.
  • 15. A method for producing a catalyzer/swirl generator arrangement according to claim 14, wherein a smooth or flat second web material is placed onto a corrugated or folded first web material, and wherein the web materials placed on top of each other are wound onto a spindle.
  • 16. The method according to claim 15, wherein the corrugations or folds in the first web material extend at a slant in relation to the longitudinal axis of the spindle.
  • 17. The method according to claim 15 or 16, wherein the corrugations or folds following each other in the direction the web materials are wound onto the spindle are constructed alternately catalytically active and catalytically inactive.
  • 18. A method for burning a fuel/oxidant mixture in an application including in a power plant installation, comprising:providing a catalyzer/swirl generator arrangement wherein the fuel/oxidant mixture is provided with a swirl and is partially burned catalytically before being fed into a combustion chamber, wherein the catalyzer/swirl generator arrangement comprises several flow channels which are continuous through the whole catalyzer/swirl generator arrangement, some of said flow channels being constructed catalytically active, and the others of said flow channels being constructed catalytically inactive, wherein the flow channels are arranged distributed around a longitudinal center axis of the catalyzer/swirl generator arrangement that extends in the main flow direction of the catalyzer/swirl generator arrangement, and the flow channels are slanted in relation to the longitudinal center axis of the catalyzer/swirl generator arrangement in such a way that the longitudinal directions of the flow channels each extend slanted in relation to a straight line that extends parallel to the longitudinal center axis of the catalyzer/swirl generator arrangement.
Priority Claims (1)
Number Date Country Kind
2001 2298/01 Dec 2001 CH
Parent Case Info

This application claims priority under 35 U.S.C. §§119 and/or 365 to 2001 2298/01 filed in Switzerland on Dec. 14, 2001; the entire content of which is hereby incorporated by reference. This application claims priority under 35 U.S.C. §119 to U.S. Provisional Application No. 60/286,995 entitled CATALYTIC STRUCTURE FOR HOMOGENEOUS FLAME STABILISATION and filed on Apr. 30, 2001, the entire content of which is hereby incorporated by reference.

US Referenced Citations (9)
Number Name Date Kind
5202303 Retallick et al. Apr 1993 A
5328359 Retallick Jul 1994 A
5512250 Betta et al. Apr 1996 A
5518697 Dalla Betta et al. May 1996 A
5601426 Pfefferle Feb 1997 A
5634784 Pfefferle et al. Jun 1997 A
5817909 Lescuyer et al. Oct 1998 A
5876196 Knopfel et al. Mar 1999 A
6179608 Kraemer et al. Jan 2001 B1
Foreign Referenced Citations (6)
Number Date Country
42 02 018 Apr 1993 DE
0 620 402 Oct 1994 EP
0 767 345 Apr 1997 EP
0 833 105 Apr 1998 EP
A-59-136140 Aug 1984 JP
A-2-259331 Oct 1990 JP
Provisional Applications (1)
Number Date Country
60/286995 Apr 2001 US