The present invention relates to a direct smelting plant for producing molten metal from a metalliferous feed material such as ores, partly reduced ores and metal-containing waste streams.
A known direct smelting process, which relies principally on a molten bath as a reaction medium, and is generally referred to as the HIsmelt process, is described in International Application PCT/AU96/00197 (WO 96/31627) in the name of the applicant. The disclosure in the International application is incorporated herein by cross reference.
The HIsmelt process as described in the International application in the context of producing molten iron includes:
(a) forming a bath of molten iron and slag in a direct smelting vessel;
(b) injecting into the bath: (i) a metalliferous feed material, typically iron oxides; and (ii) a solid carbonaceous material, typically coal, which acts as a reductant of the iron oxides and a source of energy; and
(c) smelting metalliferous feed material to iron in the metal layer.
The term “smelting” is herein understood to mean thermal processing wherein chemical reactions that reduce metal oxides take place to produce molten metal.
The HIsmelt process also includes post-combusting reaction gases, such as CO and H2, released from the bath in the space above the bath with oxygen-containing gas and transferring the heat generated by the post-combustion to the bath to contribute to the thermal energy required to smelt the metalliferous feed materials.
The HIsmelt process also includes forming a transition zone above the nominal quiescent surface of the bath in which there is a favourable mass of ascending and thereafter descending droplets or splashes or streams of molten metal and/or slag which provide an effective medium to transfer to the bath the thermal energy generated by post-combusting reaction gases above the bath.
In the HIsmelt process the metalliferous feed material and solid carbonaceous material are injected into the molten bath through a number of lances/tuyeres which are inclined to the vertical so as to extend downwardly and inwardly through the side wall of the direct smelting vessel and into a lower region of the vessel so as to deliver at least part of the solid materials into the metal layer in the bottom of the vessel. To promote the post-combustion of reaction gases in the upper part of the vessel, a blast of hot air, which may be oxygen-enriched, is injected into an upper region of the vessel through a downwardly extending hot air injection lance. Offgas resulting from the post-combustion of reaction gases in the vessel is taken away from the upper part of the vessel through an offgas duct. The vessel includes refractory-lined water cooled panels in the side wall and the roof of the vessel, and water is circulated continuously through the panels in a continuous circuit.
The HIsmelt process enables large quantities of molten metal, such as molten iron, to be produced by direct smelting in a single compact vessel. In order to achieve this it is necessary to transport large quantities of hot gas to and from the direct smelting vessel, transport large quantities of the metalliferous feed material, such as iron-containing feed materials, to the vessel, transport large quantities of the molten metal product and slag produced in the process away from the vessel, and circulate large quantities of water through the water cooled panels—all within a relatively confined area. These functions must continue throughout a smelting operation—which desirably extends over at least 12 months. It is also necessary to provide access and handling facilities to enable access to the vessel and lifting of equipment between smelting operations.
A commercial HIsmelt direct smelting plant based on a 6 m diameter vessel (internal diameter of refractory hearth) has been constructed at Kwinana, Western Australia. The plant is designed to operate the HIsmelt process and produce 800,000 tonnes per year of molten iron in the vessel.
The applicant has now carried out research and development work to design a larger scale commercial HIsmelt direct smelting plant to produce in excess of 1 million tonnes per year of molten iron via the HIsmelt process.
The applicant has been confronted with a number of problems in scaling up the HIsmelt process and has produced an alternate design for a HIsmelt direct smelting plant.
The present invention relates to a direct smelting plant that is an alternative design for the commercial HIsmelt direct smelting plant mentioned above.
The direct smelting plant of the present invention can also be used to carry out other direct smelting processes.
According to the present invention there is provided a direct smelting plant for producing molten metal from a metalliferous feed material using a molten bath based direct smelting process that includes:
(a) a fixed direct smelting vessel to hold a molten bath of metal and slag and a gas space above the bath, the vessel including a hearth and a side wall;
(b) a solids feed assembly to supply solid feed material, including metalliferous feed material and carbonaceous material, from a solid feed material supply location away from the vessel into the vessel;
(c) an oxygen-containing gas feed assembly to supply an oxygen-containing gas from an oxygen-containing gas supply location away from the vessel into the vessel;
(d) an offgas duct assembly to facilitate flow of offgas from the vessel, the offgas duct assembly including two offgas ducts of matching diameter extending outwardly from the vessel;
(e) a metal tapping assembly to tap molten metal from the bath during a smelting operation; and
(f) a slag tapping assembly to tap slag from the bath during a smelting operation.
The applicant has identified that a single offgas duct for the flow rates of offgas produced by a HIsmelt process producing 2 million or more tonnes per year of molten metal is not a desirable option from a structural engineering viewpoint and as such cannot be readily constructed off-site and transported to site for assembly.
Preferably the offgas ducts extend outwardly from an upper section of the side wall of the vessel.
Preferably the upper section of the side wall is cylindrical.
Preferably the side wall of the vessel includes:
(a) a lower cylindrical section,
(b) the upper cylindrical section that has a smaller diameter than the lower section, and
(c) a transition section that interconnects the upper and lower sections.
Preferably the offgas duct assembly includes two matching offgas ducts of matching length. The term “matching” is understood herein to mean that the length of the ducts is the same.
Preferably the offgas ducts define a V-shape when viewed from above the vessel.
Preferably an angle between the offgas ducts that is described by the axes of the offgas ducts is 50-90°, more preferably 55-80°, and more preferably 60-80°.
Preferably the offgas ducts are inclined upwardly at an angle of 5-10° to the horizontal.
Preferably the offgas ducts are positioned with respect to the cylindrical upper section of the side wall so that the central axes of the ducts intersect each other and a radial line that extends from a central vertical axis of the vessel away from the ducts. In other words, the axes of the offgas ducts are not radials from the central vertical axis of the vessel.
The applicant has identified that positioning the offgas ducts as described in the preceding paragraph is preferable to positioning the ducts so that the axes of the ducts extend radially from the central vertical axis of the vessel. The reason for this preference is that the section of the side wall that is between the offgas ducts is a larger section in terms of the arc described by the section, and this is an advantage from the structural viewpoint of this section of the side wall.
Preferably the oxygen-containing gas feed assembly includes (i) a gas injection assembly including a plurality of gas injection lances to inject the oxygen-containing gas into the vessel that extend through openings in the vessel and (ii) a gas delivery duct assembly extending from a gas supply location away from the vessel to deliver the oxygen-containing gas to the gas injection assembly, the gas delivery duct assembly including a single gas supply main connected to the gas injection lances to supply the oxygen-containing gas from the gas supply location to the lances, and the offgas ducts being positioned at a height intermediate the gas supply main and the transition section of the side wall of the vessel.
Preferably the transition section of the side wall of the vessel includes the openings for the gas injection lances and the lances extend through the openings into the vessel, and at least some of the openings in the transition section are positioned at least partially below the offgas ducts whereby the lances are spaced equi-radially around the vessel.
Preferably the gas delivery duct assembly includes a plurality of members that connect together the gas supply main and the gas injection lances, and each connection member includes a spool that extends from an inlet end of one gas injection lance and an expansion joint that is connected at one end to the spool and at the other end to one of the outlets of the gas delivery main, and the axes of the offgas ducts are radially spaced such that the openings in the transition section are located at a position underneath the offgas ducts such that gas injection spools and/or lances that extend downwardly and inwardly to the openings from the gas supply duct have sufficient clearance from the ducts for installation and removal of the spools and/or lances.
Preferably the offgas duct assembly includes at least one flow control valve to control the flow of offgas from the vessel.
Preferably the plant includes at least one said flow control valve connected to each offgas duct to control the flow of offgas through the duct.
Preferably the metalliferous material includes iron ore.
The present invention is described in more detail hereinafter by way of example with reference to the accompanying drawings, of which:
The direct smelting plant shown in the Figures is suitable particularly for smelting metalliferous material in accordance with the HIsmelt process as described in International Patent Application No. PCT/AU96/00197 (International Publication No. WO 96/31627).
The plant is not confined to smelting metalliferous material in accordance with the HIsmelt process.
The following description is in the context of smelting iron ore fines to produce molten iron in accordance with the HIsmelt process.
The present invention is not confined to the production of molten iron and extends to direct smelting any metalliferous material.
The following description focuses on a direct smelting vessel of the direct smelting plant and apparatus, such as solids and gas injection lances, that are directly associated with the vessel.
The direct smelting plant also includes other apparatus, including apparatus for processing feed materials for the vessel upstream of the vessel and apparatus for processing products (molten metal, molten slag, and offgas) produced in the vessel. Such other apparatus is not described herein in detail because it is not the focus of the present invention but it nevertheless forms part of the plant. Such other apparatus is described in other patent applications and patents in the name of the applicant and the disclosure in these patent applications and patents is incorporated herein by cross-reference.
With reference to the Figures, in the context of the present invention, the main features of the embodiment of the direct smelting plant shown in the Figures are:
(a) a fixed direct smelting vessel 3 to contain a molten bath 41 of metal and slag and a gas space 43 above the bath;
(b) a solid feed assembly that includes 12 solids injection lances 5a, 5b to supply solid feed material, including metalliferous feed material and carbonaceous material, into the vessel;
(c) an oxygen-containing gas feed assembly to supply an oxygen-containing gas to the vessel which includes:
(c)(i) a gas injection assembly in the form of 4 gas injection lances 7 to inject the oxygen-containing gas into the gas space and/or the bath in the vessel; and
(c)(ii) a gas delivery duct assembly that includes a ring main 9 and a plurality of members 49, one associated with each gas injection lance 7, that connect the ring main 9 and the gas injection lances 7 to deliver the oxygen-containing gas, typically air or oxygen-enriched air, to the gas injection lances 7; and
(d) an offgas duct assembly that includes two offgas ducts 11 to facilitate flow of offgas from the vessel away from the vessel;
With reference to
The vessel 3 includes (a) a hearth that includes a base 21 and sides 23 formed from refractory bricks, (b) a side wall 25 that extends upwardly from the hearth, and (c) a torispherical roof 27. In order to place the size of the vessel 3 into context, a vessel 3 that is designed to produce 2 million tones per year of molten iron requires a hearth diameter (internal) of around 8 m.
The side wall 25 of the vessel 3 is formed so that the vessel includes (a) a lower cylindrical section 29, (b) an upper cylindrical section 31 that has a smaller diameter than the lower section 29, and (c) a frusto-conical section 33 that interconnects the two sections 29, 31.
It is evident from the following description and the drawings that the 3 sections 29, 31, 33 of the side wall 25 of the vessel divide the side wall 25 into 3 separate zones. The lower section 29 supports the solids injection lances 5a, 5b. The frusto-conical section 33 supports the gas injection lances 7. Finally, the upper section 33 in effect, is an offgas chamber from which offgas leaves the vessel.
The side wall 25 and the roof 27 of the vessel 3 support a plurality of water-cooled panels (not shown) and the plant includes a cooling water circuit. With reference to
The frusto-conical section 33 of the side wall 25 of the vessel 3 includes openings 35 for the gas injection lances 7. The lances 7 extend through the openings 35. The lance openings 35 include mounting flanges 37, and the lances 7 are mounted on and supported by the flanges 37. The lance openings 35 are at the same height of the vessel 3 and are positioned at equi-spaced intervals around the perimeter of the side wall 25 of the vessel 3.
With reference to
With reference to
The access doors 45 are in the form of steel plates that are welded to the sides 23. When access to the interior of the vessel 3 is required, the plates are cut away from the side 23 of the hearth and replacement plates are welded in position after the work in the vessel 3 has been completed. The access doors 45 are at the same height of the vessel 3. The access doors 45 are spaced at least 90° apart around the circumference of the vessel 3. This spacing makes it possible for refractory wall demolition equipment to extend through the doors 45 into the vessel and demolish a substantial part of the refractories of a refractory-lined side wall while the vessel is hot. In addition, the access doors 45 are sufficiently large, typically 2.5 m in diameter, to allow bob-cat or similar equipment access to the interior of the vessel 3.
With reference to
In use, the four gas injection lances 7 of the gas injection assembly inject an oxygen-enriched hot air blast from a hot gas supply station (not shown) located some distance away from the reduction vessel 11. The hot gas supply station includes a series of hot gas stoves (not shown) and an oxygen plant (not shown) to enable an oxygen-enriched air stream to be passed through the hot gas stoves and into a hot gas delivery duct 51 (
The purpose of the gas injection lances 7 is to inject a sufficient flow rate of the oxygen-enriched hot air at a sufficient velocity so that the hot air penetrates a fountain, typically an annular fountain, of molten metal and slag that is projected upwardly within the vessel 3 as part of the HIsmelt process and the oxygen-enriched hot air combusts combustible gas, such as carbon dioxide and hydrogen released from the bath, that is in the fountain. Combustion of the combustible gas produces heat that is transferred to the molten bath when the molten metal and slag moves back downwardly into the bath.
The gas injection lances 7 are straight-forward injection lances in terms of basic construction and do not include swirlers for imparting swirl to oxygen-enriched air flowing through the lances. As is indicated above, research work of the applicant found that gas injection lances 7 operating without swirl could achieve comparable performance to lances operating with swirl.
The gas injection lances 7 extend downwardly through the frusto-conical section 33 of the side wall 25 of the vessel 3 into the upper region of the vessel 3. The lances 7 are equi-spaced around the frusto-conical section 33 and are at the same height. The lances 7 are positioned to extend downwardly and outwardly to inject hot air towards the lower section 29 of the side wall 25. It is important to note that it is undesirable that oxygen-containing gas contact the side wall 25 of the vessel—high temperatures generated by combustion at the side wall are undesirable from the viewpoint of vessel life. Consequently, the lances 7 are arranged so that tips 53 of the lances 7 are points on a horizontal circle.
The above-described downward and outward injection of oxygen-containing off-gas is also desirable from the viewpoint of avoiding combustion of reaction gases, such as CO, in a central vertical core of the vessel, generally identified by the numeral 139, in
As can best be seen in
The ring main 9 includes 4 outlets 65.
The connection members 49 of the gas delivery duct assembly connect together the ring main 9 and the gas injection lances 7.
The hot connection member 49 for each gas injection lance 7 includes a spool 61 that extends from an inlet end of the lance 7 and an expansion joint 63 that is connected at one end to the spool 61 and at the other end to an outlet 65 of the ring main 9.
In use, the gas injection lances 7 receive oxygen-enriched hot air flow via the ring main 9 and the connection members 49 that connect the lances 7 to the ring main 9. The ring main 9 delivers the same flow rate of hot air to each lance 7.
With reference to
(a) positioning the lance 7 vertically with the tip 53 of the lance 7 in a required position—indicated by the circular icons 55 in FIGS. 6 and 8—and then,
(b) with the lance tip 53 fixed, pivoting the lance 35° in a vertical plane that intersects the lance tip 53 and is perpendicular to a radial plane that intersects the lance tip 35 and then,
(c) with the lance tip 53 fixed, rotating the lance 30° outwardly towards the radial plane.
The gas injection lances 7 are arranged to be removable from the vessel 3.
Specifically, each lance 7 can be extracted by detaching the spool 61 and the expansion joint 63 of the associated connection member 49 from each lance 7 and the ring main 9, thereafter unbolting the lance 7 from the mounting flange 37 of the lance opening 35 in the frusto-conical section 33 of the side wall 25, and thereafter connecting the lance 7 to an overhead crane (not shown) and lifting the lance 7 upwardly from the opening 35.
Replacement lances 7 can be inserted into the vessel 3 by the reverse procedure to that described in the preceding paragraph.
The 12 solids injection lances 5a, 5b of the solids feed assembly extend downwardly and inwardly through openings (not shown) in the side wall 25 of the lower section 29 of the side wall 25 of the vessel 3 and into the slag layer (not shown) of the molten bath 41. The lances 5a, 5b are arranged so that the tips of the lances are points of an imaginary horizontal circle. The side wall 25 includes mounting flanges 69 and the lances 5a, 5b are mounted onto and supported by the flanges 69.
With reference to
The solid materials are entrained in an oxygen-deficient carrier gas. All of the lances 5a, 5b are the same external diameter and are positioned at the same height of the vessel 3. The lances 5a, 5b are equi-spaced around the circumference of the lower section 29 of the side wall 25 and are arranged so that the iron ore injection lances 5a are arranged in pairs and there is a coal injection lance 5b separating each adjacent pair of iron ore injection lances 5a. The pairing of the iron ore lances 5a to inject hot iron ore into the vessel reduces piping access issues around the vessel.
In use, the iron ore injection lances 5a receive hot iron ore fines and fluxes via a hot ore injection system and the coal injection lances 5b receive coal and fluxes via a carbonaceous material injection system during a smelting operation.
With reference to
With reference to
The outer diameter of the coal supply lines 75 is less than, typically 40-60% of, the outer diameter of the hot ore branch lines 75. While the internal diameter of the lances 5a, 5b is preferably the same, the need to insulate the hot ore supply lines 75 and the hot ore branch lines 77 significantly increases the outer diameter of the lances. Typically, the hot ore branch lines 75 have the same outer diameter in a range of 400-600 mm and the coal supply lines 77 have the same outer diameter in a range of 100-300 mm. In one particular example, the hot ore branch lines 75 have an outer diameter of 500 mm and the coal supply lines 77 have an outer diameter of 200 mm.
The solids injection lances 5a, 5b are arranged to be removable from the vessel 3.
Specifically, the solid feed assembly includes an assembly to support each solids injection lance 5a, 5b during removal of the lance from the vessel and insertion of a replacement lance into the vessel 3. The support assembly for each lance 5a, 5b includes an elongate track (not shown) extending upwardly and outwardly from the side wall 25 of the vessel 3, a carriage (not shown) movable along the track, and a carriage drive (not shown) operable to move the carriage along the track, with the carriage being connectable to the lances 5a, 5b to enable the lance to be supported on the track and moved upwardly and downwardly by operation of the carriage drive and thereby extracted from the vessel 3. The support assembly is described in International applications PCT/2005/001101 and PCT/AU2005/01103 in the name of the applicant and the disclosure in the International applications is incorporated herein by cross-reference.
As will be evident from the above description, the direct smelting plant accommodates removal and replacement of 16 lances comprising the 4 gas injection lances 7 and the 12 solids injection lances 5a, 5b. The vessel 3 is a relatively compact vessel. This compactness of the vessel 3 and the positions of the ring main 9 and the gas ducts 11 in relation to the vessel 3 places tight space constraints on the removal and replacement of the lances 7, 5a, 5b.
With reference to
The access zones 97a are outboard of the ring main 9 and inboard of the outer perimeter 91 of the superstructure 89. There are 12 access zones 97a in total, corresponding to the 12 solids injection lances 5a, 5b. The access zones 97a enable removal and replacement of the solids injection lances 5a, 5b.
The access zones 97b are inboard of the ring main 9. There are 4 access zones 97b in total, corresponding to the 4 gas injection lances 7. The access zones 97b enable removal and replacement of the gas injection lances 7.
The pair of offgas ducts 11 of the offgas duct assembly allow offgas produced in a HIsmelt process operating in the vessel 3 to flow from the vessel 3 for downstream processing before being released to the atmosphere.
As is indicated above, the HIsmelt process preferably operates with air or oxygen-enriched air and therefore generates a substantial volume of offgas and requires relatively large diameter offgas ducts 11.
The offgas ducts 11 extend from the upper section 31 of the side wall 25 at an angle of 7° to the horizontal.
As can best be seen in
With reference to
With further reference to
With further reference to
In use, the cooled offgas from the offgas cooler 111 is processed as required, for example by being used as a fuel gas in stoves (not shown) or a waste heat boiler (not shown) to recover chemical energy form the offgas, and thereafter released into the atmosphere as a clean offgas.
The direct smelting plant also includes a metal tapping assembly that includes a forehearth 13 to tap molten iron continuously from the vessel 3. Hot metal produced during a smelting operation is discharged from the vessel 3 through the forehearth 13 and a hot metal launder (not shown) connected to the forehearth 13. The outlet end of the hot metal launder is positioned above a hot metal ladle station (not shown) to supply molten metal downwardly to ladles located at the station.
The direct smelting plant also includes an end metal tapping assembly to tap molten iron from the vessel 3 at the end of a smelting operation out of the lower part of the vessel 3 and to transport the molten iron away from the vessel 3. The end metal tapping assembly includes a plurality of metal end tap holes 15 in the vessel 3.
The direct smelting plant also includes a slag tapping assembly to tap molten slag from the vessel 3 periodically from the lower part of the vessel and to transport the slag away from the vessel 3 during a smelting operation. The slag tapping assembly includes a plurality of slag notches 17 in the vessel 3.
The direct smelting plant also includes a slag end tapping assembly to drain slag from the vessel 3 at the end of a smelting operation. The slag end tapping assembly includes a plurality of slag tap holes 19 in the vessel 3.
In a smelting operation in accordance with the HIsmelt process, iron ore fines and a suitable carrier gas and coal and a suitable carrier gas are injected into the molten bath through the lances 5a, 5b. The momentum of the solid materials and the carrier gases causes the solid materials to penetrate the metal layer of the molten bath 41. The coal is devolatilised and thereby produces gas in the metal layer. Carbon partially dissolves in the metal and partially remains as solid carbon.
The iron ore fines are smelted to molten iron and the smelting reaction generates carbon monoxide. Molten iron is removed continuously from the vessel 3 via the forehearth 13.
Molten slag is removed periodically from the vessel 3 via the slag notches 17.
The gases that are transported into the metal layer and generated by devolatilisation and smelting reactions produce significant buoyancy uplift of molten metal, solid carbon and slag (drawn into the metal layer as a consequence of solid/gas/injection) from the metal layer which generates upward movement of splashes, droplets and streams of molten metal and slag, and these splashes, droplets and streams entrain slag as they move through the slag layer. The buoyancy uplift of molten metal, solid carbon and slag causes substantial agitation of the slag layer, with the result that the slag layer expands in volume. In addition, the upward movement of splashes, droplets and streams of molten metal and slag—caused by buoyancy uplift of molten metal, solid carbon and slag—extend into the space above the molten bath and forms the above-described fountain.
Injection of the oxygen-containing gas into the fountain via the gas injection lances 7 post-combusts reaction gases, such as carbon monoxide and hydrogen, in the vessel 3. Heat generated by the post combustion is transferred to the molten bath when molten material falls back into the bath.
Offgas resulting from the post-combustion of reaction gases in the vessel 3 is taken away from the vessel 3 through the offgas ducts 11.
Many modifications may be made to the embodiment of the present invention described above without departing from the spirit and scope of the invention.
By way of example, whilst the embodiment described above includes 2 offgas ducts 11, the present invention is not limited to this number of offgas ducts 11 and extends to any suitable number of offgas ducts 11.
In addition, whilst the embodiment described above includes a ring main 9 to deliver the oxygen-containing gas to the gas injection lances 7, the present invention is not limited to this arrangement and extends to any suitable gas delivery assembly.
In addition, whilst the embodiment described above includes 4 gas injection lances 7, the present invention is not limited to number and the arrangement of the lances 7 and extends to any suitable number and arrangement of the lances 7.
In addition, whilst the embodiment described above includes 12 solids injection lances 5a, 5b, with 8 lances 5a being iron ore injection lances arranged in pairs and the remaining 4 lances 5b being coal injection lances, the present invention is not limited to this number and arrangement of the lances 5a, 5b.
In addition, whilst the embodiment described above includes a forehearth 13 to tap molten iron continuously from the vessel 3, the present invention is not limited to the use of the forehearth and to continuous tapping of molten iron.
Number | Date | Country | Kind |
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2006901032 | Mar 2006 | AU | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/AU2007/000247 | 3/1/2007 | WO | 00 | 12/31/2008 |
Publishing Document | Publishing Date | Country | Kind |
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WO2007/098550 | 9/7/2007 | WO | A |
Number | Name | Date | Kind |
---|---|---|---|
5489325 | Keogh et al. | Feb 1996 | A |
5865876 | Watkins et al. | Feb 1999 | A |
6368548 | Innes | Apr 2002 | B1 |
6379424 | Dry | Apr 2002 | B1 |
6399016 | Burrow | Jun 2002 | B2 |
6423114 | Burke | Jul 2002 | B1 |
20030011114 | Dunne et al. | Jan 2003 | A1 |
20040256773 | Dry et al. | Dec 2004 | A1 |
20080202061 | Ions et al. | Aug 2008 | A1 |
20090166937 | Hayton et al. | Jul 2009 | A1 |
20090194919 | Dry et al. | Aug 2009 | A1 |
20090218737 | Hayton et al. | Sep 2009 | A1 |
20090309275 | Loiacono | Dec 2009 | A1 |
Number | Date | Country |
---|---|---|
0 446 860 | Sep 1991 | EP |
1 652 941 | May 2006 | EP |
2000146452 | May 2000 | JP |
WO 9631627 | Oct 1996 | WO |
WO 9842878 | Oct 1998 | WO |
WO 0022176 | Apr 2000 | WO |
WO 0224963 | Mar 2002 | WO |
WO 2004090173 | Oct 2004 | WO |
WO 2005080608 | Sep 2005 | WO |
WO 2005090613 | Sep 2005 | WO |
WO 2006010208 | Feb 2006 | WO |
WO 2006010210 | Feb 2006 | WO |
Number | Date | Country | |
---|---|---|---|
20090166937 A1 | Jul 2009 | US |