USRE37922E1 - Method and apparatus to determine and control the carbon content of steel in a BOF vessel - Google Patents
Method and apparatus to determine and control the carbon content of steel in a BOF vessel Download PDFInfo
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- USRE37922E1 USRE37922E1 US09/246,991 US24699199A USRE37922E US RE37922 E1 USRE37922 E1 US RE37922E1 US 24699199 A US24699199 A US 24699199A US RE37922 E USRE37922 E US RE37922E
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
- C21C5/42—Constructional features of converters
- C21C5/46—Details or accessories
- C21C5/4673—Measuring and sampling devices
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
- C21C5/30—Regulating or controlling the blowing
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D21/00—Arrangements of monitoring devices; Arrangements of safety devices
- F27D21/02—Observation or illuminating devices
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J1/00—Photometry, e.g. photographic exposure meter
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D19/00—Arrangements of controlling devices
- F27D2019/0006—Monitoring the characteristics (composition, quantities, temperature, pressure) of at least one of the gases of the kiln atmosphere and using it as a controlling value
- F27D2019/0012—Monitoring the composition of the atmosphere or of one of their components
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/10—Reduction of greenhouse gas [GHG] emissions
- Y02P10/122—Reduction of greenhouse gas [GHG] emissions by capturing or storing CO2
Definitions
- This invention is directed to a method and apparatus for controlling or determining the carbon content of a heat in a BOF vessel, and more particularly, to a method for determining the in-blow carbon content and the First Turn Down Carbon (FTDC), in low carbon steel BOF heats containing 0.06% or less carbon.
- FTDC First Turn Down Carbon
- the heat may have to be reblown to further reduce the carbon level. This increases production time and cost, and causes excess refractory wear.
- the excess refractory wear is due to the iron oxides that are formed in the slag during the reblow. Iron oxides in the slag make the slag more corrosive to the refractory lining.
- BOF control systems Another problem encountered with BOF control systems is dealing with the hostile environment adjacent the hot BOF vessel.
- the radiant heat emitted from a BOF vessel during the steelmaking process overheats sensitive electronic equipment located near the vessel and causes system failures. Dust and fume released from the vessel also settles on equipment located throughout the steelmaking shop, including the various sensor devices used to control the steelmaking process.
- the dust and fume causes control equipment sensors to become fouled and dirty, and results in poor readings and inaccurate metallurgical analysis.
- the foregoing objects can be attained by measuring a drop in visible light intensity emitted from a BOF vessel with a light sensor housed within a temperature regulated case having a sighting window including air wipe means to shield the light sensor from steelmaking dust and fume.
- the drop in visible light intensity is measured from a point of maximum light intensity emitted from the BOF vessel in relation to the amount of oxygen blown into the BOF vessel from such point of maximum light intensity, to the end of the oxygen blow.
- the light intensity and oxygen readings are used to compute continuous, real time in-blow % carbon levels until an aim carbon content is reached for the heat.
- FIG. 1 is a schematic view showing the preferred system used to carry out the steps of the method to determine carbon content of a BOF heat.
- FIG. 2 is an elevation view of the preferred embodiment of the light sensor shown in the preferred system of FIG. 1 .
- FIG. 3 is an enlarged view showing a portion of the light sensor of FIG. 2 .
- FIG. 4 is a graph showing a BOF heat having a 0.053% FTDC.
- FIG. 5 is a graph showing a BOF heat having a 0.045% FTDC.
- FIG. 6 is a graph showing a BOF heat having a 0.028% FTDC.
- FIG. 7 is a flow chart of one program that may be used to determine in-blow carbon content and FTDC based upon flame drop measurements and oxygen blown.
- FIG. 1 shows the preferred embodiment of the sensor system 10 for carrying out the steps of the method to determine in-blow % carbon content and FTDC levels of BOF heats.
- in-blow carbon content shall mean realtime carbon levels determined at any point during an oxygen blow
- FTDC shall mean First Turn Down Carbon determined at the end of the first oxygen blow into a BOF.
- the system comprises a sensor device 1 , an oxygen source 2 , and a Programmable Logic Controller 3 , (PLC).
- the sensor device 1 comprises a case or housing 5 to hold various electronic components of the sensor device including a light meter 4 having means to amplify light intensity signals to a level suitable for use in the PLC, a power supply 6 , and a cold air supply 7 to prevent the hot steelmaking environment from overheating the sensor device.
- the sensor device further includes a sighting window 8 that extends through a wall of the case 5 to expose the light meter 4 to visible light emitted from the mouth of the BOF vessel.
- An air wipe 9 emanates from the open sighting window 8 to prevent dust and fume from entering the interior space of the case. The air wipe 9 encircles the light sensitive portion of the light meter 4 and shields it from the steelmaking dust and fume.
- the sensor device is designed to generate light intensity signals when it is exposed to light emitted from the mouth of the BOF vessel, and the signals are sent to the PLC for processing.
- the oxygen source 2 includes means to generate signals that correspond to the amount of oxygen blown during the heat, and these signals are also sent to the PLC for processing.
- the light intensity signals and the oxygen blown signals provide data to continuously calculate in-blow % carbon content of the heat during the oxygen blow.
- the PLC receives and processes the light and oxygen signals to provide a continuous in-blow % carbon content reading in real time based upon the drop in visible light intensity in relation to the amount of oxygen blown, hereinafter referred to as “the flame drop method.”
- In-blow % carbon content predictions based upon the flame drop method are found to contain an error of prediction of about 0.004% carbon.
- the preferred embodiment of the sensor device 1 comprising a case 5 having a hinged lid 11 to provide an opening 12 for access to the interior space 13 of case 5 .
- a gasket or seal 14 extends along the periphery of the opening 12 , and the gasket cooperates with hinged lid 11 to prevent dust or fume from entering the interior space 13 when the lid 11 is in its closed position.
- a cold air supply 7 shown as a vortex tube in the preferred embodiment, extends through a wall of the case to inject cold air 15 A into the interior space 13 . The cold air cools the interior space 13 .
- a thermometer 16 is also attached to a wall of case 5 . The thermometer includes a temperature probe 17 that extends into interior space 13 to provide an inside space temperature reading on the thermometer. The inside temperature reading is used to control the interior temperature of the case by regulating the cold air supply 7 .
- the cold air supply is shown comprising a vortex tube cooler.
- any known air conditioning device having means to regulate temperature, may be used to supply cold air to the interior space 13 .
- the vortex tube 7 comprises an air inlet 18 through which pressurized air 15 is introduced into a vortex chamber 19 comprising a cold air vent 20 that injects cold air 15 A into the interior space 13 , and an exhaust tube 21 for venting hot air exhaust 15 B to the atmosphere.
- the vortex tube further includes a valve mechanism having a valve screw 42 that extends through a wall of the exhaust tube 21 to regulate the temperature of the cold air 15 A being injected into the interior space 13 .
- the temperature of the cold air is either increased or decreased by turning the valve screw 42 in either a clockwise or counter clockwise direction. This decreases or increases the flow of the hot air exhaust and in turn either raises or lowers the temperature of the cold air 15 A.
- the light meter 4 is housed within the interior space 13 of case 5 .
- a model P401025 Davis Instruments light meter is used.
- any suitable light meter capable of measuring the visible light intensity emitted from the mouth of a BOF vessel may be used with the sensor apparatus 1 .
- the Davis light meter has a selenium photo-voltaic cell 22 separate from its amplifying circuit 23 . This light meter arrangement makes it possible to independently mount the light sensitive cell 22 and the amplifying circuit 23 within case 5 .
- the light sensitive cell 22 is attached to a slidable adjustment 24 , and the amplifying circuit 23 to a fixed non-conductive mounting board 25 that is attached to a wall of the case.
- An electrical wire 26 connects the photo-voltaic cell 22 to the amplifying circuit 23 , and the amplifying circuit increases the level of the light intensity signals received from the flow of electrons that respond to visible light falling on photo-voltaic cell 22 .
- a power source (not shown) supplies power to the light meter 4 through line 27 , and the amplified electrical signals from the light meter are transmitted through line 28 to the PLC shown in FIG. 1 .
- the power supply may be either internal as shown by reference number 6 in FIG. 1, or external as shown by the outside power line 27 in FIG. 2 .
- the slidable adjustment 24 includes a mounting plate 29 , a clamp arrangement 33 attached to a first end of the mounting plate, and a screw mechanism 32 attached to a second end of the mounting plate opposite the clamp arrangement 33 .
- the mounting plate 29 also includes elongated slots 30 .
- a Pin or fastener 31 having one end fixed to the mounting board 25 , extends through each slot 30 to slidably attach the mounting plate 29 to the non-conductive mounting board 25 .
- the screw mechanism includes a first threaded boss 34 attached to the non-conductive mounting board 25 , and a second threaded boss 35 attached to the mounting plate 29 .
- a threaded shaft 36 having an adjustment knob 37 located at one end thereof extends through the threads of the first and second boss. The threaded shaft 36 provides a force to move the mounting plate 29 within the limits of engagement between the elongated slots 30 and pins 31 when shaft 36 is rotated in either a clockwise or counter clockwise direction.
- the clamp arrangement 33 is located opposite the screw mechanism 32 and includes a back plate 38 attached to mounting plate 29 and positioned in a direction parallel to the sighting window 8 .
- Clamp 33 also includes a transparent front plate 39 positioned adjacent the sighting window 8 and attached to the back plate by fasteners 40 .
- the photo-voltaic cell 22 is positioned between plates 38 and 39 , and the fasteners are tightened to clamp cell 22 between the two plates and hold it in place, adjacent and parallel to the sighting window 8 .
- the cold air 15 A injected into the interior space 13 from the cold air vent 20 , provides a cold air flow throughout the interior of case 5 .
- the cold air How travels in a direction toward the open sighting window 8 and cools the electronic components housed within the case.
- the cold air encircles the photo-voltaic cell 22 positioned adjacent the open sighting window 8 , and it exits through the window to provide an air wipe 9 .
- the air wipe 9 prevents dirt, dust and fume from entering the interior space 13 through the sighting window 8 and thereby maintains the transparent plate 39 , and the light sensitive surface of the photo-voltaic cell 22 , in a clean condition.
- the apparatus is not limited to a photo cell having a disk shape configuration.
- the shape of the photo cell is not important to the scope of this invention, and it may comprise any suitable shape such as a square, rectangle, etc., and still be considered encircled by the air wipe 9 .
- the screw mechanism 32 may be rotated to move the photo cell in a direction toward the sighting window. This will reduce the air gap 41 and increase the velocity of the air wipe 9 .
- the screw mechanism is rotated until the air wipe velocity is increased to a level that prevents dust and fume from contaminating the light sensitive surface of the photo-voltaic cell 22 .
- the screw mechanism may be rotated in the opposite direction to increase the air gap 41 and reduce the velocity of the air wipe.
- Degree of Flame Drop A ratio between a decrease in light (DLI/TLI) intensity (DLI) at any point in time between the maximum LI and the end of the oxygen blow, and an increase in light intensity (ILI) from the start of the oxygen blow to a point of maximum LI.
- DCF decrease in light
- ILI increase in light intensity
- the FTDC variables were then correlated through statistical regression analyses to develop an FTDC equation that could be used to determine the in-blow % carbon content for any low carbon heat. This was done by first defining the DO 2 , DLI/ILI and DO 2 kink variables as follows to simplify the calculations:
- the X 2 variable is a ratio between the two LI quantities, (DLI/ILI) and is a measurement of the degree of flame drop in a BOF.
- the LI values used in this work are expressed in arbitrary units. Because X 2 is only a ratio between two LI quantities, the units in which LI is measured have no effect in characterizing the intensity of the flame. As long as the units of LI measurement are consistent, any unit of measurement, either arbitrary or absolute, may be used to measure the LI of the flame emitted from the BOF vessel.
- FTDC a + bX1 + cX1 2 + ⁇ dX1 3 + ⁇ ⁇ eX2 + fX2 2 + gX2 3 + ⁇ hX1X2 + iX1X2 2 + ⁇ ⁇ ⁇ ⁇ jX1 2 ⁇ X2 ⁇ + k ⁇ X3 Eqaution ⁇ ⁇ 1
- the FTDC variables were correlated through statistical regression analyses to develop an FTDC equation to determine the in-blow % carbon content for any low carbon heat. This was done by first defining the X 1 , X 2 and X 3 variables as disclosed above. The values for FTDC, X 1 , X 1 2 , X 1 3 , X 2 , X 2 2 , X 2 3 , X 1 X 2 , X 1 X 2 2 , X 1 2 X 2 and the squareroot of X 3 for the heats 1 through 300 were then listed in separate columns on a Microsoft Excel Worksheet.
- the linear regression program provided with MicroSoft Excel was run with FTDC being the dependent variable and the values of X 1 through the squareroot of X 3 being the independent variables.
- the program output specifies the values of the coefficients “a” through “k”.
- the value of “a” is the same as the “Intercept”, (the value of “a” is the same as FTDC when X 1 , X 2 and X 3 are equal to zero).
- the value for “b” is the same as the coefficient for the variable X 1
- “c” is the same as the coefficient for X 1 2 , and so on, through to the last value showing “k” the same as the coefficient for the squareroot of X 3 .
- FTDC 0.09993125 + 0.03013298 ⁇ ⁇ ( X1 ) - 0.0587246 ⁇ ⁇ ( X1 2 ) - 0.0266337 ⁇ ⁇ ( X1 3 ) - 0.0879685 ⁇ ⁇ ( X2 ) - 0.0666153 ⁇ ⁇ ( X2 2 ) + 0.12504982 ⁇ ⁇ ( X2 3 ) + 0.10246922 ⁇ ⁇ ( X1X2 ) - 0.2269549 ⁇ ⁇ ( X1X2 2 ) + 0.14953375 ⁇ ⁇ ( X1 2 ⁇ X2 ) - 0.0003159 ⁇ ⁇ ( Squareroot ⁇ ⁇ of ⁇ ⁇ X3 ) Equation ⁇ ⁇ 2
- the calculated values for the coefficients “a” through “k” vary from BOF to BOF. In general, their values are dependent upon shop conditions and the type of BOF vessel observed. Some vessels emit more visible light than others due to such conditions as skull build up at the mouth of the vessel and the physical features of the vessel design.
- the “a” through “k” values may also depend upon the location of the light meter with respect to the BOF. Therefore, it can be seen that it is necessary to determine the values of “a” through “k” for each BOF vessel before % carbon is determined using the flame-drop method.
- the calculated coefficient values “a” through “k” are entered into a program that is written based upon the program diagram shown in FIG. 7 .
- Code for one such possible program is attached herewith as Appendix A. It should be understood, however, that the attached code in Appendix A is only one example of many such codes that can be written following the program diagram shown in the drawings.
- the program shown in FIG. 7 calculates real time % carbon using the FTDC equation.
- FTDC equation is not important.
- the equation is only a means to carry out the steps of the invention for determining % carbon based upon the flame-drop method.
- a polynomial equation is one way to describe the variation of FTDC with variables X 1 , X 2 and X 3 .
- other forms of equations involving logarithmic, exponential, higher order polynomial terms or a combination of any of these terms may be used for carbon prediction.
- Neural Network programs may also be used to predict carbon for this purpose.
- the in-blow % carbon content is determined by running a computer program that calculates continuous realtime % carbon based upon an FTDC equation similar to the one disclosed. As the predicted % carbon falls to within a range of approximately 0.05% C or below, a continuous display showing the predicted % carbon is given to the operators until the end of the blow is reached. In the two curves plotted in FIGS. 4 and 5, the realtime O 2 and LI signals are relayed to the PLC for processing until the computer readout indicates that the % carbon in the steel bath has been reduced to the desired aim carbon level for the end product. The oxygen blow is then stopped, and the steel is poured into a ladle for further processing such as continuous casting into finished products.
- the third BOF heat example shown in FIB. 6 depicts a curve that continues past a “kink” in the LI measurements.
- the kink in the LI curve is an indication of a smaller post combustion flame, and a lower visible light level at the mouth of the BOF vessel. Flame reduction and lower light intensity are a result of the oxygen blow reducing the excess carbon in the steel bath to a level where suddenly a somewhat constant flame, having a low light intensity level, is observed at the mouth of the BOF vessel because of the small amount of CO in the off-gas. Consequently, the steady low level of the light intensity gives LI measurements that generate the kink in the LI curve shown in FIG. 6 .
- the values for X 1 , X 2 and X 3 can be calculated continuously as the heat is being blown, and the in-blow % carbon content of the heat can be determined in realtime until the aim carbon is predicted by the PLC output.
- a point of maximum LI is reached after about 500,000 SCF of O 2 is blown into the vessel.
- the light intensity drops from a high of approximately 730, and the oxygen blow continues until a metal composition of 0.053% carbon is reached.
- the PLC receives continuous realtime LI and O 2 signals from the sensor device 1 and the oxygen supply 2 , and displays continuous in-blow % carbon content for the heat starting at about 0.05% carbon and below until the end of the oxygen blow is shut down.
- the 0.053% carbon level is reached at a light intensity of about 480 corresponding to a DO 2 of approximately 45,000 SCF.
- an LI curve for a low carbon BOF heat is shown having an FTDC of 0.045% carbon.
- a point of maximum LI is reached at about 780 at just under 500,000 SCF of oxygen, and the 0.045% carbon level is predicted at a light intensity of about 400 corresponding to a DO 2 of approximately 40,000 SCF.
- the program calculates the X 1 , X 2 and X 3 values and continuously predicts the in-blow % carbon content.
- a BOF heat having an FTDC of 0.028% carbon.
- the oxygen is blown past the point of DO 2 kink shown in the LI curve.
- the “kink” occurs at the stage of the steelmaking process where the excess carbon has been reduced by the oxygen to such a low carbon level that the small amount of CO in the off-gas suddenly produces a somewhat constant low light level flame as described above. Consequently, the dark post combustion flame at the mouth of the BOF vessel produces X 2 variables that produce the “kink” in the LI curve.
- Control of the oxygen blow is more critical through the DO 2 kink portion of the heat.
- the PLC readout must be watched to prevent overblowing the heat and consuming excessive amounts of carbon.
- the heat shown in FIG. 6 reaches its point of maximum LI at about 710 at 360,000 SCF of oxygen.
- the LI intensity then drops until it reaches the “kink” at an LI measurement of about 280.
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Abstract
Description
Delta Oxygen | Amount of oxygen blown, is SCF, | ||
(DO2) = | from a point of maximum LI to the end | ||
of the oxygen blow. | |||
Degree of Flame Drop | A ratio between a decrease in light | ||
(DLI/TLI) = | intensity (DLI) at any point in time | ||
between the maximum LI and the end | |||
of the oxygen blow, and an increase in | |||
light intensity (ILI) from the start | |||
of the oxygen blow to a point of | |||
maximum LI. | |||
Delta Oxygen | The amount of oxygen blown, in SCF, | ||
(DO2kink) = | from a “kink” in LI measurements to | ||
the end of the oxygen blow. | |||
TABLE A | |||||
Heat - FTDC | | X2 | X3 | ||
1. | 0.032 | 1.206 | 1.057 | 2.990 | ||
2. | 0.021 | 1.412 | 1.297 | 1.250 | ||
3. | 0.043 | 0.580 | 0.722 | 0.000 | ||
| | | | | | | | |||
| | | | | | | | |||
299. | 0.028 | 1.142 | 1.149 | 0.951 | ||
300. | 0.056 | 0.173 | 0.354 | 0.000 | ||
Claims (65)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/246,991 USRE37922E1 (en) | 1995-10-31 | 1999-02-08 | Method and apparatus to determine and control the carbon content of steel in a BOF vessel |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/550,590 US5603746A (en) | 1995-10-31 | 1995-10-31 | Method and apparatus to determine and control the carbon content of steel in a BOF vessel |
US09/246,991 USRE37922E1 (en) | 1995-10-31 | 1999-02-08 | Method and apparatus to determine and control the carbon content of steel in a BOF vessel |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08/550,590 Reissue US5603746A (en) | 1995-10-31 | 1995-10-31 | Method and apparatus to determine and control the carbon content of steel in a BOF vessel |
Publications (1)
Publication Number | Publication Date |
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USRE37922E1 true USRE37922E1 (en) | 2002-12-10 |
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Family Applications (2)
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US08/550,590 Ceased US5603746A (en) | 1995-10-31 | 1995-10-31 | Method and apparatus to determine and control the carbon content of steel in a BOF vessel |
US09/246,991 Expired - Lifetime USRE37922E1 (en) | 1995-10-31 | 1999-02-08 | Method and apparatus to determine and control the carbon content of steel in a BOF vessel |
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US08/550,590 Ceased US5603746A (en) | 1995-10-31 | 1995-10-31 | Method and apparatus to determine and control the carbon content of steel in a BOF vessel |
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US (2) | US5603746A (en) |
EP (2) | EP0859866B1 (en) |
JP (1) | JP3251296B2 (en) |
KR (1) | KR100321670B1 (en) |
CN (1) | CN1068633C (en) |
AT (1) | ATE202150T1 (en) |
AU (1) | AU709663B2 (en) |
CA (1) | CA2235499C (en) |
DE (1) | DE69613388T2 (en) |
ES (1) | ES2159755T3 (en) |
TW (1) | TW331574B (en) |
WO (1) | WO1997016571A1 (en) |
ZA (1) | ZA967866B (en) |
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Also Published As
Publication number | Publication date |
---|---|
US5603746A (en) | 1997-02-18 |
EP1046720A1 (en) | 2000-10-25 |
JPH11514703A (en) | 1999-12-14 |
CA2235499A1 (en) | 1997-05-09 |
CN1068633C (en) | 2001-07-18 |
DE69613388T2 (en) | 2002-04-25 |
EP0859866B1 (en) | 2001-06-13 |
ATE202150T1 (en) | 2001-06-15 |
KR100321670B1 (en) | 2002-11-01 |
JP3251296B2 (en) | 2002-01-28 |
CA2235499C (en) | 2002-10-22 |
CN1196757A (en) | 1998-10-21 |
AU6968396A (en) | 1997-05-22 |
MX9802959A (en) | 1998-11-29 |
KR19990063751A (en) | 1999-07-26 |
ZA967866B (en) | 1997-06-12 |
AU709663B2 (en) | 1999-09-02 |
DE69613388D1 (en) | 2001-07-19 |
WO1997016571A1 (en) | 1997-05-09 |
ES2159755T3 (en) | 2001-10-16 |
TW331574B (en) | 1998-05-11 |
EP0859866A1 (en) | 1998-08-26 |
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