Converter and Fire Refining Practices Edited by A. Ross, T. Warner, and K.

Scholey TMS (The Minerals, Metals & Materials Society), 2005

PRODUCTIVITY INCREASE IN A PEIRCE-SMITH CONVERTER USING THE COP KIN AND OPC SYSTEM
Thomas Prietl1, Andreas Filzwieser2 and Stefan Wallner3
1

Christian Doppler Laboratory for Secondary Metallurgy of the Non-Ferrous Metals University of Leoben, Franz-Josef-Strasse 18, 8700 Leoben, Austria 2 RHI Non-Ferrous Metals Engineering GmbH Magnesiststrasse 2, 8700 Leoben, Austria 3 RHI Refractories, Business Unit Industrial Wienerbergstrasse 11, 1100 Vienna, Austria Key Words: Gas stirring, COPKIN, endpoint, OPC Abstract

The use of gas stirring systems through the furnace bottom is common for anode and holding furnaces in the copper industry The first implementation of a gas stirring COP KIN system in a Peirce-Smith converter was performed at the New Boliden smelter, Rnnskar, Sweden. In addition to other benefits, a decrease in process time and a decrease of the oxygen content in the blister copper were observed. To determine the effects of the gas stirring system and the process endpoint, an optical production control Semtech OPC system was used. The light emission of the converter flame as an optical process parameter provides qualitative on-line process information, and is also used for endpoint determination of the slag making process, on-line control of iron content in white metal, quality control of slag etc. The results, benefits and risks of using the COP KIN and OPC system for a Peirce-Smith converter are reported. Introduction In order to meet stricter product-quality criteria, increasing productivity demands, tighter energy and environmental constraints, increasing fluctuations in raw-material composition etc., pyrometallurgical processes are getting more and more complex and thereby more difficult to operate and optimize. At the same time, cost-benefit arguments cause the smelting plants and also the individual processes to become larger with increasing throughput rates, meaning that a modest efficiency increase in one single process step might have a significant effect on the plant profitability. Process optimization and control are becoming increasingly important. In most facilities the operation is guided by static models, based principally on process modeling, operator experience and the accumulated information on material input and output. The conversion of copper in a traditional Peirce-Smith (PS) converter might be used to illustrate the different but complementary nature of this steady-state optimization and dynamic production control, which can assist in maintaining stable process operation in the face of disturbances. Examples of disturbances that might enter the conversion process are unforeseen changes in quality and tonnage of incoming matte and silica, availability and grade of cold charge, operator interventions, shift changes, timing of cranes etc. In the conversion of copper in a PS converter, some of the more important entities to optimize are blister-copper quantity, sulfur, oxygen and impurity contents of blister copper, slag composition and slag temperature. They can all be controlled by adjustment of the input to the process.
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Temperature, for instance, is controlled by the adjustment of air-blow rate, oxygen enrichment and additions of cooling material. Blister copper quantity and quality are controlled by optimization of the endpoints of the various blowing steps and the slag quality. The latter, in turn, is controlled via silica additions. Obviously there are many means for affecting and controlling the process and thereby the resulting output. On the other hand, there are very few objective means for finding out the most appropriate action at a given point in time once the process has started. Or, to be more specific, there are very few means by which to retrieve objective information on the instantaneous status of the process, for instance as regards to slag quality or instantaneous oxygen stage. The highly aggressive environment in smelters has hampered the implementation of sensors for on-line measurements, which is a necessity for true dynamic control. Consequently, true dynamic production control has developed at a slow pace.

The RHI COP KIN system The increasing costs of the production process lead to the development of new refining processes. The gas treatment with different gases (inert and reactive) is one possibility of such a technology. Removal of unwanted particles from molten melt by flotation is one of the most useful melt cleaning techniques used by the industry. Increasing the kinetics of chemical refining reactions between slag and metal is another effect of the gas treatment. Gas injection through the furnace bottom has been practiced in the steel industry (ladles) for more than 30 years and also in the non-ferrous industry (e.g. anode furnaces, holding furnaces, Peirce-Smith converter etc.). There are several reasons why the non-ferrous industry does not use stirring systems to an adequate extent. In the past no supplier would warranty the engineering, hard ware and start-up know-how for a completely proven gas stirring system and the risk was fully with the smelter. This was the primary reason that 2002 the RHI Non-Ferrous Metals GmbH based in Leoben, Austria was founded. Today RHI provides a complete gas stirring system called the COP KIN (Copper Kinetics) system. This system can be easily adapted to the needs of each customer. The gas control station is the main part of the COP KIN system. The gas station is equipped with a certain number of gas inlets e.g. for nitrogen, air and/or natural gas and also a certain number of outgoing pipes to the purging plugs. To guarantee a consistent stirring action the gas pressure must be carefully monitored in real time by the control panel. A minimum pressure of 6 bar for the inlet gas is required to ensure the gas station has the flexibility to keep the mass flow at a constant level. The software controls each plug individually to achieve a constant flow rate. This software is runs independently of the furnace computer system on site and allows a constant monitoring and adjustment of the gas flow rates as required in the treatment phases of the process. Depending on the particular application different gas mixes and flow rates per single plug can be programmed. In the case of an emergency, several safety devices are installed, e.g. if an inlet gas line is blocked for some reason the control station will immediately switch to the back-up second incoming gas line immediately and an alarm will be given. After defining the need and targets of a gas stirring system the right type, number and position of the plugs have to be calculated. For this engineering work the CFD software Fluent is used. In Figure 1 the parts of the COP KIN system are shown [1].

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control panel

porous plug with well block

gas control station

Figure 1: COP KIN system The purging plugs are produced in various designs as a consequence of the design and refractory improvements over the years. The lifetime of individual plugs is governed by their exposure to chemical, operational, mechanical and thermal conditions. The most common purging plugs in the non-ferrous industry are fired porous plugs, which are characterized by a high opening rate, an optimal bubble formation and a long in-service lifetime, but other plug types are also used (Figure 2) [2]. The porous plugs are covered with stainless steel and include thermocouples, which are connected to the gas control station, to monitor the plug wear. Today it is known from longstanding experience that the wear of a porous plug using inert gas only (e.g. nitrogen) is similar to the wear of the surrounding lining. It is also possible to use air or pure oxygen as a purging gas (reaction gas), but this results in increased plug wear. For these reasons a changeable plug arrangement was developed. To have the possibility to change plugs in such a short time and under hot conditions leads to a higher purging performance because it is now contingent to also use reaction gases. Non-changeable systems are often taken when changeable systems are not required. In Peirce-Smith (PS) converters a changeable system is not necessary because the normal tuyere zone repair could also be used to change the plugs.

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Figure 2: Purging plug types Application of the COP KIN system in a Peirce-Smith converter The dominant copper smelting technology today is the combination of flash furnace, PS converter and anode furnace, which has been widely used in the copper smelters worldwide. In 2002 the first COP KIN system was installed in one of the PS converters at the copper plant New Boliden, Rnnskr, Sweden. Initial trials have indicated that the use of an additional bottom gas stirring system provides metallurgical benefits. The first test trial was carried out with two purging plugs to determine if the wear of the plugs in the converter cause operational problems. After a normal operating period of 12 weeks, it was evident that no specific wear had occurred using the porous plugs. In a second trial, four plugs were installed and the operational safety and stability was evaluated. In a third and fourth test campaign the advantages of using the COP KIN system during a whole converter lifetime (time between relining) were carried out. At Boliden to convert matte with a copper content of approx. 60 % into blister copper (98 98.5 % Cu), eight steps need to be performed: 1. 2. 3. 4. 5. 6. 7. 8. Charging First slag blowing First slag tapping Matte blowing Second slag tapping Copper blowing Tapping of the copperoxidic slag Copper tapping

The implementation of the COP KIN system in a PS converter will affect the following benefits on the various process steps:

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Charging When the fist ladle of matte is charged into the converter it is not used as a metallurgical reactor because the tuyere zone is out of the blowing position. To have the possibility to blow air through the porous plugs to start the first slag blowing, the iron slagging reaction will start immediately and the converter will be in operation from the very beginning. First slag blowing and matte blowing During these two steps the COP KIN system is used to boost the stirring effect in the dead zone opposite the tuyeres. Different tests with various flow rates of purging gas were used during these two steps. For the endpoint determination of the two periods the Optical Production Control (OPC) system was available. First and second slag tapping With the use of the COP KIN system it is possible to individually control the flow rate of each plug. Operating the plugs near the converter endwalls at a maximum flow rate (300 l/min) and all other plugs at a minimum flow rate (10 l/min) will create a certain slag movement to the charging/tapping door. This will result in easier slag work combined with improved separation of slag and white metal. To remove most of the fayalite slag after the matte blowing step is important because the less fayalite slag remaining in the converter, the more effective the slag work during the copper blowing will be; and the lower the amount of copperoxidic slag that will be produced. Copper blowing In the copper blowing process the white metal is converted into blister copper (equation 1, 2). Cu2S + 3/2 O2 2 Cu2O + Cu2S Cu2O + SO2 6 Cu + SO2 (1) (2)

While the white metal is still present in the bath, the purging gas will help to minimize the dead zone in the converter and increase the homogenization in the bath. At the end of the copper blow a copper oxide rich slag forms. Several effects can be seen as a result of using nitrogen as the purging gas: The desulfurization is initiated earlier due the decreased partial pressure of SO2 in the bath; result of the rising gas bubbles. The oxygen efficiency increases due to improved agitation The surface between the slag and the blister copper increases as well as the interaction rate between both. The amount of copperoxidic slag decreases

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Copperoxidic slag tapping As mentioned before with the COP KIN system it is possible to control the flow rate of each plug separately and so a certain movement of the slag towards the tapping door can be achieved. Copper tapping To discharge a PS converter with 300 tons of blister per cycle, takes at least on hour. With nitrogen as purging gas the converter can be used as a metallurgical reactor and the sulfur content can be reduced during the discharging period. If a COP KIN system is also installed in the anode furnace these two purging systems can work concurrently and further optimize the process operation. The aims at Boliden were to achieve better slag tapping, lower sulfur and oxygen contents in the blister copper, less copperoxidic slag and as a result in consequence a reduction in process time. Boliden has a specific PS converter process, because there is no possibility in the anode furnace for an oxidizing step, so the have to reach a sulfur level of less than 100 ppm has to be reached in the converter. To reach this level it is necessary to over-blow the melt, which subsequently produces a high amount of copperoxidic slag. To compare the data from converter 1, which was equipped with the COP KIN system, with the values from the other two converters without a stirring system, the Optical Production Control (OPC) system was used. It was also important for a specific converter driven by the operating teams and for the endpoint determination of the different blowing steps at the converters. In the following paragraph the OPC system is explained [3-7].

The Semtech OPC system For about 15 years Semtech has developed and industrialized a remote-sensing technology, based on optics and spectroscopy, for continuous on-line process monitoring and production control of various pyrometallurgical processes; the Semtech OPC (Optical Production Control) System. The light emitted by the off-gas flames of a pyrometallurgical process is composed of heat radiation from particles and droplets and discrete radiation from atoms and molecules in the vapor phase. The radiation from the latter shows up at well-defined wavelengths, which are characteristic for each atom and molecule and with intensities which depend on the gas-phase concentration (e.g., the vapor pressure) of the light-emitting atoms and molecules. The presence and concentration of a specific atom or molecule in the off-gases is, on the other hand, determined by the thermodynamics and kinetics inside the furnace, e.g., oxidation stage, slag composition and temperature. Thus, by analyzing spectroscopically the light emitted by the off-gases, it is possible to obtain information on what is occurring inside the furnace. The interest in spectroscopic methods to control smelting processes is triggered by a number of attractive features inherent in optical measurements: They can be performed remote, e.g. without introducing any physical sensor into the furnace, They can be performed on-line, e.g. sampling is not a prerequisite for the measurement, They facilitate the detection of short-lived constituents like radicals, They can provide continuous real-time information, They are insensitive to electronic noise.
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In principle the OPC system consists of One to four light-weight telescopes, which focus light from the off-gas flames into Optical fibers. The fibers transmit the light to the OPC Server where it enters A spectrometer. The dispersed light is registered by A multichannel detector and the spectroscopic information is evaluated in terms of optical process parameters by A PC. The optical process parameters are displayed on-line as trend curves (Figure 3) on color monitors in front of the.

Figure 3: Semtech OPC trend curves at the end of the copper blowing step One server can handle the input from up to four telescopes and thereby be used for simultaneous control of the production in four furnaces or the status at different locations in one furnace. Figure 4 shows the general layout of the OPC system designed for use at four PS copper converters.

Figure 4: Schematic layout of Semtech OPC system monitoring the instantaneous process status in four PS converters

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The small, robust telescope focuses light from the off-gas flame into an optical fiber. The focal length of the telescope is very short as compared to the distance to the converter mouth. In this way the light entering the fiber emanates from various parts of the flame. Thus it represents the average composition of the gas phase that is the average status of the melt. This is in contrast to, for instance, conventional sampling via the tuyeres of a PS converter, in which case the analysis generally yields information on the local conditions in the neighborhood of the tuyeres. For instance, it generally appears that close to the end of a copper-making step a blister sample via a tuyere shows higher oxygen content than a spoon sample taken via the converter mouth. The fiber is connected to a conventional spectrometer equipped with a CCD camera with the output analyzed on a PC. The spectroscopic information is presented in the form of trend curves and displayed on color monitors in front of the converter operators and exported to existing data collection systems. Figure 5 shows an on-line recording from a full converting cycle in a PS converter. The diagram is a xy-plot of the current values of three different Optical Process Parameters versus real time. The graph exemplifies what can be seen on a client monitor at the end of the cycle noting that during the cycle the graph develops gradually. Basically the optical process parameters included in Figure 5 represent time-resolved registrations of the intensities of selected emission bands of the PbS (yellow curve) and PbO (green curve) molecules and the ratio between the intensities of selected emission bands of the CuOH and PbO molecules (red curve) [8, 9].
1,0 Optical Process Parameters (arbitrary unit) 0,9 0,8 0,7 0,6 0,5 0,4 0,3 0,2 0,1 0,0 11.00

12.00

13.00

14.00 Real time

15.00

16.00

17.00

Figure 5: On-line recording of the optical process parameters PbS, PbO and CuOH/PbO during a copper converting cycle The behavior of the Optical Process Parameters PbS and PbO during converting can be seen to be in qualitative agreement with the thermodynamic prediction of their vapor pressures (Figure 3). As long as the FeS and SiO2 contents of the matte match, that is as long as a fluid slag is being formed, PbS takes on a high and PbO a low value. When the end of a slag-forming step is approached PbS starts to decrease and PbO increases, the reason being the increasing oxygen potential as the matte is being depleted of iron. Thus, close to the end of a step the Optical Process Parameters gives continuous information on the iron content of the white metal. During the copper-making step the vapor pressure of PbS and the corresponding Optical Process Parameter are low while the PbO vapor pressure and the optical parameter PbO are high. The abrupt change in the value of the Optical Process Parameter CuOH/PbO close to the end of the step reflects a phase change, namely the disappearance of the white-metal phase and the onset of the copper-oxide production.
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The OPC technology has been tested and also permanently implemented at a variety of metallurgical processes. Naturally the useful spectroscopic information varies between different processes. However, a common feature of all Optical Process Parameters is that the oxygen potential or the oxidation stage inside the furnace determines their behavior. Consequences of using a Semtech OPC System for process optimization are shown in Figures 6, 7 and 8. OPC ok means that the Semtech OPC system was in operation, not ok the opposite [10, 11, 12].

0,6 0,5 Relative frequency 0,4 0,3 0,2 0,1 0,0 0 2 4 6 8 10 12 14 16 18 20 22 24 26 % Cu in slag OPC not OK OPC OK

Figure 6: Copper losses in slag

0,30 0,25 Relative frequency 0,20 0,15 0,10 0,05 0,00 10 15 20 25 30 35 40 45 50 55 60 % Fe3O4 in slag OPC OK OPC not OK

Figure 7: Fe3O4 in slag

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0,25

0,20 Relative frequency

0,15

0,10

0,05

0,00 200 220 240 260 280 OPC OK 300 320 340 360 380 400 420 Total blowing time / cycle (minutes) OPC not OK

Figure 8: Total blowing time

Results of the tests using the COP KIN and OPC system at a PS converter The aim at the New Boliden smelter was to make possible a more complete and faster tapping process of different slags by using eight purging plugs. Special attention was paid to the second fayalite slag. This has, when it is carried in large amounts into the blister copper blowing a phase, a disadvantageous effect on the properties of the subsequent copperoxide rich slag. Furthermore, a better tapping of the fayalite slag would reduce the amount of copper oxide-rich slag. At Boliden, because of a lack of an exhaust system for the SO2-containing waste gas, it is not possible to further lower the sulfur content by oxidation in the anode furnace. For this reason the sulfur content in the blister copper must be adjusted to about 100 ppm in the converters already and in order to achieve such a low sulfur content, there must be an over oxidation of the melt. The oxygen contained in the copper, which causes problems when the anodes are cast, must then be removed at great effort via a reduction process in the anode furnace. The excessive oxygen content causes a high by the large number of Cu2O precipitates in the solidified metal so that the ears of the anodes break off. By carrying out several experiments with various rates of purging with nitrogen or air, it was investigated whether the time needed to reach a sulfur content of 100 ppm in blister copper could be reduced. Furthermore it was investigated whether the desired sulfur content could be achieved with a lower oxygen demand by having the purging bubbles lower the SO2-partial pressure in the melt. The results with the developed optimal purging program are shown in the following Figures. In Figure 9 the position of the porous purging plugs in the PS converter is detailed.

Figure 9: Position of the plugs in the PS converter

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The optimal purging rates during the various process steps were carried out in several different experiments and the result, the performed purging program, is apparent in Figure 10. The whole purging program consists of divers sub-programs.

Figure 10: Performed purging program With the performed purging program it was possible to lower the sulfur content and the amount of dissolved oxygen in the blister copper by increasing oxygen efficiency (Figure 11).

75 70,0 70 65 60 55 50 45 40 conv 1 with purging plugs conv 2 all conv 3 all 67,1

sulfur content [ppm]

2 3
51,0

Figure 11: Sulfur content in the blister copper; converter one was equipped with the purging plugs The oxygen in the blister copper in converter one was more than 1000 ppm lower than the other converters without the COP KIN system. Also, the time to reach the endpoint after the copper turn (the white metal phase is gone) could be abbreviated (Figure 12).

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30 [min] for 300 tons and 700 Nm3/min 29 28 27 26 25 24 23 22 21 20 conv 1 with purging plugs conv 2 all

29,1 27,3

3 2
22,9

conv 3 all

Figure 12: Time needed to reach the endpoint after copper turn With the sub-programs used during the slag tapping steps a forced movement of the slag to the charging/tapping door was seen. This is reflected in a better tapping of the fayalite slag and a lower amount of copperoxidic slag at the end of the conversion process (Figure 13).

27
26,0

26 25 tons copperoxidic slag 24 23 22 21 20 19 18 17 Konvertoren

18,6 21,8

3
1

conv 1 with purging plugs

conv 2 all

conv 3 all

Figure 13: Produced amounts of copperoxidic slag It was possible to achieve good results with the use of the COP KIN and Semtech OPC system during this pilot project. Total savings have been calculated from the theoretical and experimental data for 350 production days. By reducing the copper-oxide rich slag by one ton, there is a timesavings of 0.5 minutes. Furthermore, 2.6 minutes for the copper blowing can be reduced (according to New Boliden) by an increase in the oxygen utilisation by 1%. Besides this there is an average savings of 5 minutes during the final copper blowing period (experiment results). By using the plugs, the copper-oxide rich slag could be reduced by approx. 5 tons, i.e., 2.5 minutes can be saved. In total, a savings of approx. 10 minutes could be saved during one blowing cycle. If both systems are installed in all of the three converters, at New Boliden, you will get approximately 22 blowing cycles (6600 tons of blister in a 300 tons converter) more per year. For 350 production days and an average price for the blister copper of 300, a benefit of 1.98 million /year occurs.

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Another important factor is the oxygen content in the blister copper. The consumption of ammonia in the anode furnace (at New Boliden) depends on that amount. With the amounts of oxygen in the blister copper using the COP KIN and Semtech OPC system, savings in process time in the anode furnace operation are also possible. In the future the New Boliden copper plant is going to install the COP KIN system in all converters. Conclusion Using the COP KIN and Semtech OPC system in the converter production control i. e. shorter blowing times, less copper losses in slag a.s.o. can be achieved. For both systems the working reliability and economy were sufficiently examined. References [1] A. Filzwieser, T. Prietl, P.L. Lennart and P. Olsson: Implementation of the RHI COP KIN System in Peirce-Smith-Converters, RHI Bulletin, Vol. 1, 2003. [2] L. Kneis, B. Trummer and B. Knabl: The Hybrid Plug An innovative Purging Plug for steel ladles, RHI Bulletin, Vol. 2, 2004. [3] H. Antrekowitsch, T. Prietl, A. Filzwieser: Splgastechnik in der Kupferindustrie, BHM 149, Heft 5, 2004. [4] H. Antrekowitsch: Gas treatment in the secondary metallurgy of non ferrous metals, Proceedings of EMC, 2003. [5] A. Filzwieser, J. Kleicker, K. Caulfield and S. Wallner: The COP KIN System Fundamentals and mathematical modeling, Proceedings of Copper 2003/Cobre2003, Santiago, Chile, 2003. [6] J. Rigby, A. Filzwieser, J. Kleicker, K. Caulfield and S. Wallner: The COP KIN System Performance and benefits a world wide overview, Proceedings of Copper 2003/Cobre 2003, Santiago, Chile, 2003. [7] K. Gamweger and A. Filzwieser: AL KIN A Gas Purging System for Furnaces in the Aluminum Industry, BHM 149, Heft 1, 2004. [8] W. Wendt, M. Aldn, B. Bjrkman, T. Lehner and W. Persson: Controlling copper conversion via optical spectroscopy, JOM 39, 14-17 (1987). [9] W. Persson, W. Wendt and H. Bertheussen: On-line optical process control in steel making, JOM 41, 17-19 (1989). [10] W. Persson, W. Wendt and S. Demetrio: Use of optical on-line production control in copper smelters, Copper 99/Cobre 99, Phoenix, 1999. [11] W. Persson and W. Wendt: From Research to Reality 15 Years with Optics and Spectroscopy for Production Control in Metallurgical Industry, Conference of Metallurgists, Montreal, 2002.

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[11] W. Persson and W. Wendt: Optical Spectroscopy for Process Monitoring and Production Control in Ferrous and Non-Ferrous Industry, Process Control and Optimization in Ferrous and Non-Ferrous Metallurgy, Chicago, 2003.

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