EP1301642A1

EP1301642A1 - Method and device for reducing the oxygen content of a copper melt

Info

Publication number: EP1301642A1
Application number: EP01956290A
Authority: EP
Inventors: Heinrich Schliefer; Alexander Khoury; Stefan Schneider
Original assignee: Norddeutsche Affinerie AG
Current assignee: Aurubis AG
Priority date: 2000-07-21
Filing date: 2001-06-21
Publication date: 2003-04-16
Anticipated expiration: 2021-06-21
Also published as: CN1443248A; CN1271225C; US7264767B2; EP1301642B1; US20040007091A1; AU2001278370A1; WO2002008476A1; DE50105546D1; ATE290613T1; DE10035593A1

Abstract

Reducing the oxygen content of a copper melt comprises melting the copper initially in a shaft furnace, and subsequently feeding it to a treatment furnace via a transporting channel so that rinsing gas in the region of both the channel and the treatment furnace rises by flowing from the porous plugs. The rinsing gas containing 30-70% reduction gas and 70-30% inert gas flows from at least one of the plugs. The melt is electrically heated/moved in the treatment furnace. An independent claim is also included for an apparatus for reducing the oxygen content of a copper melt comprising a treatment furnace (1) having an inlet (2), a central part (12) and an outlet (3). Preferred Features: The reduction gas is provided with carbon monoxide, preferably carbon dioxide. The porous plug is made of Al2O3, SiC, SiO2 or MgO.

Description

METHOD AND DEVICE FOR REDUCING THE OXYGEN CONTENT OF A COPPER MELT

The invention relates to a method for reducing the oxygen content of a copper melt, in which at least one flushing stone is arranged in the lower region of the copper melt, from which at least one flushing gas emerges which rises in the copper melt.

The invention further relates to a device for reducing the oxygen content of a copper melt, which is essentially designed as a self-contained treatment vessel or a closed treatment furnace and in which the copper melt can be tempered and / or mixed by means of electric current.

Many processes are already known for producing copper and its alloys with very low impurity levels, for example less than 50 ppm, and / or with very low oxygen levels, for example less than 5 ppm. Be in technology Similar processes are also used for other metals (e.g. aluminum and iron).

The objective of the different technologies according to the state of the art usually includes the following:

Removal of reaction products and / or impurities and / or slags and / or individual / several elements located in the liquid metal.

In this context, the use of filters, for example, the provision of residence times for settling, the treatment by additives which react with the contaminants, the use of physical separation processes such as e.g. Flushing, applying vacuum, etc. in one or more steps, in combination with the above technologies or in individual use of these technologies in order to achieve the desired refining effects.

These processes have become known and have found widespread use in the treatment of aluminum and steel and their alloys, while they are only partially used in the copper industry.

In the manufacture of copper, poling with tree trunks and with reducing gases to remove the oxygen content has been generally used since ancient times. The addition of reducing elements such as phosphorus and lithium or boron in the form of, for example, is also known Mother alloys. Filters, slag sumps, vacuum chambers / ovens and / or settling times are also used to clean the metal.

All of the methods listed above are used for copper to reduce very high levels (e.g. greater than 200 - 2000 ppm) of impurities and / or oxygen and are widely used. It is also known that deoxidizers such as' e.g. Phosphorus can also be used as an alloying element to achieve certain material properties.

For the production of very clean copper materials, electrolytically refined copper (cathodes) is used almost continuously as the base material, whose level of contamination due to the previous refining steps (thermal and chemical) is below 100 ppm for internationally listed grades.

In the subsequent subsequent thermal processing steps by melting and casting, further process steps, in part by the technologies listed above, further reduce the impurity content and / or the oxygen content, or eliminate the contamination level caused by the melting and casting or which is still present ,

For example, the electrical melting of copper cathodes is used as a discontinuous or continuous standard process for reducing the oxygen content below 5 to 15 ppm, the cathodes additionally being used some processes beforehand to increase the melting capacity or to remove adhering / enclosed impurities up to 950 ° C via gas burner.

The melting then takes place in an electric furnace provided with charcoal and / or reducing, largely hydrogen-free protective gas, preferably in induction furnaces. Subsequently, the liquid copper is transferred through a, if necessary, electrically heated channel, which is also flooded with reducing / protective gas, into a warming / buffering / settling furnace, likewise usually designed as an induction furnace, which is also covered with charcoal and / or is flooded with reducing / protective gas. After leaving this furnace, the melt is transferred via an, if necessary, also electrically heated and flooded with reducing / protective gas channel into an electrically heated tundish, which is also covered with charcoal and / or flooded with reducing / protective gas. The liquid metal from the tundish usually reaches the partly through a ceramic valve in the bottom. likewise with a reducing / protective gas and / or, for example, a mold covered with soot, in which the metal solidifies continuously and is withdrawn continuously or discontinuously.

This standard method described is essentially based on a reducing atmosphere in the furnace and the channels and in particular on the large exchange area between metal and reducing / protective gas within the transfer in the channels and on the long residence time inside the furnace. Within and in addition to this standard process, processes are also known which operate the above process steps in part without or only partially with reducing / protective gas. Also known are processes which only attempt to achieve low oxygen contents over long dwell times of the liquid metal in an induction furnace covered with charcoal.

Furthermore, methods are known which carry out the treatment of the liquid metal by vacuum in addition to and / or to the above standard method or its modifications.

From DE-OS 36 40 753 it is already known to blow a mixture of a gaseous hydrocarbon and an inert gas into the copper melt to remove oxygen from a copper melt. The blowing can be done by using a porous brick or by using a special nozzle.

From DE-OS 20 19 538 a further method and a device for degassing and cleaning metal melts are known. In particular, the reduction of the oxygen content of a copper melt when using purging stones is described, from which an inert gas emerges which rises in the copper melt. Reducing or oxidizing gases can be added to the inert gas.

The prior art devices and methods are not sufficient for this suitable, reproducible and to reduce the oxygen content of the molten metal to a proportion of less than 5 ppm with sufficient production speed and reasonable costs when carrying out the process.

It is therefore an object of the present invention to provide a method of the type mentioned in the introduction in such a way that a given oxygen content can be reproducibly and at reasonable and lower costs compared to the prior art, as described above, in large-scale industrial use.

This object is achieved in that the copper is first melted in a gas-fired shaft furnace and then passed to a treatment furnace via a likewise gas-fired trough.

A device according to DE 2 517 957 C 2 can be used as the shaft furnace.

In this case, both in the region of the channel and / or in the region of the treatment furnace, the purging gas emerges through the copper melt by flowing out of the purging stones from below, the purging gas being composed of at least one of the purging stones in a composition with 30% to 70% reducing gas and 70% up to 30% inert gas flows out. The shaft furnace is designed in such a way that copper with low oxygen, hydrogen and gas contents is continuously melted and transferred to the trough. Another object of the present invention is to construct a device of the type mentioned in the introduction in such a way that a reduction in the oxygen content of the copper melt can be carried out in a continuous process and at an appropriate production speed.

This object is achieved in that in the area of the bottom and the sides and in the outlet area of the treatment furnace, flushing stones are arranged in such a way that a vertical flow is formed within the copper melt from the rising flushing gas, and in addition the treatment furnace is a completely closed system with controlled conditions for Forms metal and gases.

Basically, the method and the device are suitable for being operated continuously in full. The casting of the copper melt can also be carried out batchwise depending on the treatment furnaces used. In particular, it is contemplated that the starting material should first be melted down in an inexpensive gas-fired shaft furnace.

The method and the device according to the invention make it possible to produce copper continuously with an oxygen content of less than 5 ppm and with a density greater than 8.9. Both the investment costs for the manufacture of the manufacturing plant and the operating costs in DM / t reduced when performing the method compared to the prior art.

Exemplary embodiments of the invention are shown schematically in the drawing. Show it:

Figure 1

a cross section through a treatment furnace and

Figure 2

a block diagram to illustrate the material flow.

It can be seen from the schematic cross-sectional illustration in FIG. 1 that the processing of the copper melt takes place within a treatment furnace (1). The treatment furnace (1) is provided with an inlet part (2) and a pouring part (3). The copper melt is preferably transferred from above into the inlet part (2) via an inlet (4). A level height of the melt is provided within the inlet part (2) in such a way that a space (6) remains between the melt and an inlet cover (7) in the vertical direction above a fill level (5). The melt is provided within the inlet part (2) with a cover layer (8), which can be made of soot or charcoal, for example. The inlet (4) extends in the vertical direction into the melt, so that the melt is fed in below the cover layer (8). In the embodiment shown, one or more inlet flushing plug (s) (10) is arranged in the area of an inlet bottom (9), from which the flushing gas mixture rises to reduce the oxygen content of the melt.

The inlet part (2) is coupled to a connecting channel (11) to the central part (12) of the treatment furnace (1). The connecting channel (11) extends below the fill level of the melt in the treatment furnace (1). In particular, it is contemplated to arrange the connection channel (11) immediately above the inlet floor (9) and to locate an upper boundary of the connection channel (11) at a distance from the inlet floor (9) such that the inlet channel (11) is directed vertically upwards is limited to about half the fill level of the melt within the inlet part (2).

In the area of the central part (12) there is a crucible-like or tunnel-like depression (13) into which the melt flows. According to the embodiment in FIG. 1, it is particularly contemplated to arrange an entrance floor (15) in the area of an entrance (14) of the central part (12) at a height that is approximately the same as or a lower level of the entrance floor (9) of the entrance part (2 ) corresponds. One or more sink (s) (16) can be positioned in the area of the entrance floor (15) or above the entrance floor (15).

The melt within the central part (12) can also be provided with a cover layer (8). A gas collection space (17) is arranged above the cover layer (8) and is delimited in the vertical direction by an oven cover (18). The furnace cover (18) has a gas outlet (19).

In the area of a bottom (20) of the middle part (12) one or more sink (s) (21) is arranged. The sink (s) (21) is / are preferably placed in such a way that a flow of the melt within the depression (13) is generated by rising gas bubbles in such a way that the flow direction points upwards in a central region and in edge regions a flow direction in the vertical direction is realized downwards. These flow directions are e.g. deflected by electric fields and / or inductors so that the exchange reactions between sink and melt are strengthened / extended. This ensures that melt flowing into the area of the central part (2) is first directed towards the bottom (20) and that this ensures sufficient contact with the flushing gas flowing out of the flushing plug (s) (21). The flow formed can, if necessary, be supported by a provided electrical heater.

The middle part (12) is connected to the pouring part (3) via an outflow channel (22). The outflow channel (22) has a height localization similar to the connecting channel (11). An upper height limit of the outflow channel (22) is provided at about half the fill level of the melt within the pouring part (3). in the The area of a channel bottom (23) of the outflow channel (22) can have one or more sink (s) (24) arranged.

In the area of a transition of the central part (12) into the outflow channel (22), an exit floor (25) is provided, which extends approximately at the same height as the channel floor (23) and the entrance floor (15). One or more sinks (26) can be placed in the area of the exit floor (25) or above the exit floor (25).

The melt can also be provided with a cover layer (8) inside the pouring part (3) and a free space (28) is provided between the pouring cover (27) and the filling level above the cover layer (8). In the area of a pouring base (29) there is a pouring opening (30) for discharging the melt.

The highly schematic illustration in FIG. 2 shows that the starting material (31) to be melted is first fed to a melting furnace (32) and then transported via a trough (33) into the area of the treatment furnace (1). A flushing gas can be applied both in the region of the channel (33) and in the region of the inlet part (2), the pouring part (3) and the middle part (12). In each case, feed lines (35) for the purge gas are shown.

Melting with gas in the shaft furnace, the shaft of which acts like a heat exchanger, is much more efficient and therefore more energy-efficient than that Melting using electricity in the induction furnaces of the standard processes.

The molten and already preset liquid metal (e.g. with regard to oxygen, total gas content and impurities) flows continuously from the tap hole into the gas-fired channel (33), which is controlled and equipped in a similar way to the cathode shaft furnace.

The copper reaches the treatment furnace (1), which can also be a casting furnace, from the gas-fired and / or electrically heated and covered and / or closed channel (33).

Within the channel length, in addition to the slag sump, further sumps can be arranged which are heated by inductors and in which flushing stones are arranged in the bottom and / or from above such that an intimate mixture of the liquid metal with the flushing gases takes place in these sumps. These swamps are connected to the trough (33) either directly or through siphons.

The inductors mentioned above can be channel inductors as well as crucible inductors. The channel (33) can be arranged to be stationary or movable, depending on the use of one or more treatment / casting ovens.

Transferring with gas heating, like melting, is much more efficient and therefore more energy-efficient than transferring with the completely electrically heated channels (33) of the standard method.

The treatment furnace (1) is preferably a self-contained, fireproof brick-lined vessel. This can be arranged in a stationary or movable manner, furthermore only be present once or several times, depending on the casting technology and / or the power design.

The pretreated liquid copper coming into the treatment furnace ^* (1) is removed from the channel (33), for example via a floor drain under a bath or in a shallow inflow in the inlet area (2) of the treatment furnace, which is covered with reducing agents, for example charcoal and sealed with lids against the atmosphere initiated.

The bottom (9) and / or the sides and / or the cover (7) of the inlet part (2) are equipped with flushing nozzles so that an intimate mixing of the incoming copper with flushing gas is ensured. The inlet part (2) can also - depending on its capacity - be provided with inductors as in the channel (33).

The ^' so ^' further treated liquid copper ^• arrives from the egg inlet part (2) directly or via a siphon to the middle part (12) of the treatment furnace (1). This part of the furnace is also sealed off from the atmosphere with a cover (18) and the metal strip in it is covered with reducing agents, for example soot.

The bottom (20) and / or the sides and / or the entrance and exit areas of the middle part (12) are equipped with flushing nozzles so that an intimate mixing of the incoming copper with the flushing gas is guaranteed.

In addition, the bottom (20) is provided with one or more inductor (s) and / or an electromagnetic stirrer, so that the melt is additionally moved and thereby an intimate mixture with the purge gases, with which e.g. Continuous operation of incoming and outgoing copper and with the charcoal cover takes place and, if necessary, the melt in the treatment furnace (1) is kept at the required pouring temperature or brought to it.

From the central part (12), the melt reaches the pouring part (3) directly or via a siphon, which is also filled with reducing agents, e.g. covered with charcoal and sealed with lids (27) against the atmosphere.

Depending on the design, flushing stones and inductors can also be installed in the pouring part (3) similarly to the pouring part (2). The melt then enters the mold / mold under bath via a ceramic valve and a ceramic tube including a nozzle under the bath.

Depending on the casting process, the mold can also be flanged directly to the pouring part (3) under the bath, so that the ceramic valve mentioned above is then omitted. If the mold is flanged over the bath, a corresponding mechanical or electromagnetic one can be used between the pouring part (3) and the mold Pump can be installed in a closed version, or if the mold is closed, the melt is drawn through the solidified strand into the mold using a known method.

The non-flanged mold and the liquid metal in the upper part of the mold are e.g. covered by protective gas and / or by soot and / or by soot-charcoal mixtures against the atmosphere.

Flanged and non-flanged molds are also covered with protective gas at the metal outlet end against the atmosphere. The metal is now frozen, but still hot.

The protective gas used in the channel (33), in the treatment furnace (1) and in the mold essentially consists of inert gas such as e.g. Argon, nitrogen and from CO / C02 mixtures, the mixing ratios of inert gas ranging from 100% to 70% depending on the injection location and of C0 / C02 varying from 0% to 30% depending on the injection location when used according to the method described as for the invention Have proven effective.

In general, it is expedient to provide a proportion of the reducing gas in the range from 40% to 60% of the total gas volume consisting of reducing gas and inert gas in the area of the flushing stones. The proportion of the reducing gas is typically about 50%. All of the above shares represent volume shares. The proportion of the reducing gas in the furnace atmosphere should be in the range from 10% to 40%. The proportion is typically about 20%. The proportion of oxidizing gas components in the furnace atmosphere is about 0% to 10%. Typically there is a share of 5%.

The rinsing stones, their internal formation and their arrangement in the refractory lining or in the lids and thus with their bath height or their blowing depth as well as their local distribution and number in the channel (33) and in the treatment furnace (1) depends on the respectively existing or to be interpreted parameters.

Claims

P a t e n t a n s r u c h e

Method for reducing the oxygen content of a copper melt, in which at least one flushing stone is arranged in a lower region of the copper melt in the vertical direction, from which at least one flushing gas emerges which rises in the copper melt, characterized in that the copper is initially in a shaft furnace is melted and then passed via a transport trough to a treatment furnace that both in the region of the transport trough and in the treatment furnace the purging gas rises in the copper melt by flowing out of the purging stones and that the purging gas in at least one of the purging stones in a composition with 30% up to 70% reducing gas ^" and 70% to 30% inert gas and that the melt is heated / moved electrically in the treatment furnace.

2. The method according to claim 1, characterized in that the purge gas is used in a composition with 40% to 60% reducing gas and 60% and 40% inert gas.

3. The method according to claim 1 or 2, characterized in that the purge gas is used in a composition with about 50% reducing gas and about 50% inert gas.

4. The method according to any one of claims 1 to 3, characterized in that the copper melt in the treatment furnace (1) is heated and stirred by an induction heater.

5. The method according to any one of claims 1 to 4, characterized in that the copper melt is inductively heated and stirred in the region of a channel (33) between the melting furnace and the treatment furnace (1).

6. The method according to any one of claims 1 to 5, characterized in that the melt in the treatment furnace (1) and / or the channel (33) is covered by a cover layer (8) which contains carbon.

7. The method according to any one of claims 1 to 6, »characterized in that the reducing gas is provided with a proportion of carbon monoxide.

8. The method according to any one of claims 1 to 7, characterized in that the reducing gas is provided with a proportion of carbon dioxide.

9. The method according to any one of claims 1 to 7, characterized in that a material with proportions of A1 ₂ 0 ₃ , SiC, Si0 ₂ , and MgO is used for the sink stones.

10. The method according to any one of claims 1 to 7, characterized in that a porous material is used as sink stones.

11. The method according to any one of claims 1 to 7, characterized in that within a central part (12) of the treatment furnace (1) a flow within the copper melt is generated in the vertical direction.

12. The method according to any one of claims 1 to 7, characterized in that the flow in the copper melt is oriented in regions in the vertical direction upwards and in regions in the vertical direction downwards.

13. A device for reducing the oxygen content of a copper melt, which is essentially designed as a treatment furnace and has an inlet, a central part and a spout and in which at least one inductor is used for tempering the copper melt, characterized in that in the region of a bottom

(20) of the central part (12) at least one sink (21) is arranged and that the central part (12) has a cross-sectional configuration in such a way that a vertical flow of the rising purge gas is formed within the copper melt.

14. The apparatus according to claim 13, characterized in that in the region of a transition of the central part (12) to the inlet part (2) at least one sink (16) is arranged.

15. The apparatus according to claim 13 or 14, characterized in that in the region of a transition of the central part (12) to the pouring part (3) at least one output sink (26) is arranged.

16. The device according to one of claims 13 to 15, characterized in that a connecting channel (11) between the central part

(12) and the inlet part (2) is arranged below a melting level.

17. The device according to one of claims 13 to 16, characterized in that an outflow channel

(2) between the middle part (12) and the pouring part (3) is arranged below the melting level.

18. Device according to one of claims 13 to 17, characterized in that a gas collection space (17) is arranged above the melt in the central part (12).

19. Device according to one of claims 13 to 18, characterized in that above the A free space (6) is arranged in the melt in the inlet part (2).

20. Device according to one of claims 13 to 19, characterized in that a free space (28) is arranged above the melting level in the pouring part (3).

21. Device according to one of claims 13 to 20, characterized in that in the region of the outflow channel (22) between the central part

(12) and the pouring part (3) at least one outlet flushing block (24) is arranged.

22. Device according to one of claims 13 to 21, characterized in that the treatment furnace (1) is provided with at least one magnetic stirrer.

23. Device according to one of claims 13 to 22, characterized in that at least one sink is arranged in the region of a side wall of the treatment furnace (1).