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Pyrometallurgical Refining of Copper in an

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 Title of Publication Edited by
TMS (The Minerals, Metals & Materials Society), Year

Pyrometallurgical Refining of Copper in an Anode Furnace

H. Antrekowitsch1, C. Wenzl1, I. Filzwieser2, D. Offenthaler2

1
Christian-Doppler-Laboratory for Secondary Metallurgy of Nonferrous Metals
Franz-Josef-Straße 18; Leoben, 8700, Austria
2
Department of Nonferrous Metallurgy
Franz-Josef-Straße 18, Leoben, 8700, Austria

Keywords: copper, thermodynamic, anode furnace, refining, refining electrolysis

Abstract

The decreasing quality of the input materials in copper recycling leads to a higher content of
impurities in the anode copper. Therefore an improvement of the pyrometallurgical refining
process is necessary to produce high quality anodes for the copper refining electrolysis. In order
to improve the metal/slag reactions as well as the volatilisation by selective oxidation in the
anode furnace, the behaviour of the most important accompanying elements (e.g. nickel, tin,
lead, zinc etc.) at different reaction conditions has to be investigated. This requires knowledge
about thermodynamic conditions like the reaction order and the activity coefficient at the
copper refining process. Additionally the interactions between different elements, but especially
those for nickel, have been investigated as a function of the temperature, the content of the
elements and the slag composition. These investigations were done at the Christian Doppler
Laboratory for Secondary Metallurgy of Nonferrous Metals.

Introduction

The raw materials for copper winning contain besides copper also numerous other elements like
nickel, lead, tin, zinc and iron. During the refining procedure of the copper these elements are
removed by using different techniques like the selective vaporization and oxidation as well as
the refining electrolysis. Nearly all copper which is won by the pyrometallurgical way (about
85 %) passes through the copper refining electrolysis, even so is most of the secondary copper.
In the electrolysis the impure copper is anodically dissolved and crystallized at the cathode
without impurities. The space time yield (currently about 0.03 t/m3) and the specific energy
consumption (about 0.4 kWh/kg Cu) represent the main key figures of the process. In order to
guarantee an economical process operation it is therefore necessary to optimize those two
operating figures to the highest possible extent. By increasing the current density we face the
problem of anode passivation, so that the electrochemical dissolution nearly stops [1]. The
consequences are a lower electricity yield as well as higher potential drops which in turn result
in an increased specific energy consumption. Due to the necessity of remelting the remaining
anodes a large amount of copper has to be fed again to the anode furnace. The passivation
behavior of the anodes is strongly dependent on their chemical composition, in this context the
contents of accompanying elements like As, Bi, Sb, Pb, O and Ni are of great importance. In
many companies but especially in recycling plants the removal of those elements is very
difficult since the raw material and further also the accompanying elements are more or less
given. To economically process scrap it is often even necessary to feed low grade material [2].
Considering these aspects, there is an absolute necessity to realize further optimizations in the
field of pyrometallurgical refining in the anode furnace. In this context the behavior and
reactions between metal and slag as well as the conditions for a volatilization are of great
importance. This is because those conditions directly influence the composition of the refined
copper and the anodes respectively and as a consequence also the composition of the anode
slimes.
During the converting period of the black copper and during the following pyrometallurgical
refining all base metals as well as a part of the copper are oxidized, so that slags with high
contents in different metal oxides are generated. The latter together with the oxygen potential
strongly influence the liquidus area of the slag. At present these slags are recycled to the shaft
furnace where the accompanying elements either accumulate in the flue dust or are transferred
into the black copper. In order to break up this closed loop of several elements and to discharge
them from the process it should be tried to reduce the metal oxides contained in the anode
furnace- and converter slag. This reduction step is becoming of increasing importance since the
quality of the scrap is continuously decreasing and therefore makes, with respect to the
necessity of unloading the refining electrolysis, a further optimization of the pyrometallurgical
refining absolutely necessary. Additionally it is of special interest, that the slags are very
homogenous and have a low viscosity, so that a high mass transfer, ensuring high reaction rates,
can be guaranteed [3].

Behavior of the accompanying elements in the anode copper

If the accompanying elements aren’t completely removed during the pyrometallurgical refining
different compounds are formed in the anodes, which cause problems at the electrolytic refining
process [4]. The anodes now represent multiphase alloys, since the various elements form solid
solutions as well as intermetallic compounds. Whereas Cu-Ag, Cu-Sb, Pb-Bi and Pb-Sb are
representative binary systems for the solid solutions, Cu-Sb or Cu-Se at a higher contents of Sb
and Se are examples for intermetallic compounds.
In figure 1 the behaviors of the various phases that occur in the anodes of a secondary copper
plant are observable. The framed phases represent products, which can be found in the anode
mud, in the electrolyte or in the cathodes.

Figure 1: Behavior of different phases at the refining electrolysis [4]

If the impurities are phase separated with the copper matrix or in the form of a solid solution or
intermetallic compounds respectively, is of great importance for the qualitative and quantitative
electrochemical dissolving. The mechanically inserted impurities are formed by suspension of
impurity phases in the electrolyte. In figure 2 the characteristics of the anodic dissolving
process in the electrolyte close to the anodes are described schematically. For this special
reasons an optimization of the pyrometallurgical refining has to be one of the main objectives
of further investigations [5].

Figure 2: Schematic description of the electrochemical dissolving of the copper anode at the
refining electrolysis

Thermodynamic fundamentals

Activity

The activity of a metal oxide (aMO) is the driving force for the dissolution of the corresponding
metal in the slag [6]. The activity coefficient is indirectly proportional to the solubility. At low
contents of the metal (M) in the copper and of the metal oxide (MO) in the slag Henry`s law is
valid [7]. The activity coefficient of a metal oxide is a function of temperature, oxygen potential
and slag composition. The influence of the temperature on the activity coefficient is shown in
figure 3.
 18 0,35

16
0,3
14
0,25
12

γ CuO0,5, γ NiO, γ SnO

γ ZnO, γ PbO
10 0,2

8 0,15
6
0,1
4
0,05
2

0 0
1000 1100 1200 T[°C] 1300 1400 1500

CuO0,5 NiO SnO PbO ZnO

Figure 3: Activity coefficient of the metal oxide in a fayalitic slag [6]

Values for the activity coefficient of several metals in liquid copper are summarized in table 1
and shown as a function of temperature in figure 4.

Table I: Activity coefficients in liquid copper

metal RTlnγM0 [cal] γM0 references
Fe(l) 9300-0.41T 15.95(1573K) [4]
Fe 12.6 [5]
Ni(l) 2340 2.11(1573K) [4]
Pb(l) 8620-2.55T 4.37(1573K) [4]
Sn(l) -8900 0.058(1573K) [4]
Zn(l) -5640 0.165(1573K) [4]

35 0,3

30
0,2
25

0,2
γ Fe, γ Ni, γ Pb

20
γ Sn, γ Zn

15
0,1

10
0,1
5

0 0,0
1000 1100 1200 T[°C] 1300 1400 1500
Fe(l) Ni(l) Pb(l) Sn(l) Zn(l)

Figure 4: Activity coefficient of several metals in liquid copper

Distribution coefficient

The distribution coefficient (equation 1) describes the distribution of the accompanying

elements between slag and metal and is therefore an indicator for the efficiency of the metal
extraction [8].
LM =
(% M ) (1)
[% M ]
In the slag the different metals M (e.g. Cu, Ni, Zn, Pb, Sn etc.) exist in the form of oxides, as
demonstrated by the reaction in equation 2. Equation 3 shows the corresponding equilibrium
constant to this reaction.

[M ] + n O 2 (g ) ↔ (MOn ) (2)
2

aMOn
K MOn = n
(3)
aM ⋅ pO22

The distribution coefficient is directly proportional to pO2n/2 if the behavior of the metal M in
the copper and of the metal oxide MO in the slag obeys Henry`s law.

Accompanying elements of copper

The impurities that are fed with the input materials (scrap, sludge, dust, slag etc.) have to be
removed from the liquid copper during smelting by converting and refining [9].
Among the accompanying elements it has to be differentiated [10] between:
• Base metals with a high enthalpy of formation of the oxide, that have to be transferred into
the slag in several process steps (e.g. Fe, Al, Si, P, Zn Sn and Be).
• Elements that are partly reduced with the copper and therefore have to be separated by
accumulation in semi products or by the electrolytical refining process. Such metals are
beside the noble metals elements like As, Sb, Ni and Pb that have a enthalpy of formation of
the oxide which is similar to that of copper.

It should be ensured that the accompanying elements are not distributed in several phases
(metal, slag, dust) but accumulate in just one of those phases [11].
During the smelting process most impurities are at least partly transferred into the slag or the
dust. As an exception merely Ni and the precious metals (Au, Ag, platinum group metals), with
their noble character avoiding oxidation, are solved in the copper and so form the anode mud in
the refining electrolysis.
During converting, the base accompanying elements are either volatilized or transferred into the
slag by selective oxidation. The formed converter slag is then recycled to the shaft furnace
again. Due to this practice all accompanying elements are either reinserted or pass on to further
process steps. Since also the off gas is cleaned there are hardly any losses of elements [10].

The accompanying elements can be removed from the copper by injection of air on the one
hand or by the use of oxidizing slags on the other hand [11]. If air injection is used the
oxidizing behavior of the elements depends on the gas flow rate and the temperature.
After the oxidation of Zn and Sn the oxygen content of the liquid copper increases continuously
until a critical value is reached, that also allows the oxidation of lead.
In a liquid Cu-Pb-O metal phase the oxidation rate of lead is lower than in a Cu-Zn-Sn-Pb-O
phase, indicating that the activity coefficient of lead oxide (γPbO) has a lower value in slags
where Cu2O coexists with ZnO and SnO [11].
Even though by increasing the flow rate higher oxidation rates of the accompanying elements
can be realized, this practice generates larger amounts of slag and therefore causes higher
copper losses [11]. The oxygen content of the liquid copper increases rapidly with temperature.
Whereas the oxidation reactions of Zn and Sn are exothermic and therefore an increased
temperature decreases the oxidation rates of those elements, the oxidation rate of Pb is hardly
dependent on temperature [11].
In this context the most important aim of the pyrometallurgical refining process is to produce a
slag with a low copper content and a high absorption potential for the accompanying element
oxides. In order to be able to describe the behavior of each element it is necessary to determine
the activity and the distribution coefficient of the corresponding elements in thermodynamic
experiments and calculations.

Copper losses in the slag

In the slag copper exists in form of enclosed metal drops, Cu0, as well as in the solved form of
Cu+.

Enclosed metallic copper

It are physical slag properties like density, surface tension and viscosity that determine the
amount of enclosed copper. These copper losses can either be decreased, by giving the metallic
drops enough time for sedimentation or by lowering the slag-viscosity by reducing the content
of magnetite in the slag. At higher temperatures the influence of the slag melting point and the
slag-viscosity vanishes certainly, but fuel consumption and as a consequence also process costs
increase. From this point of view the overall objective of the investigations should be to
guarantee a low slag-viscosity at lower process temperatures.
The sedimentation rate of the enclosed metal particles can be estimated by Stoke`s law [12].

2 g ⋅ (ρ D − ρ S ) ⋅ rD2
v= ⋅ (4)
9 µS

v sedimentation velocity [m/s]

g acceleration of gravity [m/s²]
ρD, ρS density of the enclosed particles and of the slag [kg/m³]
rD radius of the enclosed particles [m]
µS viscosity of the slag [kg/m.s]

According to Stoke’s law small metal particles will settle rather slow. By the injection of gas
into the slag/metal system more metal is transported into the slag by the gas bubbles. The rising
gas bubbles are covered with a layer of liquid metal that bursts when the bubbles are entering
the slag. That’s why the amount of enclosed metal increases with the flow rate. By the higher
turbulences the sedimentation of bigger particles is retarded too[12].

Solved oxidic copper

The content of copper oxide in the slag depends first of all on the pO2 but also on the
temperature and the slag composition [13].
Oxidic copper dissolves in the slag according to the following reaction (5).
 1
Cu (l ) + O2 (g ) ↔ CuO0,5 (l ) (5)
4
aCuO0,5 (l )
K= 1
(6)
aCu (l ) ⋅ pO42

The temperature dependence of the equilibrium constant is determined by equation (7) and
graphically shown in figure 5 [14].

7361
ln K = − 2,639 (7)
T

25

20

15
K(CuO0,5)

10

0
1000 1100 1200 1300 1400 1500
T[°C]

Figure 5: Equilibrium constant for the oxidic dissolution of copper as a function of temperature.

Figure 6 shows the correlation between the copper content and the oxygen potential. For the
dissolution of copper in siliceous slags Henry`s law can be applied, whereby the activity
coefficient of CuO0,5 shows marginal dependence of the slag composition. The solubility
decreases with increasing content of SiO2 and CaO. Furthermore also the addition of CaO,
MgO and Al2O3 to SiO2 saturated fayalitic slags decreases the copper solubility[8].
 Figure 6: Solubility of copper in FCS slags as function of pO2 [21] (R and Q represent the slag
composition and the basicity respectively)

Equation (8) results from the validity of Henry`s law and the limited solubility of copper:

(%Cu ) = k ⋅ aCuO 0,5

(8)

The activity coefficient of copper oxide can be calculated according to equation (9):
1
K ⋅ M Cu ⋅ aCu (l ) ⋅ nT ⋅ pO42
(γ CuO0 ,5 )= (%Cu )
(9)

In the system of CaO-FeOx-SiO2 high values of γ CuO0,5 (maximum 13) are achieved at values of
Q between 0.45 to 0.55 and of R of about 0.2 [21]

Total copper losses

The total copper loss depends not only on the copper solubility of the slag but also on the total
slag amount, that is indirect proportional to the iron content of the slag [13]. If copper exists in
oxide form, the copper content in the slag and the total amount of in fayalitic slag dissolved
copper can be reduced by decreasing the content of SiO2.
During melting and refining copper losses can be minimized by:
• Reducing conditions in the melting aggregates (but the formation of solid metallic iron has
to be absolutely avoided)
• An oxidic atmosphere at the refining process, that is as low as possible but high enough to
remove the impurities.
• A slag composition that guarantees a low copper solubility as well as a small amount of
copper inclusions.
 Nickel losses in the slag

As an important alloying element for copper nickel is introduced by feeding secondary material.
Although nickel is oxidized easier than copper it is removed as nickel sulphate in the refining
electrolysis by precipitation from the electrolyte.
The nickel containing slags from the converter and the anode furnace are fed to the shaft
furnace. The losses of nickel through the shaft furnace slag are with 0.5% rather low. The
highest nickel contents can be found in the black copper and the converter slag [10].
The oxidic dissolution of Ni in the slag takes place according to the following reaction:

aNiO (l )
K= 1
(10)
aNi (l ) ⋅ pO22
1
Ni (l ) + O2 ( g ) ↔ NiO (l ) (11)
2

Experimental

The number of experiments were calculated by the software MODDE 7.0. Furthermore a
stoichiometric amount of reducing agent was used for the reactions. For the calculation of this
amount it was assumed that all non ferrous metal oxides (CuO0.5, NiO, PbO, SnO, ZnO) in the
slag are reduced to metal. Although iron should remain in the slag, it should be reduced from
FeO1.5 to FeO. The addition of iron was necessary for the exact ratio of Fe/SiO2. Additionally
iron served as reducing agent for the oxides of Zn, Pb, Sn, Ni and Cu whereas the iron itself is
oxidized to FeO, which is produced also by the reduction of FeO1.5. The ratio of Fe/SiO2 and of
CaO/SiO2 were the investigated parameters in these experiments. The composition of the slag
for the investigations is given in table II.

Table II: Composition of the anode furnace slag

[%] [%]
Cu 28.500 As 0.016
Fe 6.9 Ag 0.035
Pb 4.9 SiO2 11.0
Sn 3.1 Al2O3 4.5
Ni 2.6 MgO 1.8
Sb 0.2 CaO 2.0

The investigations were carried out in an induction furnace. For the experiments a sintered
alumina crucible with a height of 38 mm, a diameter of 32 mm and a wall thickness of 1 mm
was used. The crucible was fed with the anode furnace slag (table II) and several additions
(SiO2, CaO, Al2O3, MgO, Graphite). The reaction time for each experiment was 4 hours.
After 4 hours the thermocouple was removed and the crucible was cooled down in the furnace.
To investigate the viscosity of the slag the temperature was kept constant at 1300°C during the
experiment. It turned out that a higher basicity increases the viscosity of the slag at this
temperature, which in turn leads to a higher metal content in the slag.
The experiments mainly focused on the behavior of Ni, which can strongly influence the
electrolysis, and Cu. Since the Ni distribution in the anodes depends on the solidification
conditions, the Ni content fairly varies at the cross section of the anodes, which then causes
different conditions during the electrolysis. The distribution of the element Ni along the cross
section of an anode as a function of the solidification conditions is shown in figure 7. As it can
be seen it is very important, if the form of the primary copper crystals is either dendritic (figure
8) or globulitic (figure 9).
1,13

1,11

1,09

1,07

nickel in % spheriodal
1,05
dendritic

1,03

1,01

0,99

0,97
0 0,5 1 1,5 2
cross section of the anode in cm

Figure 7: Ni distribution along the cross-section of the anode as a function of the solidification
conditions

Figure 8: Dendritic microstructure of anode copper

Figure 9: globulitic microstructure of anode copper

The copper and nickel content of the slag as a function of the CaO/SiO2 und Fe/SiO2 ratio is
given in figure 10. It has to be considered, that these investigations have been carried out at a
temperature of 1300 °C. Therefore the viscosity of the slag influence the reaction and the
sedimentation of the liquid metal. In industrial operation these circumstance have to be
considered at higher basicities to get a slag with a low viscosity.

Figure 10: Cu and Ni content as a function of the CaO/SiO2 and Fe/SiO2 ratio at a temperature
of 1300 °C and a stoichiometric amount of the reduction agent.

The copper and nickel content of the slag under the investigated conditions can be calculated
according to equations (12) and (13):

Fe CaO Fe CaO
(%Cu ) = 16.0670 − 6.3432 ⋅ − 3.2606 ⋅ + 4.7056 ⋅ ⋅ (12)
SiO2 SiO2 SiO2 SiO2

(% Ni ) = 2.3085 − 1.8055 ⋅ Fe + 0.2773 ⋅ CaO + 0.3278 ⋅ Fe ⋅ CaO (13)

SiO2 SiO2 SiO2 SiO2

Further experiments at higher temperatures (1400 °C) have shown, that the content of the
elements but especially that of copper decreases significantly. Due to this fact in future
investigations also the temperature will be a parameter that has to be varied. Although this
practice will increase energy costs, it is justified by an increased process yield and an improved
slagging of the accompanying elements.

Conclusion

Due to the lower quality of the input materials and the necessity for a continuous increase of the
space time yield the pyrometallurgical refining step in the primary and secondary copper
industry has to be optimized. The changed process conditions also change the behavior of the
accompanying elements at selective oxidation and evaporation reactions. For the description of
the process conditions and for further investigations knowledge about parameters like viscosity,
temperature and basicity of the slag is essential. The investigations showed, that the
temperature is one of the most important parameters for influencing the slag viscosity.
 The continuous improvement of the pyrometallurgical refining process in copper secondary
metallurgy is of great importance for an unproblematic operation of the final refining
electrolysis. The different elements strongly influence the refining electrolysis where they cause
e.g. passivation of the anodes which results in a lower yield of the whole process. Further
investigations should enable the production of anode copper, which can be inserted into the
refining electrolysis without any restrictions, although low quality scrap is used.

References

1. Jin, Sh. E. Ghali and A. Adnot: XAES study on the passivation of copper anodes in
H2SO4-CuSO4 solution. Proc. Emerging Separation Technologies for Metals and Fuels,
TMS, 1993, 169 - 182
2. Gumowska, W. and I. Sedzimir: Influence of the lead and oxygen content on the
passivation of anodes in the process of copper electro-refining. Hydrometallurgy 28
(1992), 237 - 252.
3. Bach, X., A.C. Feneau und B. Gongarinoff: Anodenprobleme bei der elektrolytischen
Kupferraffination. Erzmetall (1969), Beiheft, B120 - B127
4. Buhrig, E., K. Hein und H. Baum: Verteilung von Fremdelementen bei der
Kristallisation von Kupfer. Metall 33 (1979), 592 - 596
5. Lange, H.-J., K. Hein und D. Schab: Anodenprozesse bei der Raffinationselektrolyse.
Freiberger Forschungshefte (1977), 29 - 49
6. Degterov S. A. und A. D. Pelton: A thermodynamic database for copper smelting and
converting. Metallurgical and Materials Transactions B, Vol.30B, August 1999, 661-
669
7. Krajewski W. und Krüger J.: Schlacken beim Schmelzen von Kupfer und Kupferstein.
Schlacken in der Metallurgie, Hrsg. Koch K., Düsseldorf, Verlag Stahleisen, 1984
8. Kim H. G. und H. Y. Sohn: Effects of CaO, Al2O3 and MgO additions on the copper
solubility, ferric/ferrous ratio and minor-element behavior of iron-silicate slags.
Metallurgical and Materials Transactions B, Vol.29B, June 1998, 583-590
9. Biswas A. K. und W. G. Davenport: Extractive Metallurgy of Copper, 3rd edition. 1994,
Pergamon Press, ISBN 0-08-042124-5
10. Hanusch K. und H. Bussmann: Behavior and removal of associated metals in the
secondary metallurgy of copper. Third International Symposium on Recycling of
Materials and Engineered Materials, The Minerals, Metals and Materials Society, 1995,
171-188
11. Nakashima K., K. Yamamoto, E. Shibata, H. Tahori und K. Mori: Oxidation rate of
impurities in liquid copper by gas and slags. Second International Conference on
Processing Materials for Properties, San Francisco, November 2000
12. Poggi D., R. Minto und W. G. Davenport: Mechanisms of metal entrapment in slags.
JOM, Vol.21, November 1969, 40-45
13. Reddy R.G. und C.C. Acholonu: Activity coefficient of CuO0,5 in alumina saturated iron
silicate slags. Metallurgical and Materials Transactions B, Vol.15B, December 1984,
345-349
14. Yazawa A., Y. Takeda und S. Nakazawa: Ferrous calcium silicate slag to be used for
copper smelting and converting. Copper 99, Vol.VI., The Minerals, Metals and
Materials Society, 1999, 587-599
15. Vartiainen A. und M. Kytö: Olivine slags - the ultimate solution to low copper slags?.
Scandinavian Journal of Metallurgy, Vol.31, Issue 5, October 2002

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