Physical chemistry of copper smelting slags

and copper losses at the Paipote smelter

Part 1 – Thermodynamic modelling
N. Cardona*1, P. Coursol2, P. J. Mackey3 and R. Parra1
Thermodynamic modelling was used in conjunction with the results of a sampling campaign to
investigate the liquidus temperature and the copper losses in slag from the Teniente converter
(TC) and from the slag cleaning electrical furnace (EF) at the Paipote smelter in Chile. The present
paper (Part 1) describes the smelter flow sheet and discusses the results of thermodynamic
calculations. The impact of process parameters such as the Fe/SiO2 ratio, the minor oxide levels
in slag (CaO, Al2O3, MgO and ZnO), the sulphur dioxide partial pressure p(SO2), temperature and
matte composition were examined with respect to the slag liquidus and copper level in the slags.
The operating window of the Paipote TC to produce good slag quality correspond to a vessel
temperature between 1200 and 1250uC, and an Fe/SiO2 ratio in slag between 1?5 and 1?8 when
the iron content of the matte is in the range of 3–6 wt-%Fe (or 76?5–73?2 wt-%Cu). Under these
conditions, the TC slag (average total copper in slag ,6 wt-%Cu) contains less than 1 wt-%Cu as
soluble copper with approximately 90% of total copper in the slag is entrained matte; it is noted
that 0–10 wt-% solid magnetite is in suspension in the slag. As regards the EF, over the nominal
temperature range from 1200 and 1270uC, the EF slag is fully molten over a wide range of Fe/SiO2
ratios for slag containing the present level of minor oxides. An operating temperature of about
1225uC and a Fe/SiO2 ratio in the range 1?4–1?8 are considered good conditions for optimum EF
performance. The EF slag typically averages 0?82 wt-%Cu and it was estimated that under
present conditions, about 50% of this copper was as soluble copper with the balance as
entrained matte.

La modélisation thermodynamique a été utilisée en conjonction avec les résultats d’une

campagne d’échantillonnage pour examiner la température de liquidus et les pertes en cuivre
dans le laitier du convertisseur de Teniente (TC) et du four électrique (EF) de nettoyage du laitier
de la fonderie de Paipote au Chili. Le présent article (1iere Partie) décrit le schéma du procédé de
la fonderie et discute les résultats des calculs thermodynamiques. On a examiné l’impact des
paramètres du procédé, comme le rapport Fe/SiO2 dans le laitier, le niveau de CaO, Al2O3, MgO
et ZnO dans le laitier, la pression partielle du dioxyde de soufre p(SO2), la température et la
composition de la matte, sur le lı́quidus du laitier et sur le niveau de cuivre soluble dans le laitier.
La fenêtre d’opération du TC de Paipote permettant de produire une bonne qualité de laitier
correspond à une température entre 1200 et 1250C et à un rapport Fe/SiO2 dans le laitier entre
1?5–1?8 lorsque la teneur en fer de la matte est dans la gamme de 3 à 6% en poids (ou 76?5 à

1
Department of Metallurgical Engineering, Universidad de Concepción, CP 4070371, Chile
2
Coursol Consultants, 485 Av. Humphrey Apt. 3, Sept-Iles, Que. G4R-2G4, Canada
3
P.J. Mackey Technology Inc., 295 Kirkland Blvd, Kirkland, Que. H9J-1P7, Canada

*Corresponding author, email nubiacardonavalencia@gmail.com

ß 2011 Canadian Institute of Mining, Metallurgy and Petroleum

Published by Maney on behalf of the Institute
Received 27 November 2010; accepted 1 June 2011
318 DOI 10.1179/000844311X13112418194761 Canadian Metallurgical Quarterly 2011 VOL 50 NO 4
 Cardona et al. Copper smelting slags and copper losses at Paipote smelter: Part 1

73?2%Cu). Sous ces conditions, le laitier du TC contenant un cuivre moyen total d’environ 6% contient
moins que 1% en poids de Cu sous forme de cuivre soluble. Ce rapport permet de déduire
qu’approximativement 90% du cuivre total dans le laitier est sous forme de matte entraı̂née. On note
également qu’entre 0 et 10% en poids de magnétite solide est en suspension dans le laitier, dans les
conditions normales d’opération. En ce qui concerne le EF, le laitier est complètement fondu sur une
large gamme de rapports de Fe/SiO2 pour une température comprise entre 1200 à 1270uC en
considérant les niveaux actuels en CaO, Al2O3, MgO et ZnO dans le laitier. Une température de
fonctionnement d’environ 1225C et un rapport Fe/SiO2 dans une gamme de 1?4 à 1?8 sont considérés
comme des bonnes conditions pour le rendement optimal du EF. Le laitier du EF contient typiquement
une moyenne de 0?82% Cu et l’on a estimé que sous les conditions présentes, environ 50% de ce
cuivre se trouvait sous la forme de cuivre soluble, le reste étant sous la forme de matte entraı̂née.
Keywords: Paipote smelter, copper smelting, slag cleaning, copper losses, thermodynamics

Introduction of 92 000 t/year of copper anodes. Figure 1 presents a

The Paipote smelter also known as the Hernan Videla
Lira smelter is part of ENAMI (Empresa Nacional de
Minerı́a) in Chile. Located 8 km southeast of the city of
Copiapó, the plant’s mandate upon commissioning in
1952 was to treat concentrates from small and medium
size mining companies of the Atacama region. The plant
continues to handle such feed, covering a wide range
of copper, gold and silver concentrates, copper pre-
cipitates from hydrometallurgical operations and direct
smelting high grade ores. With such a wide range of feed
materials, the smelter has a well developed procedure for
planning and controlling the feed blend so as to provide
as uniform a charge as possible to the Teniente converter
(TC) smelting furnace. In spite of this, it is noted that
even small unexpected changes in the feed material can
affect the slag quality, copper losses and the deportment
of minor elements.
It is now recognised that copper losses in smelting slags
are made up of chemically soluble copper and as mecha-
nically entrained copper (as matte or a metallic phase).1
The chemically soluble copper is in the form of cationic
copper (Cuz)2,3 and thus dependent on the partial pressure
of oxygen p(O2),4,5 the matte composition1,2,5 and the slag
composition.6,7 The mechanical loss component8–10
mainly depends on a number of physical factors includ-
ing the density of matte and slag, bath fluid dynamics and
slag viscosity.
In the present study, thermodynamic modelling was
performed using the FactSage 6?1 software11–14 to evaluate
the chemistry and copper losses in TC and electric furnace
(EF) slags at the Paipote smelter. The main parameters
evaluated were: the Fe/SiO2 ratio in slag, the matte
composition, the partial pressure of SO2 p(SO2) and the
minor oxide levels in slag (CaO, MgO, Al2O3 and ZnO).
The liquidus temperature and the proportion of solid
phases present were calculated under smelting conditions.
The copper solubility and the slag sulphide capacity were
obtained from the equilibrium calculations.
Description of smelter flow sheet
The Paipote smelter in Chile has a nominal capacity of
340 000 t/year of dry concentrate producing an average
simplified flow diagram of the plant. The TC operates as
the main smelting unit with slag treated in an EF for
copper recovery. Operating with oxygen enrich-
ed air, the TC typically treats 1000 t/day of copper
concentrate plus solid reverts in a range of 40–100 t/day,
with an average of 80 t/day of silica flux. Matte at
,74?5 wt-%Cu and 4 wt-%Fe is transferred to Peirce–
Smith converters, with the resulting blister refined in the
anode furnace before anode casting. The anodes are
normally shipped to Codelco’s las Ventanas plant for
electrorefining. After skimming, Peirce–Smith converter
slag is cast and later crushed and returned to the TC
and/or the EF as internal reverts; the same procedure is
followed for anode furnace slag. Upon tapping, the TC
slag is transferred by ladle to the EF. The key operating
parameters of the TC and EF units are given in Table 1.
The Paipote EF can treat about 800 t/day of liquid TC
slag and can handle up to 150 t/day of solid reverts. The
added coarse sized coke serves to reduce magnetite (as solid
and liquid) in the slag. The produced matte is tapped and
returned by ladle to the TC, while EF slag is transported to
the slag dump. Typical matte and slag compositions for
both the TC and EF furnaces are given in Table 2.
At the EF, the metallurgical coke premixed with reverts
is continuously introduced as solid charge through drop
holes in the furnace roof. It has been found that adding
coke this way improves the reduction efficiency by
minimising the tendency for the coke to burn at the slag
surface. It has also been found that optimum conditions
in the EF include maintaining a good slag bath and
minimum matte levels (by proper scheduling), and
regulating correct coke/revert additions. Overreduction
of slag needs to be controlled as this can lead to the
formation of excessive amounts of metallic copper at the
furnace bottom15; this is undesirable as the copper layer
tends to retain metallic impurities such as As, Sb and
Bi,6,16 thus affecting plant anode quality when such
copper is recycled back to the smelter.
As would be expected, the performance of the EF for
slag cleaning depends on both the EF operation itself and
also the TC slag chemistry. The present paper is intended
to provide both an understanding and optimisation of the
slag chemistry and copper losses in slag at Paipote.

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Cardona et al. Copper smelting slags and copper losses at Paipote smelter: Part 1

1 Simplified flow diagram for Paipote smelter (TC: Teniente converter; EF: electric furnace; PSC: Peirce–Smith converter;
AF: anode furnace)

Methodology calculations, one parameter was varied at a time in

In mapping the process chemistry, the number of
degrees of freedom were fixed for the TC and EF
according to the Gibbs phase rule4 using industrial
parameters (such as gas, slag, matte compositions, etc)
to define the reference values (refer to Table 2). In the
order to evaluate its impact on the slag liquidus, the
copper solubility in slag and magnetite levels. It is
noted that minor elements, such as Pb, As, Sb, Bi, Cr
and Ni, are at very low levels in Paipote matte and slag,
and because of this were neglected in the present
calculations.

Table 1 Key operational date for TC and EF (Paipote smelter 2008–2009)

Furnace Key operating parameters Range

Teniente converter Dry concentrate feed/t/day 850–1100 (avg. 1000)

Solid reverts charge/t/day 40–100 (avg. 80)
Oxygen enrichment/% 36–39 (avg. 38)
Specific blowing rate/Nm3 per tonne of concentrate 380–520
Slag production/t/day 530–640
Slag temperature/uC 1180–1250 (avg. 1220)
Fe/SiO2 in slag/wt-%/wt-% 1.4–1.8 (avg. 1.65)
Fe3O4 in slag (Satmagan)/wt-% 19.3–24.5 (avg. 21.4)
Matte production/t/day 250–320
Matte temperature/uC 1080–1150
Matte grade/wt-%Cu 72–76 (avg. 74.5)
Electric furnace Solids reverts charge/t/day 90–135
Coke charge/kg/tonne of slagzreverts 12–14
Energy consumption/kWh/tonne of solidszslag 134–175
Södeberg electrodes 3 of 0.89 m diameter
Slag production/t/day 520–610
Slag temperature/uC 1180–1270 (avg. 1220)
Fe/SiO2 in slag/wt-%/wt-% 1.4–2.1 (avg. 1.6)
Fe3O4 in slag (Satmagan)/wt-% 4.2–9.1 (avg. 6.9)
Matte production/t/day 90–120
Matte temperature/uC 1080–1120
Matte grade/wt-%Cu 69.5–74.9 (avg. 72.4)

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 Cardona et al. Copper smelting slags and copper losses at Paipote smelter: Part 1

Table 2 Slag and matte compositions for the TC and for the EF Paipote’s averages for 2008–2009

Furnace Oxide or element Teniente converter Electric furnace

Slag composition/wt-% FeO 54.6 56.9

SiO2 25.7 27.9
Al2O3 3.45 3.65
ZnO 1.85 1.8
CaO 0.7 0.85
MgO 0.73 0.83
PbO 0.18 0.1
Cu 6.17 0.82
S 1.59 0.6
Others 0.1* 0.25{
Fe/SiO2 1.65 1.6
Matte composition/wt-% Cu 74.6 72.4
Fe 4.1 6.7
S 20.9 20.9
Zn 0.19 0.25
Pb 0.13 0.21
As 0.05 0.13
Sb 0.02 0.05
Gas p(SO2)/atm 0.25 …
*Totals: As and Sb.
{Totals: As, Sb and Cr2O3.

The liquidus calculations were performed using the
FactSageTM databases13 and the modified quasichemical
model11,12 for matte, copper and slag liquid solutions.17–19
It considers the copper solubility in slag as Cuz and the
related parameters are based mainly on data from
‘sulphur free’ experiments (some information included
data obtained under matte–slag equilibrium conditions17).
The solubility of sulphur in the present multicomponent
slag was calculated using the Reddy–Blander model as
modified by Pelton et. al.20
In order to establish the slag liquidus lines delimitat-
ing the operating windows for each furnace, all possible
solid phases in the particular system were consider-
ed: spinel ([Fe2z,Zn2z,Mg2z]{Fe3z,Al3z}2O4), olivine
([Mg2z,Fe2z,Zn2z,Ca2z]2SiO4), pyroxene ([Fe2z,Mg2z,
Ca2z]SiO3) and tridymite (SiO2); a full description of the
chemistry of the solid solutions has been provided by Jung
et al.21,22 The thermodynamic properties of tridymite (pure
SiO2) were taken from the FactSage database.
The following parameters for calculations on the TC
were fixed according to the current operational conditions
and slag composition: [Fe]matte, [Cu]matte, [Fe/SiO2]slag,
[Al2O3]slag, [MgO]slag, [CaO]slag, [ZnO]slag, p(SO2), the
total pressure (1 atm) and the temperature.
As regards the EF, the chemical activities of Cu2S, FeS
and Fe were fixed according to the matte composition
(%Cu, %Fe and %S). It can be determined from plant
data that the Paipote EF matte is deficient in sulphur
(that is, contains less sulphur than that required to fully
account for the metals as stoichiometric sulphides). In the
present study, the sulphur deficiency was approximated
to be 0?25 wt-%, based on the average Cu, Fe and S levels
in matte as given in Table 2, and with an estimated
oxygen level of 0?35 wt-% oxygen.17,23 Equation (1) was
then used to calculate the molar sulphur deficiency (this
was then converted to a wt-% term).
XCu
Sulphur deficiency (mol)~Xs { {XFe zXo (1)
2
The sulphur deficiency value was assumed to be constant
over the range of matte grades considered. The other
degrees of freedom were fixed according to the Paipote
EF slag composition ([Fe/SiO2]slag, [Al2O3]slag, [MgO]slag,
[CaO]slag and [ZnO]slag), the operating temperature and
total gas pressure (1 atm).
Results and discussion
Impact of Fe/SiO2 ratio on TC slag liquidus
During FeS oxidation in the TC, the resulting local
equilibrium with the matte and slag could be represented
by reaction (2)
3(FeS)matte z5O2 ~(Fe3 O4 )slag z3SO2 (2)
Magnetite in slag is controlled with silica flux according
to reaction (3)
(Fe3 O4 )slag z2SiO2 ~(Fe2 SiO4 )slag z3=2O2 (3)
Maintaining the correct Fe/SiO2 ratio in slag is thus
quite important for the production of a good quality
slag. Running with more silica than required is undesir-
able as in addition to requiring more smelting heat, it
can also lead to slag having a higher viscosity. Figure 2
illustrates the effect of the Fe/SiO2 ratio of the TC slag
liquidus for conditions when the minor oxide compo-
nents, the iron level in matte and the p(SO2) are fixed
(Table 2). It is noted that the resulting partial pressure
of oxygen p(O2) under such conditions was calculated as
1028 atm.
Bath smelting processes such as the TC or the
Noranda reactor process usually operate at spinel
saturation (magnetite saturation).24,25 The ranges of
normal operating conditions (Fe/SiO2 ratio and tem-
perature) are shown by the dotted square in Fig. 2; the
average condition for Paipote are indicated by the ‘star’
point. It is seen that the slag is at about 20uC below the
calculated slag liquidus. The spinel saturation line can be

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Cardona et al. Copper smelting slags and copper losses at Paipote smelter: Part 1
2 Impact of Fe/SiO2 ratio on calculated TC slag liquidus:
dotted square represents current operational window;
star symbol represents average operational point
(p(SO2)50?25 atm, [Fe]matte54 wt-%, [Cu]matte575?0 wt-%,
([Al2O3]slag54?0 wt-%, [ZnO]slag52?1 wt-%, [MgO]slag50?8
wt-%, [CaO]slag50?8 wt-%)
seen to also be quite sensitive to the Fe/SiO2 ratio, with
the liquidus increasing by y14uC per increment of 0?1 in
the Fe/SiO2 ratio.
Impact of minor oxides components (CaO,
Al2O3, MgO and ZnO) on TC slag liquidus
Minor oxides such as CaO, Al2O3, MgO and ZnO enter
in the slag via the concentrate feed, flux, from coal ash
and from refractory dissolution. Such oxides can then
affect the slag liquidus temperature depending on the
slag composition and level of oxidation.26–30 Figure 3
illustrates the effect of the Fe/SiO2 ratio and minor oxide
components on the TC slag liquidus when the iron level
in matte and the p(SO2) are held constant.
According to the equilibrium calculations, CaO,
Al2O3, MgO and ZnO all increase the slag liquidus
under spinel saturation. The oxides CaO and the Al2O3
increase the liquidus by approximately 12 and 10uC per
wt-% of oxide respectively; the oxides MgO and the ZnO
similarly affect the liquidus but to a lesser degree, unless
the level of MgO is above about 4%. The above
behaviour of these minor oxides (Al2O3, MgO and
CaO) is in general agreement with that reported by
Kongoli and Yazawa27 and Henao et al.28
Impact of p(SO2) and iron level in matte on on
TC slag liquidus
The slag liquidus increases with p(SO2) and with a lower
content of Fe in matte (or higher matte grade); these two
parameters are influenced by the oxygen potential;24,25
thus, a high oxygen potential can raise the liquidus at
spinel saturation.27 The effect of p(SO2) and FeS activity
on the spinel liquidus can be explained by the
equilibrium between the matte and the slag containing
magnetite (as Fe2z and Fe3z cations) in reaction (4)
322 Canadian Metallurgical Quarterly 2011 VOL 50 NO
(FeS)matte z3(Fe3 O4 )slag ~(FeO)slag zSO2 (4)
 1=3  
1 pSO2
ðFe3 O4 Þslag ~ ðFeOÞslag (5)
K4 a(FeS)
When the Fe/SiO2 ratio and the slag composition are
fixed, the chemical activity of FeO is therefore also fixed.
In this case, it can be seen that the magnetite activity in
slag in equation (5) is related to the p(SO2) and to the
%Fe in matte which in effect fixes the a(FeS). It can be
seen that a lower p(SO2) level and a higher %Fe in matte
(lower matte grade) will reduce the Fe3O4 activity, and
hence lower the slag liquidus at magnetite saturation.
As seen in Fig. 4a, the slag liquidus at the typical Fe/
SiO2 ratio of 1?7 increases by 20uC as the p(SO2) is
increased from 0?1 to 0?4. However, for the present
conditions at Paipote, the p(SO2) is maintained at steady
between 0?2 and 0?3 atm (since variations in percentage
of oxygen enrichment are small), leading to small
variations in liquidus temperature of ¡4uC; hence, at
Paipote, this factor being essentially constant does not
contribute to changes in the slag melting temperature.
Figure 4b shows the impact of the %Fe in matte on
the slag liquidus. At Paipote, the iron content of the
matte can vary between 3 and 7 wt-%, leading to
significant liquidus variations (y15uC). The TC oper-
ates best at a steady blowing rate and matte grade and
under such conditions, maintaining a correspondingly
constant slag temperature and a uniform Fe/SiO2 ratio
in slag are then the key in maintaining good slag quality.
Solids fraction in TC slag
As shown above, the Paipote TC operates at an average
temperature just below the slag liquidus; this implies
that some solid magnetite would be in suspension in the
liquid slag. Such a condition advantageously allows for
a protective solid layer to build up on the refractory
face; on the other hand, an excessive amount of such
solid would rapidly increase the slag viscosity,31 hinder-
ing good matte–slag separation thereby increasing the
amount of entrained matte in the slag.
Figure 5 shows the effect of the Fe/SiO2 ratio and of
the iron level in matte respectively on the percentage of
solid spinel formed in the slag (essentially as magnetite)
within the normal temperature range of the TC
operation. As shown in Fig. 5a, solid spinel in slag is
estimated to occur at 1180uC when the Fe/SiO2 ratio is
above 1?3. At the average operating temperature of
1220uC, solid precipitation begins at an Fe/SiO2 ratio of
about 1?5, while the slag would be fully liquid with the
Fe/SiO2 ratio up to 1?8 at 1250uC; however, under the
latter conditions, there would be no protective refractory
layer formed. From the results shown on Fig. 5b and
from industrial experience, it is recognised that relatively
small variations in the %Fe level in matte can sig-
nificantly disturb the process chemistry of the TC.
At the target matte grade range at the Paipote smelter
(74–75 wt-%Cu or 4?5–3?5 wt-%Fe), with the Fe/SiO2
ratio of 1?7 and a temperature of 1220uC, it was
estimated that the slag would contain y6 wt-% solids
(essentially as magnetite); this is illustrated by the ‘star’
4
 Cardona et al. Copper smelting slags and copper losses at Paipote smelter: Part 1

3 Calculated TC slag liquidus (p(SO2)50?25 atm, [Fe]matte54 wt-% and [Cu]matte575?0 wt-%): LzTr, liquid saturated with
tridymite; LzOl, liquid saturated with olivine. (a) impact of Al2O3 ([ZnO]slag52?1 wt-%, [MgO]slag50?8 wt-%,
[CaO]slag50?8 wt-%); (b) impact of CaO ([Al2O3]slag54?0 wt-%, [MgO]slag50?8 wt-%, [ZnO]slag52?1 wt-%); (c) impact of
MgO ([Al2O3]slag54?0 wt-%, [CaO]slag50?8 wt-%, [ZnO]slag52?1 wt-%); (d) impact of ZnO ([Al2O3]slag54?0 wt-%,
[MgO]slag50?8 wt-%, [CaO]slag50?8 wt-%)

point in Fig. 5. The calculated total magnetite content of of total magnetite compares well with reported plant
the slag including the above solid component plus the data for Paipote TC slag of between 18 and 23
soluble magnetite was estimated at y20 wt-%. This level wt-%Fe3O4.15,32 It is noted that the above plant

4 Calculated TC slag lı́quidus (p(SO2)50?25 atm. ([Al2O3]slag54?0wt., [ZnO]slag52?1wt.%, [MgO]slag50?8wt.%, [CaO]slag50?8wt.%).

(a) Impact of p(SO2) at Fe/SiO251?7. (b) Impact of the iron level in matte ( [Fe]matte )

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Cardona et al. Copper smelting slags and copper losses at Paipote smelter: Part 1

5 Calculated solid fraction in TC slag (p(SO2) 50?25 atm, [Al2O3]slag54?0wt.%, [ZnO]slag52?1wt.%, [MgO]slag50?8wt.%,
[CaO]slag50?8wt.%, Fe/SiO251?7), the star symbol represents the average operational point. (a) Impact of the Fe/SiO2
ratio at [Fe]matte54?0wt.%, and [Cu]matte574?8wt. (b) Impact of the [Fe]matte at T51220uC

magnetite data were obtained at Paipote using the
Satmagan instrument.33
Copper solubility in TC liquid slag
Figure 6 shows the effect of temperature, Fe/SiO2 ratio
and %Fe in matte on the soluble copper in slag when the
minor oxide levels are fixed at the average values.
According to Fig. 6a, the copper level in the slag
(considered as soluble Cu2O) is between 0?53 and
0?63 wt-%Cu at the current operating conditions. Both
the Fe/SiO2 ratio and temperature are seen to have only
a small influence on the copper solubility in slag at a
constant matte grade.
Based on the present calculations, the proportion of
copper as soluble copper in slag was estimated to be less
than 10 wt-% of the total measured copper in Paipote
TC slag, with the balance present as entrained matte. As
shown in Fig. 6b, the level of soluble copper in slag
increases rapidly when there is less than about 3?5
wt-%Fe in matte (,75?5 wt-%Cu). Thus, in changing
from 3?5 wt-%Fe in matte to 2 wt-%Fe, the soluble
copper increases from 0?7 wt-% to nearly 1 wt-%Cu.
It is noted that for the present average Fe level in TC
matte (4 wt-%) and with Fe/SiO2 at ,1?7, the soluble
sulphur in slag is approximately 0?2 wt-% (mainly as
FeS). This level is consistent with reported data for
similar operations.5,24 The above level corresponds to
,13% of the total reported sulphur content (Table 2). It
is noted that most of the reported sulphur in slag is
associated with entrained matte. At such low levels of
soluble sulphur in the slag, the oxide dissolution of
copper is expected to be the predominant over the
copper sulphide dissolution.
Impact of Fe/SiO2 ratio and minor oxides (MgO,
Al2O3, CaO and ZnO) on EF slag liquidus
At the Paipote EF, there is no provision to add any flux
for example, to adjust the Fe/SiO2 ratio if required;

6 Copper solubility in TC slag (P(SO2)50?25 atm, [Al2O3]slag54?0wt.%, [ZnO]slag52?1wt.%, [MgO]slag50?8wt.%, [CaO]slag5

0?8wt.%), the star symbol represents the average operational point. (a) Effect of Fe/SiO2 ratio at [Fe]matte54?0wt.%,
[Cu]matte574?8wt.%. (b) Impact of the %Fe in matte at T51250uC

324 Canadian Metallurgical Quarterly 2011 VOL 50 NO 4

 Cardona et al.
7 Impact of Fe/SiO2 ratio on calculated EF slag liquidus:
dotted square represents current operational window; star
symbol represents average operational point ([Fe]matte5
6?5 wt-%, [Cu]matte572?0 wt-%, [S]matte521?5 wt-%, [Al2O3]slag5
4?0 wt-%, [ZnO]slag52?0 wt-%, [MgO]slag50?9 wt-%, [CaO]slag5
0?9 wt-%)
hence, the Fe/SiO2 ratios in the TC and EF slags are
very similar. Figure 7 shows the effect of the Fe/SiO2
ratio on the EF slag liquidus when the minor oxide levels
in slag and the iron level in matte are fixed. Figure 8
shows the impact of MgO, Al2O3, CaO and ZnO on the
EF liquidus temperature over the full range of Fe/SiO2
ratios.
The main solid phase which could precipitate out
under present EF operating conditions is seen to be the
olivine. The liquidus under this condition is only mildly
influenced by the Fe/SiO2 ratio. For a Fe/SiO2 ratio less
than 1?1, the slag readily becomes saturated with
tridymite, and the slag liquidus temperature increases
significantly. According to the present work, the Paipote
EF slag is typically at some 50 to 100uC above the
liquidus temperature, which is considered sufficient to
avoid/control any solid phase precipitation that could
occur; this condition is also effective for matte settling.
The oxide MgO has a significant effect in raising the
olivine liquidus (,25uC/1 wt-%) as shown in Fig. 8a;
higher MgO levels promote a higher concentration of
Mg2SiO4 in the olivine solid solution, and with the
Mg2SiO4 melting point being much higher than that
of Fe2SiO4, the olivine liquidus then raises sharply.
However, it is seen that the slag can contain up to 3
wt-%MgO without increasing the slag liquidus beyond
the normal temperature range. This result is consistent
with data reported by Zhao et al.29
As seen in Fig. 8b, there is a lowering of the slag
temperature corresponding to 7uC for every additional
Al2O3 in the 0–5 wt-% range at the Fe/SiO2 ratio of 1?6.
This is also in agreement with Zhao et al.30 who showed
that under reducing conditions (experiments carried out
at iron saturation), additions of up to 6 wt-%Al2O3
expanded the olivine primary phase field at lower
Copper smelting slags and copper losses at Paipote smelter: Part 1
Fe/SiO2 ratios and decreased the liquidus temperatures.
At higher alumina levels, the slag becomes saturated
with spinel, and the slag liquidus increases rapidly.
The slag liquidus temperature at olivine saturation is
also lowered by CaO additions (,5uC/1 wt-% at a Fe/
SiO2 ratio of 1?6), but the slag becomes saturated with
spinel at Fe/SiO2 ratios greater than 1?6. The behaviour
of CaO, Al2O3 and MgO in EF slag is in agreement
with work reported by Kongoli and Yazawa27 in slag
under reducing conditions: p(O2)51029–10211 atm. Fi-
nally, it can be seen from Fig. 8d that ZnO in slag
increases the slag liquidus by only ,1uC/1 wt-% (at Fe/
SiO2 ratio of 1?6); hence, the impact is quite small.
Impact of iron level in matte on EF slag liquidus
Liquidus calculations were performed on EF slag over a
range of Fe in matte from 1?75 to 16 wt-%Fe (78–60
wt-%Cu) with the results presented in Fig. 9. The impact
of %Fe in matte for levels higher than about 3 wt-% is
negligible; this is in contrast with the situation for TC
slag, where it has a stronger influence on the spinel
liquidus. This is not surprising since changes in the %Fe
in matte involve a change in the oxygen potential in the
system, mostly affecting the Fe2z/Fe3z ratio in slag.
This ratio does not influence the olivine composition (as
olivine contains iron only as Fe2z).
Magnetite solubility in EF liquid slag
As noted above, the added coke in the EF provides
suitable reducing conditions in the furnace to reduce
magnetite and copper in slag. Under certain conditions,
e.g., slag close to the electrode surfaces or at the coke/
slag interface, iron oxide reduction can proceed to the
point where metallic iron can be formed and then may
dissolve in matte. The overall reduction reaction for this
is shown by reaction (6)
a(Fe3 O4 )slag z2C~3(Fe)matte z2CO2 (6)
As noted above, the EF slag is considered to be fully
molten at the present temperature range; this implies
that all the iron (as both Fe3z and Fe2z) is fully
dissolved in the slag. Optical microscopic observations
on solidified slag samples taken at the plant confirm the
absence of solids in the EF slag.32 The equilibrium
between the iron oxides and metallic iron can be
represented by reaction (7)
3(Fe3 O4 )slag z(Fe)matte ~4(FeO)slag (7)
h i4
  a(FeO)
1 slag
aðFe3 O4 Þslag ~ (8)
K6 a(Fe)matte
The magnetite activity (equation (8)) is then related to
the chemical activity of FeO (aFeO) and the %Fe in
matte (which fixes the a(Fe)). The a(FeO) depends
essentially on the Fe/SiO2 ratio. Figure 10 shows the
effect of the Fe/SiO2 ratio and of %Fe in matte on the
soluble magnetite level in the liquid TC slag at 1220uC.
It is seen that the amount of soluble magnetite increases
with the Fe/SiO2 ratio. At iron levels lower than about
Canadian Metallurgical Quarterly 2011 VOL 50 NO 4 325
Cardona et al. Copper smelting slags and copper losses at Paipote smelter: Part 1

8 Calculated EF slag liquidus. ([Fe]mte56?5wt.%, [Cu]mte572?0wt.%, [S]mte521?5wt.%). LzTr: Liquid saturated with Tridymite,
LzSp: Liquid saturated with Spinel. (a) Impact of MgO ([Al2O3]slag 54?0, [ZnO]slag52?0wt.%, [CaO]slag50?8wt.%). (b) Impact
of [Al2O3]slag ([ZnO]slag52?0wt.%, [MgO]slag50?9wt.%, [CaO]slag50?9wt.%). (c) Impact of CaO ([Al2O3]slag 54?0, [MgO]slag5
0?9wt.%, [ZnO]slag52?0wt.%) (d) Impact of ZnO wt.% ([Al2O3]slag 54?0, [MgO]slag50?9wt.%, [CaO]slag50?9wt.%)

3?3 wt-%Fe in matte (,76 wt-%Cu), the magnetite
solubility increases rapidly and solid magnetite can be
formed.
Sulphur and copper solubilities in EF liquid slag
The reduction of copper oxide in slag in the EF occurs
by reaction with the coke (as a direct or indirect
mechanism), or by other mechanisms such as coreduc-
tion of copper oxide and magnetite with iron oxide or
liquid iron.34–36 The overall reactions for the reduction
with coke, or co-reduction by metallic iron can be
represented as follows
2(Cu2 O)slag zC~4(Cu)matte zCO2
(Cu2 O)slag z(Fe)matte ~2(Cu)matte z(FeO)slag
As noted above, the EF slag contains some dissolved
sulphur (mainly as FeS). This can react with dissolved
copper oxide in slag according to reaction (11)
(Cu2 O)slag z(FeS)slag ~(Cu2 S)matte z(FeO)slag
The presence of soluble sulphur in slag can also increase the
total level of soluble copper in slag which is in equilibrium
with matte below 65 wt-%Cu as discussed by Nagamori,4
Yazawa37 and also by Coursol et al.26 But in the present
case, even though the level of sulphur in EF slag is small,
knowledge of the slag sulphide capacity is nevertheless
considered important in understanding the mechanisms of
copper losses. This aspect is explored as follows.
The effect of the Fe/SiO2 ratio on the copper solubility
in EF slag in the temperature range of 1180–1270uC and
for the slag in equilibrium with sulphur deficient matte
containing 72 wt-%Cu (6?5 wt-%Fe) is shown in Fig. 11.
It is seen that the Fe/SiO2 has only a small impact on
copper solubility. This is due to the rather constant
(9) oxygen potential (calculated as 1029?6 atm) over the
range of Fe/SiO2 ratios examined. The temperature has
(10) a greater influence on copper solubility than the Fe/SiO2
ratio, confirming that a lower slag temperature favours a
lower copper solubility in slag.24
Figure 12 shows the effect of the iron level in EF
matte on both the soluble copper and soluble sulphur
(11) levels. As expected, the iron level in matte has an
important influence on the levels of both copper and
sulphur dissolved in slag. It can be seen that copper

326 Canadian Metallurgical Quarterly 2011 VOL 50 NO 4

 Cardona et al. Copper smelting slags and copper losses at Paipote smelter: Part 1

9 Impact of iron level in matte on calculated EF slag liquidus
(sulphur deficiency in matte of 0?25 wt-%): star symbol
represents average operational point ([Al2O3]slag5
4?0 wt-%, [ZnO]slag52?0 wt-%, [MgO]slag50?9 wt-%, [CaO]slag5
0?9 wt-%)
10 Calculated ‘‘soluble magnetite’ levels in EF slag at
1220uC; star symbol is the average operational point.
(sulphur deficiency in matte of 0?25 wt-%, [Al2O3]slag5
4?0 wt-%, [ZnO]slag52?0 wt-%, [CaO]slag50?8 wt-%,
[MgO]slag50?8 wt-%)

pyrometallurgical slag cleaning process at which the

solubility decreases, while the sulphur solubility rises
total copper soluble in slag would be minimised.
linearly, for iron levels in matte between 0?5 and 16
wt-% (78–60 wt-%Cu). The effect on copper solubility is
more marked below about 4 wt-%Fe in matte. Conclusions
Figure 13 shows that a lower Fe/SiO2 ratio results in Based on the present thermodynamic modelling of the
lower sulphur levels in slag, over the same range of Fe TC and EF processes, the key parameters for the
(wt-%) in matte as shown in Fig. 12. When the iron level production of a good quality slag with low copper losses
in matte approaches 0 wt-%, the activity of FeS and its were examined. It was shown that matte entrainment in
solubility in slag decreases to nearly zero as discussed by the TC slag is the most important component of the
Shimpo et al.38 The slope of the solubility lines in Fig. 13 observed copper level (average Cu in this slag is ,6
changes with different Fe/SiO2 ratios, thus suggesting a wt-%). The calculated level of dissolved copper in this
lower FeS activity coefficient at the higher values of the
Fe/SiO2 ratio. Iron sulphide is considered to dissolve in
the iron silicate melt by a common ion mechanism (Fe2z/
SiO4{ 22
4 , S ), but when more SiO2 is introduced (i.e. lower
Fe/SiO2 ratios), the slag becomes more ‘glass-like’, hence
having a lower solubility for S22 anions as shown.
The FactSage model used in the present work to
calculate the sulphide capacity of the slag20 is considered
more reliable when the activity of an oxide is much
greater than the activity of the sulphide for a given
element (for example, a(FeO) and a(FeS)). This situa-
tion is considered valid for the FeS–FeO sulphide–oxide
couple but not for the Cu2S–Cu2O couple. From this
perspective and from the authors’ experience, the model
appears to predict well the S22 solubility in the slag
present as FeS, but does not seem to reproduce well the
interaction between the soluble sulphur and the soluble
copper. The model appears to underestimate the inter-
action between the soluble sulphur and the soluble
copper, leading to calculated copper losses lower than 11 Impact of Fe/SiO2 ratio on calculated copper solubility in
levels reported of industrial slag,5,39 or those reported in EF slag: star symbol is average operational point
laboratory experiments.6,40 Given that a high interaction ([Fe]matte56?5 wt-%, [Cu]matte572?0 wt-%, [S]matte521?5
is in fact expected between soluble sulphur and copper, wt-%, [Al2O3]slag54?0 wt-%, [ZnO]slag52?0 wt-%, [MgO]slag5
an optimum sulphur level in slag would then exist for a 0?8 wt-%, [CaO]slag50?8 wt-%)

Canadian Metallurgical Quarterly 2011 VOL 50 NO 4 327

Cardona et al. Copper smelting slags and copper losses at Paipote smelter: Part 1
12 Calculated soluble Cu (as Cu2O) and S (as FeS) levels in
EF liquid slag at 1220uC: sulphur deficiency in matte
of 0?25 wt%; star symbol is average operational point
([Al2O3]slag54?0 wt-%, [ZnO]slag52?0 wt-%, [MgO]slag5
0?8 wt-%, [CaO]slag50?8 wt-%, Fe/SiO251?6)
slag under current operating conditions was found to be
between 0?50 and 0?63 wt-%, representing less than 10%
of the total copper content.
It was estimated that there is about 6 wt-% of solid
magnetite in suspension in TC slag (at a Fe/SiO2 ratio of
1?7); conveniently, some of this refractory-like material
precipitates on the refractory face of the vessel, thus
forming a protective layer. At Fe/SiO2 ratios above 1?8,
or with mattes containing less than 3 wt-%Fe, higher
amounts of solid magnetite would be present in the slag,
thus also contributing to higher levels of entrained
matte. The present study confirmed the optimal condi-
tions for TC operations as follows: %Fe in matte of
between 3 and 6 wt-%, the temperature range between
1200 and 1250uC and the Fe/SiO2 ratio in slag between
1?5 and 1?8.
As regards the EF, it was found that Paipote EF slag
would be fully molten (no solids present) under current
operating conditions (Fe/SiO2 ratio in slag of 1?6 and
temperature range of 1180–1250uC). The slag superheat
was found to be between 50 and 100uC, thus allowing
for efficient settling of entrained matte. On the other
hand, at Fe/SiO2 ratios above 1?8, there is an increase
in the soluble magnetite content, along with higher
sulphide slag capacity in slag, while at lower Fe/SiO2
ratios, the slag viscosity increases, thus hindering good
settling of entrained matte.
Based on the present study, the level of soluble copper
in Paipote EF discard slag is expected to be in the range
0?36–0?53 wt-%Cu. This is considered to represent the
minimum achievable level of copper in EF discard slag.
Plant data show an average of 0?82 wt-%Cu in slag;
hence, the soluble copper represents y50% of the total
copper losses (range: 43–65%), with the balance being as
entrained matte.
328 Canadian Metallurgical Quarterly 2011 VOL 50 NO
13 Impact of Fe/SiO2 ratio and of %Fe in matte on EF liquid
slag at 1220uC on calculated sulphur solubility in EF slag:
sulphur deficiency in matte of 0?25 wt-%; star symbol is
average operational point ([Al2O3]slag54?0 wt-%, [ZnO]slag
52?0 wt-%, [MgO]slag50?8 wt-%, [CaO]slag50?8 wt-%)
As a practical application of this work, the graphs
presented in the present paper can be used by smelter
personnel to evaluate the effect of changes in feed
materials and/or changes in furnace operating condi-
tions at the plant on slag characteristics.
Acknowledgements
The first author (NC) wishes to thank ‘Comision
Nacional de Investigación Cientı́fica y Tecnológica
(CONICYT)’ of Chile for its financial support during
this study. The authors also thank the personnel of the
Hernan Videla Lira Smelter; their collaborative attitude
has led to great synergies between fundamentals and
applied aspects of this project.
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