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Multicomponent Thermodynamic Databases for Complex Non-ferrous
Pyrometallurgical Processes
Conference Paper · August 2018
DOI: 10.1007/978-3-319-95022-8_68
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3. Introduction
The non-ferrous pyrometallurgy industry is providing increasing volumes of pri-
mary metal and is recycling an ever-widening variety of metals. These develop-
ments bring with them a number of challenges including issues associated with
source materials scarcity, the increasing compositional and structural complexity of
modern devices, environmental impact and sustainability.
The rapid increases in computer power, the ability to collect and analyse large
volumes of data, the ability to measure change and control equipment in industrial
plant, has created opportunities to further improve the performance of existing
operations. The implementation of practices that take advantage of accurate process
models would enable improved process stability, process and feed optimization,
improved campaign planning, and ultimately the widespread implementation of
feed-forward process control systems in pyrometallurgical processes. These actions
have the potential to increase process throughput, metal recoveries and to enable the
efficient treatment of complex but profitable feed sources. The research program
outlined in this paper, on the development of the robust thermodynamic databases
and process models, is driven by the need to respond to the above challenges and
with the aim of taking advantage of these new opportunities.
The availability of accurate thermodynamics databases is essential for the
development of accurate predictive models and their use in the optimisation of
pyrometallurgical processes. These databases are the foundations of the process
models—and determine the quality of the predictive outcomes. A variety of fun-
damental data are required to develop these databases including, but not limited to,
information on solidus, liquidus, phase equilibria, solid and liquid solubilities,
distribution coefficients, thermodynamic activities, vapor pressures, enthalpy
functions in multi-component, multi-phase systems.
The research program is planned to enable the development of databases that
cover the whole range of compositions and process conditions in industrial oper-
ations and technologies used in copper, lead and zinc sulfide smelting (see Table 1).
The databases includes gas, slag, matte, metal, speiss and solid phases. The major
chemical components of slag (molten oxide) phase are described by the Cu2O-P-
bO-ZnO-FeO-Fe2O3-SiO2-S chemical system; Al2O3-CaO-MgO appear principally
in smelting as contaminants or fluxes in the feed and As-Bi-Sb-Sn-Ag-Au are minor
elements that also partition between all phases present in the systems. Major
components in matte database include Cu-Fe–Pb-Zn-O-S, and in metal Cu-Fe–
Pb-Zn alloys. Common solid solutions include spinels, melilites, zincite, in addition
to stoichiometric compounds encountered in these systems (see Table 2).
The databases that are constructed contain fundamental descriptions of the
chemical behavior of the systems and are independent of the technology that is
used. This means that the databases can be used at the heart of predictive models of
pyrometallurgical processes with additional parameters that take into account fac-
tors related to furnace design, construction and operation. The database can be used
to predict the outcomes of copper, lead and zinc sulfide smelting processes,
854 D. Shishin et al.
5. including copper smelting; copper converting; copper refining in anode furnaces;
lead sintering and smelting; lead reduction; zinc and lead fuming; and copper and
lead refining to extract precious metals. The databases can be used to describe
reactions in suspended and bath smelting, blast furnaces; batch and continuous
processes.
Outline of the Overall Program
In order to develop the databases for the complete range of conditions in copper,
lead and zinc pyrometallurgy, an integrated research program of thermodynamic
modelling and experimental measurements of phase equilibria is being undertaken.
The extensive program for lead consortium companies involves a number of
focussed projects,
1. Slag/metal phase equilibria in the PbO-ZnO-CaO-FeO-Fe2O3-SiO2-Cux-
O-Al2O3-MgO slag—Pb-Cu-Fe-Zn metal alloy.
Table 2 Solution phases important for sulphide smelting of Cu, Pb, Zn and the thermodynamic
models used to describe these in the database. For details see Refs. [1–4]
Liquid Slag:
(Al+3
, Ca+2
, Mg+2
, Si+4
,Cu+1
, Fe+2
, Fe+3
, Pb2+
, Zn2+
, Sn2+
, Sb+3
, As+3
, Bi+3
, Ag+1
, Au+1
,)
(O−2
, S−2
),
Modified Quasichemical Formalism (MQF) in Quadruplet Approximation
Spinel: [Cu+2
, Fe+2
, Fe+3
, Al+3
, Mg+2
, Zn+2
]tetr
[Cu+2
, Fe+2
, Fe+3
, Al+3
, Ca+2
, Mg+2
, Zn+2
,
Vacancy0
]2
oct
O4,
Compound Energy Formalism (CEF)
Monoxide: (FeO, FeO1.5, CuO, AlO1.5, CaO, MgO), Bragg-Williams model (B-W)
Olivine: [Fe2+
, Ca2+
, Mg2+
, Zn2+
]M2
[Fe2+
, Ca2+
, Mg2+
, Zn2+
]M1
SiO4, CEF
Dicalcium silicates: (Ca2SiO4, Fe2SiO4, Mg2SiO4, Pb2SiO4, Zn2SiO4), B-W
Wollastonite: (CaSiO3, FeSiO3, MgSiO3, ZnSiO3), B-W
Melilite: [Ca2+
, Pb2+
]2[Fe2+
, Fe3+
, Al3+
, Zn2+
][Fe3+
, Al3+
, Si4+
] 2O7, CEF
Willemite: [Zn2+
, Fe2+
, Mg2+
][Zn2+
, Fe2+
, Mg2+
]SiO4, CEF
Zincite: (FeO, ZnO, MgO), B-W
Corundum: (FeO1.5, AlO1.5), B-W
Mullite: [Al+3
, Fe+3
]2[Al+3
, Si+4
, Fe+3
][O−2
, Vacancy]5, CEF
Calcium ferro-aluminates Ca(Al, Fe)2O4, Ca(Al, Fe)O7, Ca(Al, Fe)12O19
Pyroxenes: [Fe2+
, Ca2+
, Mg2+
]M2
[Fe2+
, Fe3+
, Mg2+
, Al3+
]M1
[Fe3+
, Al3+
, Si4+
]B
SiA
O6, CEF
Liquid metal/matte/speiss:
(CuI
, CuII
, FeII
, FeIII
, PbII
,AsIII
, ZnII
, SnII
, SbIII
, BiIII
, AgI
, AuI
, OII
,SII
), MQF in Pair
Approximation
Digenite-bornite: (Cu2S, FeS, PbS, ZnS, Vacancy2S)
‘Cu3As’, (Cu, As), MQF in Pair Approximation
fcc and bcc solid alloys: (Co, Ni, Mn, Cu, Fe, Pb, O, S, Zn, As, Sb, Ag, Au), B-W
Ideal gas:> 100 species, including N2, CO, CO2, S2, SO2, H2O, AsO, AsS, As4O6, PbO, PbS
Stoichiometric compounds: > 150, including SiO2, FeS2, CaSO4, CuFeO2, Ca3Al2O6, S, ZnS,
Sb2O3
856 D. Shishin et al.
6. 2. Matte formation conditions within the gas/PbO-ZnO-CaO-FeO-Fe2O3-SiO2-
CuxO-Al2O3-MgO slag and the Pb-Zn-Fe-O-S-Cu matte/alloy systems.
3. Pb refining systems equilibria within the Pb-Cu-S-As-Sb-Sn-Fe matte/metal/
speiss system.
4. Elemental Distributions between slag, matte and metal of minor elements,
including Ag, Au, As, Bi, Sn, Sb and Zn.
5. Improvement of the thermodynamic database of oxide systems: Development of
the thermodynamic database of the PbO-ZnO-CaO-FeO-Fe2O3-SiO2-Cux-
O-Al2O3-MgO slag in Pb-Cu-Fe-Zn metal alloy systems.
6. Improvement of thermodynamic database of sulphur-containing systems:
Development of the matte/metal/speiss thermodynamic database (focus on low
temperatures) and the incorporation of minor elements.
These projects cover a wide range of chemical compositions and conditions
(temperature, oxygen and sulphur partial pressures) relevant to the whole range of
key lead smelting, refining and recycling systems.
For copper consortium companies the scope of the work includes complete
experimental revision of the thermochemistry of the base system “Cu2O”-
FeO-Fe2O3-SiO2-S with the Al2O3, CaO and MgO slagging components and
As-Pb-Zn-Sn-Sb-Bi-Ag-Au other minor elements. The experiments involve deter-
mining equilibria between gas/slag/matte/blister/solid (tridymite, spinel) phases as
functions of temperature, P(O2), P(SO2)/P(S2), slag Fe/SiO2 (and equilibria with
tridymite or spinel). This development of thermodynamic database working with
the FactSage software [5] for the above system provides direct support of the
copper smelting industry sponsors.
To investigate the distribution of minor elements between phases, it is essential
to initially accurately characterise the base system, and then systematically inves-
tigate the effect of all of the key operating parameters on the thermochemistry of all
phases within the selected range of chemical compositions. Two types of experi-
ments are performed:
• Open experiments with P(O2) and P(SO2) in the gas/slag/matte and gas/slag/
metal systems controlled by the CO/CO2/SO2 gas mixtures, and
• Closed experiments undertaken in sealed ampoules for the slag/matte/metal
system.
The overall program therefore contains the following key directions:
1. Base system with slagging components—initial description at Matte Grades
between 50 and 80% Cu
Gas/Slag/Matte,
Gas/Slag/Metal [Cu-Fe-O-S-Si] x [Temperature] x [P(O2)/P(SO2)] x [Fe/SiO2—
Tridymite/Spinel] x [Al, Ca, Mg].
Slag/Matte/Metal.
2. Distribution of Minor Elements As, Zn, Pb, Sn, Sb, Bi, Ag, Au
Gas/Slag/Matte,
Multicomponent Thermodynamic Databases for Complex … 857
7. Gas/Slag/Metal [Cu-Fe-O-S-Si] x [Temperature] x [P(O2)/P(SO2)] x [Fe/SiO2—
Tridymite/Spinel] x [Al, Ca, Mg]
Slag/Matte/Metal.
The techniques developed during this program for the first time enable the
systematic accurate measurements of this kind to be undertaken, and these mea-
surements provide an important foundation for the development of the thermody-
namic database as well as for the overall quantitative description of the
thermochemistry of copper smelting
The total number of experiments needed to completely and quantitatively
characterise the whole chemical system as functions of key operational parameters
is very large. The experimental needs are therefore carefully and critically reviewed.
An overall summary of all required experiments is prepared and continuously
revised to enable systematic analysis and selection of optimum research plan to
support the development of the thermodynamic database, to close the gaps where
no data is available and to resolve discrepancies.
An example of the systematic approach undertaken for the planning of the
copper consortium experimental program is given in the following paragraph. A list
of experiments needed to characterise the whole chemical system as functions of the
key operational parameters is selected, as illustrated in Table 3:
Table 3 An example of the systematic approach taken to experimental study and modelling for
copper database development
858 D. Shishin et al.
8. • Columns 2 through 8 indicate the matrix of key parameters selected for
characterisation
• Columns 9 and 10 indicate current status of system description
Each line in Table 3 represents a series of experiments. For example,
• line 1.1 represents gas/slag/matte equilibria on a tridymite substrate for a range
of matte grades from 55 to 80 wt%Cu at base case conditions of 1200°C and P
(SO2) = 0.25 atm.
• line 1.2 presents the effect of temperature in the above system
• line 1.3—the effect of P(SO2) in the above system, as so on for all key
parameters.
In this way, the whole list of the experiments needed to quantitatively charac-
terise the system as functions of the key parameters is being carefully analysed, and
most critical experiments are selected and performed to support the development of
the thermodynamic database using FactSage package [5].
The next stage of the program is to combine and integrate the copper and lead
databases. Figure 1 illustrates the number of binary, ternary and higher order sys-
tems that must be accurately described. As the number of components are added to
the system so the number of chemical interactions and sub-systems that must be
described increases.
Fig. 1 Binary, ternary and higher order sub-systems in the system Cu2O-PbO-ZnO-Al2O3-CaO-
MgO-FeO-Fe2O3-SiO2-S-(As-Bi-Sb-Sn-Ag-Au)
Multicomponent Thermodynamic Databases for Complex … 859
9. Demonstrating Capabilities
Complete Description of the Copper-Matte-Slag-Gas System
Cu2O-Al2O3-CaO-MgO-FeO-Fe2O3-SiO2-S
The databases provide detailed descriptions of a range of effects with high accuracy.
The agreements between experimental data and databases are demonstrated in
Fig. 2a–g for slag/matte systems at 1200 °C. The sensitivity of the systems is
exemplified by the effect of oxygen pressure on copper matte grade is shown in
Fig. 2a. The extent of non-stoichiometry of matte and the relatively small influence
of temperature on this factor is shown in Fig. 2b. The Fe3+
/Fetotal ratio in slag in
equilibrium with mattes of varying grades and the influences of relatively small
concentrations of MgO are given in Fig. 2c. The compositions of the slag liquidus
as a function of matte grade for the limiting conditions of silica and spinel satu-
ration are given in Fig. 2d. The effect of alumina in slag on the dissolved sulphur in
slag is provided in Fig. 2e. The predicted and experimentally determined
Fig. 2 Calculated lines and experimental data [6–15] obtained for gas/matte/slag equilibria in the
Cu-Fe-O-S-Si system + Al2O3, CaO, MgO
860 D. Shishin et al.
Examples of the agreement between experimental data and
thermodynamic model across a wide range of measures
illustrating, as a function of matte grade, a) P(O2) at metal
saturation and at high P(SO2), b) effect of temperature on sulphur
in matte, c) effect of MgO concentration in slag on Fe3+/Fetotal in
slag, d) Fe/SiO2 ratio along the liquidus e) effect of Al2O3 in slag on
sulphur concentration in slag, f) effect of CaO concentration in
slag on dissolved copper in slag, and g) dissolved oxygen in matte.
10. concentrations of copper dissolved in slag are shown in Fig. 2f, illustrating the
complex non-linear behavior with changing matte grade. Figure 2g shows the
concentration of dissolved oxygen in matte as a function of matte grade. Please note
that the effect of P(SO2), temperature, MgO, CaO and Al2O3 in slag is available
now for all 7 diagrams in Fig. 2, but not shown due to limitations of the present
article.
Resolving Complexities in Database Development
As indicated, in constructing the optimised databases for these multi- component
systems, it is necessary to obtain not just information on the phase equilibria but
also to ensure that the parameters selected are consistent with other thermodynamic
properties. An example of this is shown in Figs. 3a–d. The binary phase diagram
for the PbO–SiO2 system at low temperatures has been investigated and charac-
terised in numerous studies. The liquidus in the silica primary phase fields has
Fig. 3 Examples of the different types of information required to select modelling parameters that
are valid across the whole range of compositions and process conditions for the lead-matte-slag-
gas system [16, 17]
Multicomponent Thermodynamic Databases for Complex … 861
11. remained uncertain until recent research due to the difficulties associated with high
vapour pressures of lead species at high temperatures in this system. Many com-
binations of enthalpy and entropy contributions can be selected to describe the
shape of the liquidus. However these parameters must also be able to describe other
thermodynamic data in related systems, such as activities of the components and
elemental distributions between phases. These properties should be consistent with
experimental data in the Pb–Fe-Si-O and Cu-Pb–Fe-O-S systems as shown in
Fig. 3b–d. The key point to note from this example is that information from dif-
ferent types of thermodynamic properties is required and must be described in order
to obtain accurate parameters for the database; phase equilibrium data on their own
are not sufficient to identify the unique parameters required to unambiguously
describe the system.
To effectively manage the complexity of the 16 component system Cu2O-P-
bO-ZnO-Al2O3-CaO-MgO-FeO-Fe2O3-SiO2-S-(As-Bi-Sb-Sn-Ag-Au) the database
development has been organised by splitting the system into two parallel, yet
integrated tasks. One involves the experimental investigation and database devel-
opment of the Cu-Fe-O-Pb-Zn-Ca–Si + (Ca–Mg) systems, that is the base slag/
metal systems [18]. The second task is the optimisation of the slag/matte/speiss
equilibria and minor element distributions between these phases.
Applications to Industrial Systems
Fluxing Diagrams
Having prepared the updated and optimised thermodynamic databases they can be
used in conjunction with the FactSage computer platform to predict specific process
outcomes.
Figure 4a shows how the liquidus surface in the Fe-SiO2 system at P(SO2) =
0.5 atm., 60%Cu matte grade changes with the presence of impurity elements
Al2O3, CaO, MgO in the slag. It can be clearly seen that the liquidus on this
pseudo-binary section moves significantly to lower Fe/SiO2 ratio in both the spinel
and silica primary phase fields with the presence of these impurities. These effects
have significant implications for practice since they demonstrate the need to adjust
the fluxing requirements of the process depending on the impurity levels in the slag;
potential savings on flux additions and minimising potential operational difficulties
through operating at conditions that are below the liquidus and potentially creating
tapping difficulties due to high %solids in slag. Figure 4b shows the sensitivity of
the system to changing temperature; here the % solids can be estimated as a
function of Fe/SiO2 ratio and temperature for a given set of operating conditions in
copper converting.
862 D. Shishin et al.
12. Pseudo-ternary Sections
The major components in lead blast furnace slags are CaO-FeO-SiO2-ZnO; Al2O3
and MgO are also routinely present in the slags at low concentrations. Using the
thermodynamic database the liquidus surface of the slag is predicted and shown in
Fig. 5a, b) for a fixed CaO/SiO2 wt. ratio and fixed Zn/Fe wt ratio respectively. The
predictions make it possible to identify the sensitivity of the system to changes in
slag composition. From Fig. 5a it can be seen that increasing the Zn/Fe ratio is
limited by the zincite, (Zn,Fe)O, solid solution primary phase field, the liquidus
temperature of which rises sharply with increasing zinc concentration. The opti-
mum total flux (CaO +SiO2) requirement for the CaO/SiO2 of 0.72 would appear to
be at approximately (CaO + SiO2)/(CaO + FeO + SiO2 + ZnO) = 0.45 by wt. In
Fig. 4 a Projection of the slag liquidus as a function of Fe/SiO2 ratio for P(SO2) = 0.5 atm. 60%
Cu matte grade. b % solids in slag as a function of Fe/SiO2 and temperature for P
(SO2) = 0.15 atm. 78%Cu matte grade
Fig. 5 Predicted liquidus surfaces of the CaO-FeO-SiO2-ZnO-Al2O3-MgO slags at lead metal
saturation for a CaO/SiO2 wt. ratio = 0.72, b Zn/Fe wt. ratio = 0.8
Multicomponent Thermodynamic Databases for Complex … 863
13. Fig. 5b) it can be seen that for Zn/Fe = 0.8 there appears to be a local minimum in
liquidus temperature at CaO/SiO2 wt. ratio between approximately 0.6–0.7.
Process Simulation
The thermodynamic databases and computer software that are now available can be
applied to not only the determination of equilibria particular cases but also to the
prediction and simulation of dynamic and multi-stage metallurgical processes. The
databases now include critical information on a wide range of elements present in
complex industrial process systems. Increasing the number of elements present in
the system increases the computation time required to undertake the Gibbs Free
Energy minimisation calculation routines particularly with the formation of com-
plex solutions. This is potential limitation to the application of this technology to
practice so it is worthwhile examining these issues and how they might be
addressed.
By way of illustration we consider the simulation or modelling of a batch
process. As in any thermodynamic calculation the first consideration is definition of
the system boundaries. If this is a closed system, with no material of energy transfer
taking place, then the outcomes of the reaction can be calculated in a single stage. In
practice, this is rarely the case, material and energy is introduced or removed
throughout the reaction; how can we deal with this and what are the implications of
different calculation strategies?
Take the example of the Peirce-Smith copper converting process. In this case
there is an oxygen containing gas blast into molten matte phase, sulphur containing
product gas that is removed from the system, slag phase generation and periodic
removal, and enthalpy losses associated with product removal and heat losses
throughout the process. An example of a detailed calculation incorporating all of the
stages undertaken in typical Peirce Smith converter was reported in [19]. Figure 6
summarized the process inputs and outputs of the calculations of the present study.
These values were obtained by considering the system as a series of linked equi-
librium batch processes; the time interval between each iteration was relatively
short (5 min); gas was removed at each iteration. Each stage ended with the slag
removal; fluxes, reverts, copper scrap were added several times during one stage.
This example demonstrates the capability of the current thermodynamic data-
bases and computer modelling systems. In the present article, calculations were
performed for the Cu-Fe-O-S-Si-(Pb-Zn-As-Bi-Sb-Sn-Ag-Au)-C-N-H chemical
system, which is of interest for industrial practice. What becomes clear is that, i) the
greater the number of chemical components the longer it takes to complete the
calculation, and ii) the accuracy of the calculations depend on the time or increment
steps considered. The smaller the steps between iterations the greater the accuracy
but the longer the computational time. The time response is an important consid-
eration if we are to introduce these tools into industrial practice. We need to select
the calculation approach that is appropriate for the application. For example, an
864 D. Shishin et al.
14. on-line “logistics” model to optimise ladle movement and charging cycles requires
a rapid response, which is more important than accuracy of the predictions below a
given level of uncertainty. On the other hand, accurate predictions may be required
to maximise minor element recovery or impurity removal.
The sensitivity of the predictions to the number of iterations or calculation steps
is illustrated in Fig. 7a, b). It can be seen that there are significant differences
between the single step calculation and many step cases for the predicted mass of
slag produced in the copper blow stages and the final sulphur in blister. Detailed
analysis shows that there will be less slag and lower sulphur in the blister as the
number of calculation steps is increased. Since the gas phase is continuously
removed from the system, there will be also differences in the total masses of
volatile metal species, such as lead and arsenic, reporting to the gas phase
depending on the calculation strategy. A single calculation provides only the overall
enthalpy change in the system, however it is desirable to be able to predict varia-
tions in temperature of the reactor during processing. Higher reaction temperature
leads to increased attack on refractories and reduced lining life; decreases in tem-
perature can result in the formation of solids in the slag with consequent increases
in slag viscosity. From a process control perspective further detailed information is
necessary to understand and avoid these potential operating difficulties.
It can be clearly seen from these examples that the use of accurate thermody-
namic databases coupled with predictive power of computer platforms provides
Fig. 6 Example of the process simulation of a typical Peirce-Smith converter cycle, consisting of
two slag blow stages and one copper blow stage
Multicomponent Thermodynamic Databases for Complex … 865
15. opportunities for optimization and improvement of metallurgical processes. Specific
applications include:
• Optimising processing conditions, e.g. fluxing, temperature, oxygen to feed ratio
and fuel utilisation.
• Increasing process stability and throughput.
• Improving metal recovery, through reduced losses of dissolved and entrained
metal in slags.
• Removing unwanted impurity elements, increasing and optimising complex
feed intake.
• Improving vessel integrity/lining life by reducing operating temperatures, tuning
slag and refractory compositions, and stabilising operating conditions.
These predictive capabilities are already being used in industry. See an example
of case study of performance of ISASMELT reactor with different types of con-
verters [20]. As confidence in the use of these tools is increased and predictions
verified by plant practice, the opportunities for the introduction of the next phase of
implementation will arise—the introduction of feed forward control of pyrometal-
lurgical reactors.
Summary
An integrated research program of thermodynamic modelling and experimental
measurements of phase equilibria is being undertaken to develop accurate and
internally-consistent thermodynamic databases that can be used to describe the
chemical equilibria in copper, lead and zinc smelting, metal production and recycling
systems. The databases contain fundamental thermodynamic descriptions of the
Fig. 7 The effect of the number of calculation steps on the predicted outcomes of a typical
Peirce-Smith converter cycle, consisting of two slag blow stages and one copper blow stage,
a mass of copper blow slag, and b the concentration of sulphur in final blister copper
866 D. Shishin et al.
16. gas-slag-matte-metal-speiss-solids phases Cu2O-PbO-ZnO-Al2O3-CaO-MgO-FeO-
Fe2O3-SiO2-S-(As-Bi-Sb-Sn-Ag-Au). The program has provided valuable new
fundamental information on phase equilibria and thermodynamic properties of
complex multi-component, multi-phase systems.
Acknowledgements The authors would like to thank Australian Research Council Linkage
program, Altonorte Glencore, Atlantic Copper, Aurubis, BHP Billiton Olympic Dam Operation,
Kazzinc Glencore, Nyrstar, PASAR Glencore, Outotec (Espoo and Melbourne), Anglo-American
Platinum, and Umicore for the financial and technical support.
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