Indian Institute of Technology

Department of Metallurgical and Materials Engineering

Final Exam: MM2080-Principles of Extractive Metallurgy

Total Marks: 90, Duration 3:00 Hrs

Date: January 2, 2021, 2:00 PM to 5:00 PM.

Instructions:

1. Attempt all the questions

2. All questions carry equal marks

3. The parameters may be assumed wherever you find necessary.

4. For calculations, Excel-Solver may be used.

5. Submit the answer sheet (Pdf and Excel Sheets) on Moodle by 5:15 PM. There will be penalty
for delayed submissions.

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1. A zinc concentrate analyzing 68% ZnS, 4% PbS, 2% CdS, 5% FeS, 4% FeS2, 10% SiO2 and
7% H2O is roasted in fluid-bed roaster. The roasted product contains CdO, Fe2O3, PbO, PbSO4,
SiO2, ZnO and ZnO.Fe2O3. Lead is evenly distributed between PbO and PbSO4. Find:

(a) The theoretical air requirement

(b) The amount and composition of the off-gases when air 15 vol% in excess of the theoretical
requirement is used.

(c) The amount and composition of the off-gases when oxygen enriched (28 vol% O2) air 10% in
excess of the theoretical requirement is used.

Use one ton of concentrate as a basis.

2. Limestone was calcined in a rotary kiln fired with natural gas. The kiln was operated at steady
state, producing 280 tons of dead-burned lime per day. The stone fed to the kiln analyzed as 96
wt% CaCO3, 2 wt% SiO2, 1 wt% Fe2O3 and 1 wt% H2O. Calculate: (a) The feed rate of
limestone (b) The chemical analysis of lime made.

3. An electric melting furnace is used to melt copper scrap. The scrap is at an initial temperature
of 25 oC. It is claimed that the overall average power consumption of the furnace is 280 kW-hr
per ton of copper melted. Estimate the thermal efficiency of this furnace, assuming the copper is
not only melted but also heated to a final temperature of 1200 oC.

Melting point of copper: 1083 oC

Heat of fusion of copper: 12,970 J

Cps = 22.64 + (6.28 x 10-3 T) J/g.mole.oK

Cpl = 31.38 J/g.mole.oK

4. Aluminum is produced by electrolysis of alumina dissolved in molten cryolite. (a) In the Hall-
Heroult process, carbon electrodes are used to accomplish electrolysis. The oxygen liberated at
the anode electrochemically reacts with carbon to produce CO-CO2 mixture in the ratio of 4:1 at
1000 oC. Write the electrode reactions. Determine the minimum voltage required for electrolysis
if the anode gas pressure is 1 atm. Calculate the amount of carbon consumed per kilogram of
aluminum produced. Assume 100% current efficiency.

5. The standard free energy changes for the following reactions are given as:

FeO(s) + CO(g) = Fe(s) + CO2 (g) ∆Go1 = -17883 +21.087. T J

Fe3O4(s) + CO(g) = 3 FeO(s) + CO2(g) ∆Go2 = 29229 -27.927. T J

(a) Calculate the temperature at which the system consisting of Fe, FeO, Fe3O4, CO and CO2
could, if possible, exist in equilibrium, and determine the corresponding value of the equilibrium
constant.

(b) If the total pressure of the system is 1 atm, will C(s) form in the system at this temperature?

(c) If the answer to part (b) is affirmative, determine the limiting value of the total pressure
below which no C(s) will deposit from the gas phase.

6. Please read the attached literature and answer the following questions:

1. Summary of the literature (within 500 words)

2. Your viewpoint on suitability of pyro metallurgy vs Hydrometallurgy process routes

considering various factors?

3. How one can utilize Ellingham diagram, Phase diagram and Predominance area diagram in
copper extraction by pyro metallurgy route? Explain with few examples.

4. What are the precious metals present in copper melt and how are they recovered?
128

Received January 9, 2018

Review Accepted for Publication April 6, 2018
©2018 Soc. Mater. Eng. Resour. Japan

Stability Diagrams for Copper-Sulfide and Copper-Recycle Systems

Applied to Extractive Metallurgical Processes

Hsin-Hsiung HUANG*, Larry G. TWIDWELL* and Courtney A. YOUNG*

* Department of Metallurgical and Materials Engineering

Montana Tech of The University of Montana, Butte MT, USA
E-mail:[email protected]

Copper sulde from ore deposits and recycled copper from collected wastes are the two main resources
for the production of copper metal. Thermodynamic calculations can be used to serve as a guide for
characterization of ore deposits and their mineralogy as well as for process development by mineral
processing and by waste separation. The concentrated ore and separated waste can then be processed by
pyro- and/or by hydro-metallurgical operations. Such operations may be controlled by oxidation-reduction
potential, temperature, complexing reagents (gas, solid or dissolved species), oxidant- reductant, and mass of
components. Commonly used stab ility diagrams for aqueous system include speciation (counting alpha) and
EH-pH (Pourbaix) diagrams and, for non-aqueous systems, are partial pressure (Kellogg), binary and ternary
phase, and Ellingham diagrams.
For multicomponent systems, the appropriate approach for the construction of the stability diagram is to
use a complete mass balance approach rather than draw the equilibrium line between two adjacent species.
Not limited to two variables, a three- dimensional diagram can also be constructed.
This paper illustrates the use of stability diagrams for investigating and interpreting how operation
variables are important with a focus on extractive metallurgical operations to produce copper. Industria l
operation conditions are marked on the diagrams.
Keywords : Thermodynamics copper extraction, Partial pressure diagram, EH-pH diagram, Ellingham
diagram, Binary and Ternary phase diagrams

Characterization and/or process operations presented in the

1 INTRODUCTION
following discussion include: Copper ore d eposit, Mineralogical
Sulfides minerals are usually the main feed for the production formation, Flotation chemistry, Smelting and converting by
of non-ferrous metals. Extractive processes involve many unit pyrometallurgy, and Leaching processes by hydrometallurgy, both
operations from ore to metal. Each operation has been thoroughly managed and natural.
researched and developed not only for the recovery of metals but The authors assume that the reader has basic knowledge about
also for the rejection of the gangue minerals. Because copper is Extractive Metallurgy of Copper which is well p resented by the
a well-recognized metal pro cessed globally at high tonnages, its Davenport Ref. [1]. Thus, only crucial processes will be presented.
extractive metallurgical treatment as various sulde minerals has Except ternary phase diagrams, most of the stability diagrams
been selected as the main focus of this paper. presented herein were constru cted by StabCal Ref. [2] with the
Not to be ignored, copper is one of the most recycled metals. temperature and composition as close to the actual process as
There is little difference in quality and performance between possible. Most of diagrams are also marked with the conditions
extracting from ore or recycling materials. Because of tight supply actually used in plant operations.
of copper from ore deposits, 34% of global copper produced is
2 COPPER ORE DEPOSIT
from recycled materials. About 60% of recycled copper is primarily
from scrap that can be charged directly to the melting furnace for Copper porphyry ore deposits occur throughout the world
rening. Secondar y recycled copper comes from consumer waste and are very important sources of copper, silver and gold. These
and electronic waste (E-waste). It too can be recycled not just for deposits initially consist of disseminated sulfide minerals in a
copper but for other valuable metals as well. rock matrix, but near-surface weathering oxidizes the suldes and
Because most of the processing steps involve many critical dissolves metals from the residual mass. These leached metals in
variables, a simplied overall reaction or list of conditions cannot solution percolate downward and are often reprecipitated in an
show the flexibility or the adjustments necessary for changing enrichment zone overlying unreacted sulfide protore. The near-
the materials and operating conditions. Various types of stab surface weathered, oxidized portion of the deposit corresponds
ility diagrams can be used and are thus illustrated based on to the oxidized region (high oxidation potential), while the non-
chemistry and thermodynamics under multi-variable conditions. oxidizing reduced enrichment zone corresponds to the reduced

Int. J. Soc. Mater. Eng. Resour. Vol.23, No.2, (Sep. 2018)

 Stability Diagrams for Copper-Sulfide and Copper-Recycle Systems 129
Applied to Extractive Metallurgical Processes

Figure 1 Illustrated copper ore deposit (Dudas et al. Ref. [3]) for
comparison to the EH-pH diagram in Figure 2. Figure 3 Ternary Cu-Fe-S mole fraction phase diagr am. This figure is
copied and edited from Figure 6.15 in Garrels and Christ Ref.
[6].

Figure 2 E H-pH diagram for Cu-CO 2-Fe-S in water. pCO 2 0.1 atm,
[S] 0.01 M, [Fe] [Cu] 0.001 M. Species and their free
energies of formation were taken from the LLnL database Ref. Figure 4 Species and their mass from Zone 1 of Figure 3 along the path
[5]. In reference to Figure 1, light gray represents the oxidi zed/ from A to I in Figure 3.
leached zone (solid and soluble species) whereas moderate
gray illustrates the enrich ment zone, and dark gray shows the
primary sulde zone. by titration. Total mass of Cu-Fe-S components were 0.1-0.2-0.15
moles, respectively. By keeping Cu and Fe amounts constant, S was
incrementally added from 0 to 0.4. The simulation path is shown
region (low oxidation potential). Figure 1 is a geologic sketch of an on Figure 3 using a long arrow labelled with the area from A to I.
idealized porphyry deposit versus the depth from the surface Ref. The results of equilibrium calculation are shown in Figure 4 with
[3], while Figure 2 is a copper EH-pH diagram in which iron, sulfur the same labels and are noted to satisfy Gibbs Phase Rule under all
and carbonate, besides copper, are considered in the calculations conditions such that no more than three solids are simultaneously
along with copper. The minerals predicted in the diag ram, solely stable although their amounts can change depending on the amount
from thermodynamic considerations, correspond extremely well of sulfur titrated. For instance, in area E, three stable species are
with minerals observed in these deposits and with the relationships observed (CuFeS2, FeS2 and FeS) with their respective masses.
between these minerals Ref. [4].
3.2 Partial Pressure Diagram–Equilibrium Line
3 MINERALOGY
versus Mass-balanced Method
3.1 Ternary Diagram of Cu-Fe-S The partial pressure diagram, aka Kellogg diagram, can be
Copper sulfide minerals are commonly associated with other constructed either by the equilibrium line or by mass-balanced
sulfides, iron sulfides in particular. The mole fraction ternary methods. The line method is used to calculate and draws
phase diagram of Cu- Fe-S is shown on Figure 3 which indicates equilibrium boundaries between two adjacent species. The mass-
three distinctive zones depending on the Cu/(Cu+Fe) ratio. Using balanced method solves equ ilibria from all species and masses
the chemical formula of minerals, Zone 1 has th e ratio less than specified for all components together for each location on the
chalcopyrite (CuFeS2). Zone 2 lies in b etween chalcopyrite and diagram. For a multicomponent system, the line method suffers
bornite (Cu5FeS4), and Zone 3 has excess copper greater than the lack of controlling indiv idual mass. Huang and Young Ref. [7]
bornite. All d iagrams in this m ineralogy section are constructed presented more detailed comparison between these two methods.
using species and their free energies of formation re-evaluated 3.2.1 Line method diagram–Suitable only for Zone 1 from
from Figure 6.16 of Garrels and Christ Ref. [6]. Cu-Fe-O-S system: The log pS2 vs log pO2 partial p ressure diagram
Species and their individual masses in Zone 1 were simulated was originally presented by Garrels and Christ Ref. [6] and has

Int. J. Soc. Mater. Eng. Resour. Vol.23, No.2, (Sep. 2018)

130 Hsin-Hsiung HUANG et al.

Figure 5 Partial pressure log pS 2 versus log pO2 diagram constructed

by line method which is only good f or Zone 1 shown on the
Figure 7 Three variables (log pS2, log pO2 and Cu/(Fe+Cu)) diagram of
ternary phase diagram in Figure 3. L ines and main component the Cu-Fe-S-O system. Only the center area of the diagram is
of Cu- Fe-S species ar e in dark gray, and ligand species Fe-S labeled with the names of the species. All different intensities of
are in light gray. Letters A-I correspond to the location indicated gray can be read from the map. Each gray contains tw o species
on Figure 3. whose abbreviations are bn(Cu 5FeS4), cc(Cu 2S), ci(CuO),
co(Cu2O), cp(CuFeS2), cv(CuS), hm(Fe2O3), mg(Fe3O4), po(FeS)
and py(FeS2).

Figure 6 Partial pressure diagram constructed by the mass-balanced

method where Cu/(Fe+Cu) 0.9 which represents the Zone 3
on the ternary diagram shown in Figure 3. Notice that there is
no chalcopyrite in this zone.

Figure 8 This is the same diagram as Figure 7 for three variables Cu-Fe-
been recalculated using StabCal. The n ew result is presented in S-O system. The diagram was clipped at Cu /(Cu+Fe) 0.62 to
Figure 5 where Cu is the maincomponent and Fe serves as the show Z one 2 species from Figure 3.
ligand. Without specifying the mass of ea ch component, this type
of diagram always assumes that the mass of ligand to be greater
than or equal to the mass main component. In other words, it
4 FLOTATION
represents only Zone 1 on the ternary diagram shown in Figure 3.
3.2.2 Mass-balanced diagram –Suitable for All Zones 4.1 Frumkin Adsorption
from Cu-Fe-O-S system: By comparison to Zone 1, the other During froth flotation, some minerals absorb collector and
Zones requires Cu/(Fe+Cu) to be greater than 0.5 and have to be change their hydrophilic surfaces to hydrophobic. Resulting
constructed by the mass-balanced method. Figure 6 shows the minerals will attach to air bubbles injected into the slurry to rise
diagram for Zone 3 using Cu/(Cu+Fe) 0.9. As indicated on the and form a froth at the top of the pulp. A separation is made when
ternary diagram, Figure 6 illustrates that chalcopyrite is not present the froth is removed by scraping into a launder thereby forming a
in Zone 3. concentrate. Non-Adsorbing minerals remain in the pulp and are
3.2.3 3-D diagram–Combine all 3 zones into one diagram: removed as tailings at the bottom of the cell.
The best way to show all 3 Zones for a partial pressure diagram Xanthate, represented by X, is a common collector that has
is to include an additional var iable of the mass ratio Cu/(Cu+Fe). been used and studied often for the flotation of copper ores.
Results from this mass-balanced calculation are shown in Figure Species HX, X-, X2 (aqueous and liquid), and CuXn and FeXn all
7 and Figure 8 after importing StabCal results into Paraview 3-D h ave been identified. In addition, Woods Ref. [9] also reported
software Ref. [8]. that electrochemically adsorbed X(chem) occurs by the surfaces
Even though the diagram canbe animated by rotation, clipping of chalcocite and Cu metal. Even though the adsorption is
and slicing, only still pictures can be presented in this paper. independent of pH, surface coverage depends not only on collector
concentration but also the potential of the minerals. The Frumkin
isotherm was modied to formulate this type of adsorption.

Int. J. Soc. Mater. Eng. Resour. Vol.23, No.2, (Sep. 2018)

 Stability Diagrams for Copper-Sulfide and Copper-Recycle Systems 131
Applied to Extractive Metallurgical Processes

shows that the average copper concentr ates is CuFe0.99S2.07 which

exp g KaAexp FE (1) is a stoichiometry that closely matches chalcopyrite. During the
1 RT smelting operation, iron is partially oxidized to FeO and Fe2O3
with O2. These oxides are then converted at high temperature into a
where, is fraction of surface coverage, a A is collector liquid phase (slag) using SiO2 and possibly other uxes.
concentration, and E is po tential. Constants g, K and can be
CuFeS2 O2 SiO2
estimated by regression from experimental data. The nal equation (3)
Matte (CuFeSuldes) Slag (FeSiOxides) SO2 (g)
for Ethyl Xanthate (EtX) chemisorption by chalcocite is:
The suldes remain as liquid matte. Using data from Figure 2
exp 4 8.4 109 X exp E (2) of Yazawa Ref. [13], the partial ternary diagram FeO-FeS-SiO2 in
1 0.016 Figure 10 was constructed. It shows how FeS-rich matte and FeS-
lean slag become two immiscible liquids by SiO2 addition. After
4.2 EH-pH Diagram of Flotaion Chemistry point A, shown on the diagram, the two phases begin to separate.
By combining all the Ethyl Xanthate (EtX) species for the Cu- 5.1.2 Matte Grade: The average matte grade from the survey
Fe-S system, the EH-pH diagram was constructed and is shown Ref. [12] is CuFe0.23S0.69. The Cu-Fe-S ternary diagram shown in
on Figure 9 using free energ ies reported by Forssberg Ref. [10]. Figure 11, originated from Schuhmann Ref. [14] and was redrawn
The diagram shows not only the predominant area of Cu plus by Davenport Ref. [1]. It is used to show the thermodynamic basis
xanthates species: EtX2 , CuEtX, EtX-, and EtX(chem). The shaded for matte composition. The symbol * on the diagram is from the
area on the diagram indicates where EtX(chem) can cover over survey Ref. [12] and clearly shows that the composition of matte is
90% of Cu2S. The diagram also indicate the EH and pH from some nearly saturated with liquid copper or solid iron.
discharged tailings from industrial otation reported by Forssberg 5.1.3 Slag Composition: The ternary diagram of FeO-Fe2O3-
Ref. [10]. For clarity, the extremely small areas are not labeled SiO2 in Figure 12, shows the thermodynamics of slag composition
with species on the diagram. Bowden and Young Ref. [11] used during the smelting operation. Indicated on the diagram, from the
voltammetry to verify the diagram under alkaline conditions. same survey Ref. [12], is the label “ A ” indicating the average
smelting temperature of 1242 at an average composition 30.5%
5 PYROMETALLURGY
SiO2. Under this average condition, according to Figure 12, FeO
About 80% of primary copper concentrate is treated by and Fe2O3 will be 51.5% and 18.0%, respectively.
pyrometallurgical operations. It starts by smelting copper
concentrate into matte and slag, then converting matte to blister 5.2 Converter Operation
copper (98.5 to 99.5% Cu) which is then electrorefined to make Remaining sulfides in the matte are further treated in the
high purity copper. Gold and other precious metals are recovered as converter by blowing air to form SO2 and produce blister copper.
slime. The basis for the operating chemical principles are presented From the survey Ref. [12], the average converter temperature is
by Davenport Ref. [1], and the survey of industrial operating 1223 , the S content in the feed materials is 22.41%, and the
conditions and production results are available in Copper 2003 Ref. purity of blister copper produced is 98.55%. The cutout Cu-S phase
[12]. Thermodynamics in this sectio n are explained using ternary diagram, shown Figure 13, indicates the direction of the reaction
and binary phase diagrams where op erating conditions from the of the matte to form blister copper and is marked with * for the
survey are also marked. temperatures and starting matte grades from the survey Ref. [12].

5.1 Smelter Operation 5.3 Pyrometallurgical Operation for Recycling Copper

5.1.1 SiO2 Separates Slag from Matte: Excluding data from Copper smelting is the most important step for treating
Russia, a survey of 45 major copper smelting operations Ref. [12] secondary source of copper for recycling. In order recover most

Figure 9 Mass-balanced EH-pH diagram of Cu sulfides under flotation

conditions. Mass of Cu- Fe-S-EtX are 2.91-2.91-5.82-1x10-4 Figure 10 Partial ternary phase dia gram of FeS -FeO-SiO2 at 1200 .
mole/L, respectively. The gray area indicates the predominance Composition of matte (o) and slag (*) under the inuence of
of EtX(chem). Symbol * repr esents the EH and pH of tailings fr SiO2 addition. Experimental points were taken from Yazawa
om otation operations taken from Forssberg Ref. [10]. Ref. [13].

Int. J. Soc. Mater. Eng. Resour. Vol.23, No.2, (Sep. 2018)

132 Hsin-Hsiung HUANG et al.

valuable metal, the smelting technology has to be adapted and

evolved from conventional method of treating sulde minerals.
The new “ black copper ” route that is commonly used consists
of both reduction and oxidation steps Ref. [15]. The combined
steps produce three output streams: liquid copper metal, slag and
exhaust gas that likely contain dust. The purpose of the operation is
to recover as much valuable metals as possible.
Due to the high investment required, only a handful of
companies are actually processing secondary recycle copper Ref.
[15]. The flowsheet of the Kosaka (Japan) operation is shown
on Figure 14 Ref. [16]. The smelting furnace is an Ausmelt that
runs under the multiple-stage batch cycled between oxidation and
reduction Ref. [17]. Three output streams are: slag to be discarded,
exhaust gas and dust which contains volatile Zn, Pb, Sn and Bi, and
Figure 11 Ternary phase diagram of Cu-Fe-S originated from Schuhmann
molten Cu which also contains precious metals as well as Ni and
Refs [1,14] showing composition of matte grades from the Co. All mixture of metals are treated and recovered as individually.
global survey Ref. [12] using the symbol *. 5.3.1 Iron Slag: Unlike copper from sulde concentrates, iron
is only a minor constituent in recycled copper. This unwanted
element is best rejected as a slag with proper ux using the phase
diagram of CaO- “ FeO ” -SiO2 Ref. [18]. Formation of an olivine
slag is the best choice, due to its low melting temperature, low
viscosity and low copper solubility Ref. [19]. The cut out diagram
with additional log pO2(g) in the area of olivine and its adjacent
minerals (Temperature 1200 ) are shown in Figure 15. Partial
oxygen pressures were calculated based on the measured Fe2O3
content (less than 4%) and free energies provided for the reaction
Ref. [20]. Below the temperature of 1200 on the liquidus
surface, the values of log pO2(g) are between -12 to -14, but, as
the temperature increases to 1500 , these log pO2(g) values can
increase to between -5.5 and -8.5.
5.3.2 Non-Ferrous Slag: To reject undesirable, non-ferrous
types of materials, the ternary phase diagram of Al2O3-CaO-SiO2
with 10% MgO system is deemed the most suitable. In this case,
the target temperature is in the area below 1200 Ref. [21]. The
Figure 12 Partial ternary phase diagr am of FeO-Fe2O3-SiO2 showing
percent compositions of SiO2-CaO-Al2O3-MgO at the center of this
composition of sl ag from the global sur vey Ref. [12]. The
areas are 53-23-14-10, respectively.
symbol A indicates the glob al average temperature of 1242
and SiO2 content of 30.57%. The area surrounded by darker 5.3.3 Ellingham Diagram: Ellingham diagrams involving
boarder covers temperature and %SiO2 from their average ± 1 oxides are a popular source to show oxidation-reduction reactions
standard deviation. between a metal and its oxide. Figure 16 shows some of selected
metals related to the copper recycling process. Assuming log pO2

Figure 13 Binary phase diagram of Cu-S-Temperature system indicating

the average converting te mperature and starting composition
of the matte grade with the symbol * from the global survey
Ref. [12].
Figure 14 Flowsheet diagram of Kosaka smelter operation (2016) Ref.
[16]

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 Stability Diagrams for Copper-Sulfide and Copper-Recycle Systems 133
Applied to Extractive Metallurgical Processes

Figure 15 The gray area of CaO- “ FeO ” -SiO2 ternary diagram represents Figure 17 Predominance diagram of log pO2(atm) versus Temperature (K)
the melting temperature below 1200 . The dashed lines determined using data from HSC Ref. [22] for the Sn-O system
separate 3 different minerals. Thicker contour lines and and showing pressure contours of log pSnO(g) as thin lines.
numbers present log pO2.

a much more aggressive lix iviant under elevated pressure and

temperature conditions. Many processes have been proposed and
developed, but only a few were successful Ref. [1]. Currently, one
of the prominent processes is chloride acid leaching Refs [23, 24].
According to the literature, there are 3 major groups of reactions to
the process.

Group 1. Oxygen can leach chalcopyrite to form soluble Cu(II)

chloride and solid elemental S and Fe2O3 :

4CuFeS2 5O2 8HCl

(4)
4CuCl2 (a) 8S 2Fe2O3 4H2O
Group 2. Cu(II) and Fe(III) chlorides can leach chalcopyrite to
form soluble Cu(I) and Fe(II) chlorides and solid elemental S:
Figure 16 The Ellingham diagram of selected metals and equilibrium
partial pressures of oxygen. The block area surrounded by CuFeS2 3CuCl2 (a) 10Cl
thick lines indicates that log pO2 ranges from -6 to -10 atm, (5-1)
4CuCl32 FeCl42 2S
and 1500 to 1700K.
CuFeS2 3FeCl2 13Cl
(5-2)
CuCl32 4FeCl42 2S
can be operated from -6 to -10 atm at temperature ranges from
1500 to 1700K, the diagram indicates: It is important to note that, at low pH, Cu(II) chloride is not capable
of oxidizing Fe chloride from 2+ to 3+.
a. Cu, Co and Ni will report to the stable molten metal; whereas,
Pb, Zn, Bi and Cd will vaporize into the exhaust. Group 3. Depending on the leaching pH, two solid phases can
b. Fe can easily be oxidized but cannot be reduced; hence it form such that Fe(III) chloride precipitates as Fe2O3 (hematite)
would stay as the slag to be discharged. when pH > 0.5, and Cu(II) chloride precipitates as Cu2Cl(OH)3
c. Sn can be easily converted to SnO2 by changing the oxygen (atacamite) when pH > 2.5.
pressure and temperature. It can also be vaporized as SnO(g)
2FeCl2 3H2O
as shown in Figure 17. (6-1)
Fe2O3 (s) 4Cl 6H

5.3.4 Partial Pressure of a Minor on a Predominance

2CuCl2 (a) 3H2O
Diagram: For vaporization purposes, it is crucial to indicate the (6-2)
Cu2Cl (OH)3 (s) 3Cl 3H
partial pressure of their gaseous species. The log pO2(g) versus
Temperature diagram for Sn is shown on Figure 17 in which the The EH-pH diagram for the Cu-Fe-S-Cl system shown in Figure 14
dominant species are Sn(l), SnO(l) and SnO2. In this regard, the is presented to illustrate the basis reactions for the chloride leach.
pressures contours of SnO(g) are also plotted in light gray. The area of chalcopyrite is painted in light gray, and elemental S
is in darker gray. The diagram indicates th e reactions by drawing
6 HYDROMETALLURGY
directional arrows from reactant to product with their group
6.1 Chloride Elevated Temperature Leach numbers as described from Equations 4 to 6-2.
Secondary copper sulfides such as Cu2S and their oxidized
products are suitable for leaching with dilute sulfuric acid at 6.2 Hydrometallurgy for Secondary Recycle Copper
ambient temperature. The processes can be chos en from dump to Most of investigations on direct leaching of secondary recycled
agitation leaching. The more refractory type of primary sulfides copper utilize traditional hydrometallurgical technology from
such as chalcopyrite requires ne grinding to particles < 15 m and leaching, and purication to metal recovery. More specic, small

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134 Hsin-Hsiung HUANG et al.

Table 1 Redox potentials of possible oxidants and metal/metal chloride

complexes. NBS database Ref. [26] is used for the calculation.

Figure 18 EH-pH diagram for the Cu-Fe-S-Cl system to illustrate the

chloride leaching reactions at 100 . The equilibrium
line method was used with the LLnL database Ref. [5] at
concentrations of [Cu] [Fe] 1, [S] 2 and [Cl] = 5 moles/
L. Arrows indicate the direction of reaction, and numerical
numbers indicated the reaction groups described in the text.

Figure 19 EH-pH diagram of Cu inuenced by ammonia and by chloride

at 25 . Concentrations of NH3:Cl-:Cu are 2:1:0.01 mole/L,
respectively. NBS database Ref. [26] was used. Figure 20 Bioleaching of metal suldes proposed by Sand Ref. [19] has
two different indirect mechanisms: (a) thiosulfate path for acid-
insoluble sulfides such as pyrite and (b) polysulfide path for
scale, and highly protable material such as printed circuit board acid soluble sul des such as chalcopyrite.
(PCB) for recovering Cu, precious metals, Zn, Ni, Sn and Pb have
been investigated with hydrochloric acid Ref. [15] and ammonia
Ref. [25] as the two leaching reagents most considered.
The EH-pH diagram of copper associated with HCl at low pH
and NH4OH at high pH is shown on Figure 19. Both reagents have
the capability to leach metal and be regenerated by O2(gas). The
chloride is represented by Equations 5-1 and 6-2; whereas, the
ammonia system is represented by Equations 6-3:
Table 1 lists reactions and equilibrium potential for chloride
leaching of important metals from PCB as well as the potentially
useful oxidants. The mixture of HCl with HNO3, even aqua regia,
is sometimes suggested. Nitric acid will serve not only as an
oxidant and also to ensure the dissolution of all metal chlorides.
Hydrometallurgical processes should not be ignored for
recycling processes. For example, as shown by the owsheet for
Figure 21 Speciation diagram of S versus EH for pyrite (FeS2) that follows
the Kosaka smelting in Figure 14, except for two pyro-furnaces, the thiosulfate path of bioleaching. S 0.0001 moles/L at
almost all sub-sequent processes involve hydrometallurgical 25C and pH 1.5.
separation and recovery of individual metals.

6.3 Bacterial Oxidation of Metal Sulfides

The mechanism of bioleaching from metal sulfides in aerobic The latest report from Sand et al. Ref. [27] proposed two different
environments has been subjected to investigation for many years. paths for biooxidation: (a) thiosulfate mechanism for acid-insoluble

Int. J. Soc. Mater. Eng. Resour. Vol.23, No.2, (Sep. 2018)

 Stability Diagrams for Copper-Sulfide and Copper-Recycle Systems 135
Applied to Extractive Metallurgical Processes

unit operations are needed to additionally recover precious

metals and other base metals. Thermodynamic calculations for
processing these valuable metals are critical:
a. Pyrometallurgy–Phase diagrams for slag formation,
predominance diagrams of Sn-O and for vaporization of SnO
gas, and Ellingham diagram for interaction between metal and
their oxides.
b. Hydrometallurgy–EH-pH diagrams for leaching of Cu using
chloride and ammonia. The tabulated equilibrium potentials
for oxidants and dissolution of metals in chloride system.

Acknowledgements
The authors would like to thank the Montana Tech Library for
Figure 22 Speciation diagram of S versus EH for chalcopyrite that follows
the polysulfide path of bioleaching with S 0.0001 moles/
their collections, and librarians for their help obtaining v aluable
L at 25C and pH 1.5. The diagram also shows in light gray the references. The authors would like to thank Dr. Yasushi Takasaki
polysulde species which are less stable than Elemental S. of Akita University for providing papers covering the Fundamental
Studies on Copper Smelting Reports published by Professor
Yazawa when he was at Tohoku University. Particular thanks to
suldes such as p yrite and MoS2, and (b) poly sulde mechanism ICMR 2017 Akita Organization for their invitation and financial
for acid soluble sulfides such as chalcopyrite and other copper support for hosting Dr. Hsin-Hsiung Huang when he lectured and
suldes. Their reaction paths are presented on Figure 20. presented at the conference (October 25-27 2017) and attended the
These two oxidation paths can be seen from their speciation eld trip to the Kosaka Smelter (October 23-24 2017). Dr. Huang
versus EH diagrams. Figure 21 is for the thiosulfate path and personally thanks faculties and staff at Akita University while in
Figure 22 is for the polysulde path. Both diagrams used dGs from Japan, particularly Dr. Kazutoshi Haga for his translations, and Dr.
Forssberg Ref. [10] but requ ired additional thiosulfate species Yasushi Takasaki for his hospitality and guidance.
were taken from HSC Ref. [22], and additional polysulde species
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