PROJECT METALLURGIST

Design of agitated leach

circuit
Reductive leaching of Copper and Cobalt ores

KAFUMBILA KASONTA JOSEPH

2021
Design of agitated leach circuit: reductive leaching of Copper and Cobalt ores
© Joseph Kafumbila 2021
[email protected]

Joseph Kafumbila Page 1

 Process simulation
Chemical engineering can be defined from many different aspects. However, all
the scientists and professionals agree that the process is the center of it. To make a
distinction from any other discipline, the role of chemical engineering could be defined
with its purpose to develop, design, construct, control, optimize and mange any process
involving physical and/or chemical changes and make this process profitable.

Process simulation as discipline uses mathematical models as basis for analysis

prediction, testing, detection of a process behavior unrelated to whether the process is
existing in reality or not. Process simulation is there to increase the level of knowledge
for a particular process and chemical engineering in general.

So, when those two concepts are put together, we can look into the chemical
engineering as a discipline defining how the process should be developed and
simulation as the tool helping us to explore the options. Chemical engineering needs to
know how the process should be designed while chemical engineers use the simulation
to explore all the process design options and define the optimal one.

Joseph Kafumbila Page 2

 Abstract
The reductive leaching of Copper and Cobalt ores using SO2 gas as reducing
reagent is a complex process. During reductive leaching of Copper and Cobalt ores,
firstly iron plays an important role as a catalyst because the direct dissolution of
Heterogenite with soluble sulfite compounds is limited by migration into the solid pores
and secondly iron has a saturation concentration controlled by the precipitation of
Copiapite. The presence of phosphoric acid coming from dissolution of pseudo malachite
precipitates Iron as Strengite. The presence of Cobalt and Manganese ions in the leach
solution produces dithionate in the first stage and Caro,s acid in the second stage by
absorbing surface oxygen of the ore. The absorption of surface oxygen by sulfite
compounds decreases the acid consumption. The presence of dithionate in the leach
solution decreases the concentration of free sulfate anions to have the electrical
neutrality of solution. The consequence of the presence of dithionate in the leach
solution is the increase of the saturation concentrations of Calcium and Iron. The
production of Caro’s acid increase the SO2 gas consumption by reducing Caro’s acid to
sulfate compounds in the reductive leach conditions. In these conditions, the prediction
of SO2 gas consumption is difficult. The purpose of this publication is the prediction of
saturation concentration of iron into leach solution and to give the leach circuit layout.

Joseph Kafumbila Page 3

 Contents

5. Agitated leach circuit 5

5.1. Design criteria 5
5.2. Major equipment sizing 5
5.2.1. Leach tank live volume 5
5.2.2. Diameter and Height of tank 5
5.2.3. Impeller power 6
5.3. Preliminary flow diagram mass balance 6
5.3.1. Test leach parameters 6
5.3.2. Iron and Phosphorous saturation concentrations in leach solution 9
5.3.3. Copiapite precipitation 36
5.3.4. Strengite precipitation 36
5.3.5. Liquid specific gravity 37
5.3.6. Leach circuit layout 38
5.3.7. Flow diagram 44
5.3.8. Preliminary flow diagram mass balance Table 44
5.3.9. Procedure of flow diagram mass balance 49
5.3.10. Procedure of flow diagram mass balance 63

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5. Agitated leach circuit
5.1. Design criteria

 Leaching feed material P80: 70 – 150 µm.

 Minimum number of leach tanks in series: 4
 Maximum solid percent in leach pulp for copper leaching: 40%.
 Maximum solid percent in leach pulp for cobalt leaching: 30%.
 Leach residence time: less than 2hours for Copper and less than 8hours for Cobalt.

5.2. Major equipment sizing

5.2.1. Leach tank live volume

Equations (5.1) and (5.2) give total live volume and live volume per tank

VLT =Vp *TR (5.1)

VLT
VL = (5.2)
N

Where “𝑉𝐿𝑇 ” is leach tank total live volume (m3), “𝑉𝐿 ” is live volume per leach
tank, “𝑉𝑃 ” is leach pulp volume flowrate (m3/h), “𝑇𝑅 ” is the retention time (hrs)
and “N” is number of tanks (minimum 4).

5.2.2. Diameter and Height of tank

Figure (5.1) gives leach tank layout. Equations (5.3) and (5.4) give the ratio D/H
and total volume of the tank.

D
=R=0.9 (5.3)
H

π π
VT = *D3 =VL + *D2 *HB (5.4)
4∗R 4

“H” is leach tank height (m), “D” is leach tank diameter (m) and “𝐻𝐵 ” is free
board (m).

Joseph Kafumbila Page 5

 Figure 5.1: Leach tank layout

5.2.3. Impeller power

Impeller power is design from impeller pumping power.

5.3. Preliminary flow diagram mass balance

5.3.1. Test leach parameters

Standard stirred leaching test on feed material gives element solubility, leach
weight loss, CO2 loss, leaching time and acid consumption. Leach solid percent used in
standard stirred leaching test is 20% of solid feed in the leach pulp at time equal to zero.
At the other hand the leach percent used in the mass balance is solid percent in the leach
pulp at the end of leach. Acid solution is added for pH control. Value of pH used in
leaching test and processing plant is 1.8 for copper leach test. Standard leaching test is
done at ambient temperature.

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5.3.1.1. Element solubility

Equation (5.5) gives the mass of element into the solid.

XEl =Msol ∗ GEl *10 (5.5)

Where “𝑋𝐸𝑙 ” is element mass (kg), “𝑀𝑠𝑜𝑙 ” is solid mass (t) and “𝐺𝐸𝑙 ” is grade of
element into the solid.

Equation (5.6) gives element leach efficiency (Cu, Fe, Al, Co, Zn, Ni, Mn, Mg and
K).

XR
LEEl =100*(1- El
) (5.6)
XF
El

R
Where “LEEl ” is the element leach efficiency (%), “XEl ” is element mass into the
F
leach residue (kg) and “XEl ” is element mass into the leach feed (kg)

Equation (5.7) gives element solubility.

XF F
El −XEl GEl ∗LEEl
SolEl = = (5.7)
Msol 10

Where “ 𝑆𝑜𝑙𝐸𝑙 ” is the solubility of an element (kg/t), “𝐺𝐸𝑙 ”is the grade of an
element in the feed ore (%) and “𝐿𝐸𝐸𝑙 ” is the leaching efficiency of an element
(%).

Equation (5.8) gives phosphoric acid solubility (PA)

SolPA =GP ∗ LEP *0.316 (5.8)

Where “ 𝑆𝑜𝑙𝑃𝐴 ” is the solubility of phosphoric acid (kg/t), “𝐺𝑃 ”is the grade of
phosphorous in the feed ore (%) and “𝐿𝐸𝑃 ” is the leaching efficiency of
phosphorous (%).

Equation (5.9) gives the CO2 production.

CO2P=GC ∗ LEC *0.367 (5.9)

Where “CO2P” is CO2 production (kg/t), “𝐺𝐶 ” is carbon grade in the feed ore (%)
and “𝐿𝐸𝐶 ” is the leaching efficiency of carbon (%).

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5.3.1.2. Total acid consumption

Equation (5.10) gives the total acid consumption.

Ac Ac Ac Ac
TAC=MLS +MAcS -MFil -MAcSM (5.10)

𝐴𝑐
Where “TAC” is the total acid consumption (kg/t of solid feed), “ 𝑀𝐿𝑆 ” is mass of
𝐴𝑐
free acid in the leach solution (kg/t of solid feed), “𝑀𝐴𝑐𝑆 ” is mass of free acid in
𝐴𝑐
the acid solution used for pH control (kg/t of sold feed), “𝑀𝐹𝑖𝑙 ” is the free acid in
𝐴𝑐
the filtrate and wash solution (kg/t of solid feed) and “ 𝑀𝐴𝑐𝑆𝑀 ” is the acid
consumed by the SMBS (kg/t of solid feed)

The chemical reaction (5.a) gives the reaction SMBS with acid. The acid
consumed by SMBS is equal to 0.516t/t of SMBS.

Na2 S2 O5 +H2 SO4 =2SO2 +Na2 SO4 (5.a)

Equation (5.11) gives the gangue acid consumption.

GAC=TAC - SolCu *1.543 (5.11)

Where “GAC” is gangue acid consumption (kg/t), “TAC” is total acid

consumption (kg/t) and “𝑆𝑜𝑙𝐶𝑢 ” is Copper solubility (kg/t).

5.3.1.3. Sulfur dioxide consumption

Value of pH used in leaching test and processing plant is 1.5 for cobalt leach test
and Iron concentration is the leach acid solution is 2.0g/L. The leach redox potential is
regulated at 350 mV (Ag/AgCl) during the leach test using SMBS (J. Kafumbila, 2020a).1
Table (5.1) gives the mass balance of elementary sulfur.

Table 5.1: Mass balance of elementary sulfur

Inlet Outlet
s s s s s s S
MFee MLS MAcS MSMB MRes MFil MOuG

1 J. Kafumbila, 2020a, Utilization efficiency of sulfur dioxide during reductive leaching of Copper
– Cobalt ores - (PDF) Utilization efficiency of sulfur dioxide during reductive leaching of
Copper -Cobalt ores (researchgate.net)

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 𝑠
Where “𝑀𝐹𝑒𝑒 ” is mass of elementary sulfur in the solid feed (kg/t of solid feed),
𝑠
“𝑀𝐿𝑆 ” is mass of elementary sulfur in the leach solution (kg/t of solid feed), “
𝑠
𝑀𝐴𝑐𝑆 ” is mass of elementary sulfur in acid solution for pH control (kg/t solid
𝑠
feed), “𝑀𝑆𝑀𝐵 ” is mass of elementary sulfur in SMBS for Redox potential control
𝑠
(kg/t of solid feed), “𝑀𝑅𝑒𝑠 ” is mass of elementary sulfur in the washed leach
𝑠
residue (kg/t of solid feed), “𝑀𝐹𝑖𝑙 ” is mass of sulfur in the filtrate and wash
𝑆
solution (kg/t of solid feed) and “𝑀𝑂𝑢𝐺 ” is mass of elementary sulfur in the leach
gas (kg/t of solid feed).

S
Equation (5.12) gives the value of MOuG .

S s s s s s s
MOuG =MFee +MLS +MAcS +MSMB -MRes -MFil (5.12)

Equation (5.13) gives the SO2 consumption (SO2C) (kg/t of solid feed).

s S
SO2C= (MSMB -MOuG )*1.998 (5.13)

5.3.1.4. Leach weight loss

Equation (5.14) gives the leach weight loss (kg/t of solid feed)

MR
LWL= (1 - Sol
)*1000 (5.14)
MF
Sol

𝑅
Where “LWL” is leach weigh loss (kg/t of feed solid), “𝑀𝑆𝑜𝑙 ” is mass of residue
𝐹
after leach test (t) and “𝑀𝑆𝑜𝑙 ” is the mass of feed before leach test (t).

5.3.2. Iron and Phosphorous saturation concentrations in leach solution

5.3.2.1. Concept

During reductive leaching of Copper and Cobalt ore, Iron is leached. When Fe
concentration reaches the saturation concentration, Fe precipitates as Copiapite
(Fe5 (SO4 )6 (OH)2 . 20H2 O). The chemical reaction (5.b) gives Copiapite precipitation
reaction (J. Kafumbila, 2020b).2 At the same time, Phosphorous containing in Pseudo
Malachite is leached. Phosphorous precipitates with Fe(III) as Strengite (FePO4 . 2H2 O)
when phosphoric acid concentration reaches the saturation concentration. The chemical

2 J. Kafumbila, 2020b, Iron precipitation during leaching of copper and cobalt ores - (PDF) Iron
precipitation during leaching of Copper and Cobalt ores: Geochemical modelling
(researchgate.net)

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reaction (5.c) gives Strengite precipitation reaction. The purpose is to determine the
saturation concentrations of Iron in equilibrium with Copiapite and the saturation
concentration of phosphoric acid in equilibrium with Strengite.

FeSO4 +2Fe2 (SO4 )3+22H2 O=Fe5 (SO4 )6 (OH)2 . 20H2 O+H2 SO4 (5.b)

Fe2 (SO4 )3 +2H3 PO4 =2FePO4 . 2H2 O+3H2 SO4 (5.c)

5.3.2.2. Calcium concentration in the leach solution

It has been observed during reductive leach of Copper and Cobalt using SO 2 gas
as reducing reagent that the concentration of Calcium is high in the leach solution
(around 0.7g/L) comparatively to the concentration of Calcium into leach solution
obtaining from ordinary leach (0.5g/L). The concentration of calcium is the saturation
concentration in equilibrium with gypsum. The increase of calcium concentration is due
to two possibilities:

 Calcium forms soluble complex compounds with sulfite compounds.

 There is a presence in the leach solution of soluble compounds with
negative charge which decrease the concentration of SO−2
4 to have the
electrical neutrality of leach solution.

In the previous simulation model of reductive leach of Copper and Cobalt ore
using SO2 gas as reducing reagent, the assumption was that the leach solution is
saturated with free SO2 gas in the last leach tanks. The saturation of leach solution with
Free SO2 has been realized at Shituru plant in the pulped tank before leach tanks after 12
hours. Leach pH and leach Eh were respectively 2.0 and 0.35V (K. Kafumbila et al,
2002).3 Free SO2 gas Free SO2 gas is in equilibrium with sulfite compounds (HSO− 3 and
−2
S2 O5 ). Firstly calcium forms soluble complex with sulfite compounds and secondly
−2
HSO− 3 and S2 O5 are considered as the soluble compounds with negative charge whose
presence decreases the concentration of SO−2 4 in the leach solution to have the electrical
neutrality of leach solution.

This model was applied to pilot plant Data (Table 5.2) (J. Kafumbila, 2020b).
This model is reviewed by taking only predominate soluble compounds into the range of
leach pH (1 to 2). The application of this new model to pilot plant data gives the
solubility of free SO2 gas as function of solution ionic strength.

3 K. Kafumbila et al, 2002, Use of sulfur dioxide as reducing agent in cobalt leaching at shituru
hydrometallurgical plant, SAIMM.

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 Table 5.2: Pilot plant solution composition

Data Eh pH Element concentration (g/L)

(V) Cu Co Al Mg Mn Zn Ca Fe
3-Jul 0.584 1.84 3.098 9.807 0.766 1.955 3.969 0.969 0.754 1.070
4-Jul 0.587 1.8 4.212 10.935 1.101 2.092 4.243 1.059 0.710 1.099
5-Jul 0.578 1.77 3.021 10.52 1.105 2.087 4.123 1.002 0.656 1.059
6-Jul 0.567 1.75 3.855 11.308 1.272 2.266 4.498 1.174 0.772 1.123
7-Jul 0.570 1.832 3.322 11.337 1.252 2.26 4.356 1.184 0.738 1.195
8-Jul 0.569 1.81 3.666 11.713 1.24 2.353 4.462 1.135 0.736 1.354
9-Jul 0.595 1.96 4.885 12.126 1.245 2.461 2.461 1.132 0.697 1.862
10-Jul 0.622 1.542 5.84 12.557 1.285 2.455 4.379 1.199 0.663 1.737
11-Jul 0.585 1.44 6.233 12.485 1.298 2.542 4.897 1.257 0.663 1.699
12-Jul 0.562 1.57 7.019 10.594 1.03 1.998 1.094 1.089 0.569 1.315
13-Jul 0.57 1.66 4.563 9.033 0.956 1.829 4.012 1.026 0.675 1.186
14-Jul 0.538 1.92 3.547 9.471 1.049 1.926 4.388 1.16 0.745 1.183
15-Jul 0.562 2.04 4.762 9.645 0.99 1.75 4.209 1.148 0.724 1.417
16-Jul 0.602 1.54 4.335 10.436 1.084 1.888 4.301 1.145 0.694 1.864
17-Jul 0.576 1.66 4.704 10.342 1.023 1.995 4.477 1.252 0.757 1.679
18-Jul 0.587 1.67 5.463 9.284 0.991 1.895 3.903 0.985 0.721 1.454
19-Jul 0.62 1.72 4.868 9.227 0.992 1.889 3.758 1.114 0.682 1.024
20-Jul 0.668 1.7 5.688 8.357 0.937 1.969 3.425 1.144 0.605 0.415
21-Jul 0.641 1.61 6.607 7.741 0.871 1.729 3.267 1.159 0.629 0.969
22-Jul 0.596 1.67 6.1 8.671 0.892 1.704 4.067 1.105 0.689 1.198
23-Jul 0.624 1.73 5.477 8.412 0.894 1.76 3.41 1.193 0.641 0.575
24-Jul 0.615 1.45 4.501 6.183 0.699 1.304 2.566 0.855 0.59 0.238
25-Jul 0.603 1.6 4.933 6.375 0.648 1.203 2.239 0.743 0.583 0.231
26-Jul 0.596 1.38 5.015 7.264 0.733 1.491 2.724 0.865 0.759 0.560
27-Jul 0.571 1.36 3.937 6.8 0.777 3.025 2.608 0.828 0.698 0.617
28-Jul 0.559 1.52 4.27 7.349 0.853 1.625 2.881 0.858 0.707 0.754
29-Jul 0.591 1.4 2.565 7.816 0.801 1.394 2.755 0.85 0.665 0.804
30-Jul 0.562 1.66 4.383 8.124 0.755 1.477 3.16 0.993 0.682 1.043
31-Jul 0.56 1.53 3.761 6.542 0.657 1.191 2.529 0.791 0.551 0.845
1-Aug 0.565 1.52 4.2 7.304 0.727 1.344 2.758 0.855 0.568 0.905
2-Aug 0.575 1.55 3.955 8.618 0.864 1.549 3.207 0.973 0.618 1.056
3-Aug 0.572 1.54 4.414 8.15 0.839 1.52 3.346 0.922 0.557 0.98
4-Aug 0.59 1.46 6.342 12.406 1.154 2.09 4.748 1.299 0.699 1.274
6-Aug 0.59 1.35 8.96 11.574 1.173 2.133 4.69 1.193 0.672 1.355
7-Aug 0.584 1.38 5.065 9.021 0.959 1.661 3.711 1.095 0.634 1.249
8-Aug 0.574 1.44 5.898 9.603 0.996 1.785 3.954 1.101 0.741 1.292
9-Aug 0.583 1.35 3.628 11.011 1.048 1.941 4.227 1.452 0.726 1.528
10-Aug 0.596 1.42 3.94 9.945 0.999 1.803 4.019 1.42 0.723 1.447
11-Aug 0.582 1.39 4.17 10.024 1.048 1.855 3.898 1.306 0.706 1.311
12-Aug 0.575 1.37 5.447 10.171 1.028 1.788 3.784 1.141 0.758 1.253
13-Aug 0.564 1.4 4.084 10.427 1.033 1.876 3.827 1.175 0.758 1.341
14-Aug 0.567 1.32 4.151 10.623 1.149 1.951 3.722 1.168 0.808 1.409
15-Aug 0.577 1.3 4.106 11.785 1.216 2.253 3.949 1.206 0.728 1.543
16-Aug 0.573 1.37 4.646 12.46 1.324 2.366 4.423 1.249 0.756 1.665
17-Aug 0.569 1.38 4.894 12.648 1.356 2.511 4.525 1.272 0.688 1.671
18-Aug 0.571 1.31 4.21 12.928 1.372 2.507 4.717 1.351 0.691 1.693
19-Aug 0.568 1.4 5.443 14.298 1.441 2.578 5.267 1.306 0.704 1.846
20-Aug 0.574 1.4 6.19 13.477 1.452 2.81 4.974 1.34 0.686 1.912
21-Aug 0.576 1.3 6.43 12.72 1.407 2.518 4.978 1.29 0.744 2.019
22-Aug 0.573 1.35 2.873 12.103 1.25 2.359 4.198 1.053 0.66 1.918
23-Aug 0.577 1.37 3.97 10.91 1.114 2.219 3.844 0.967 0.603 1.829

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5.3.2.3. Pilot plant description

As part of feasibility study, pilot plant has been operated during 2 months with
homogenous feed to recover Copper as full plate cathode from Copper-Cobalt ore. The
flow diagram of pilot plant is shown on Figure (5.2). Copper and Cobalt grades in the
feed are respectively 1.478 and 0.325%. Table (5.3) gives the mineralogical composition
of pilot plant feed.

Figure 5.2: Flow diagram of copper plant of pilot plant

The feed is leached in sulfuric acid and barren solution in the primary leach
tanks. Leaching dissolves the metals from the solids at pH 2 during 2 hours. SO 2 gas is
injected in the primary leach tanks to reduce the redox potential at 350 mV (Ag/AgCl).
The reduction of redox potential prevents the iron precipitation. The purpose of the
primary leach is to produce a copper rich solution having a low concentration of free
acid. The leach efficiencies of copper and cobalt are respectively 75 and 70%. Slurry
discharged from the primary leach is thickened.

Overflow solution is called the pregnant leach solution (PLS) and is fed to the
copper solvent extraction circuit. Underflow from the primary leach thickener proceeds
to the secondary leach. The underflow from the primary leach thickener is leached in

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sulfuric acid and barren solution in the secondary leach tanks at pH 1.5 during 6 hours.
SO2 gas is injected in the secondary leach tank to reduce the redox potential at 350 mV
(Ag/AgCl). The purposes of the redox potential reduction and the increase of free acid
concentration are to leach the remaining cobalt. The leach efficiencies of copper and
cobalt are respectively 20 and 18%. Slurry discharged from the secondary leach is
thickened. Overflow solution from this thickener reports to the storage solution tank.
Underflow from the thickener reports to the filtration circuit.

The underflow from secondary leach thickener is pumped to the vacuum belt
filter. Vacuum is applied to the belt across two zones: The first zone, called the form
zone or dewatering zone, forms the slurry into a cake on the belt and removes the
entrained leach solution. In the second zone, called the washing zone, the filter cake on
the belt is washed using wash water to remove the remaining entrained leach solution.
The leach solution is recovered from the first zone of the belt filters as filtrate. The
filtrate is pumped back to the storage tank. The filter cake moves on the filter belt from
the form zone to the wash zone and the cake is washed with water that has been
acidified to pH 3. Wash solution is pumped to the secondary copper solvent extraction.

Table 5.3: Mineralogical composition of pilot plant feed

Minerals Grade
%
Cu2(OH)2(CO3) 1.584
Cu3(PO4)2.Cu2(OH)4 0.146
2CuO.2SiO2.3H2O 0.199
CuO 0.503
CuS 0.005
Cu2S 0.005
CuFeS2 0.005
CoOOH 0.507
FeO(OH) 1.954
Ni(OH)2 0.001
CaCO3.MgCO3 0.900
MnO2 0.127
ZnS 0.007
SiO2 77.139
UO3 0.004
Mg2SiO4 5.381
Ca2SiO4 0.011
CaCl2 0.025
Al2SiO5 11.471
Cr2O3 0.026
CdO 0.001

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 In the primary copper solvent extraction; Copper is thus recovered from the PLS
into an organic liquor, which contains an extractant within a diluent. The PLS aqueous
solution is stripped of copper and is now referred to as the copper raffinate. The copper
raffinate stream is returned to storage tank. The loaded organic stream (LO) from the
extraction circuit is stripped with spent copper electrolyte (SE) from the copper
electrowinning (EW) section. Stripping produces the advance electrolyte and stripped
organic, the latter being recycled to Cu SX.

Secondary Cu SX consists only of an extraction stage, designed to strip any

residual copper from the solution before it proceeds to iron precipitation. From the
stripped organic, a portion of the stripped organic stream is returned to the secondary
SX.

Copper metal is electro-deposited from the advance electrolyte onto stainless

steel blanks, known as cathodes, over a 6-day cycle. Spent copper electrolyte is returned
to the copper SX circuit.

5.3.2.4. Leach redox potential

The leach redox potential is mixed redox potential. The mixed potential is an
electrode potential resulting from a simultaneous action of more than a single redox
couple. The approximation is that the leach redox potential is close to equilibrium redox
potential for all single redox in the leach pulp.

5.3.2.5. New model of reductive leach of Copper and Cobalt ores with sulfite
compounds

This simulation model of reductive leach of Copper and Cobalt ores is

established with predominate soluble compounds in the range from 1 to 2 pH. In the
leach solution, the molarity is equal to molality because the concentrations of element
are low.

 Solid compounds

The solid compounds are the following: CaSO4 . 2H2 O and FePO4 . 2H2 O

The chemical reactions (5.d) and (5.e) give the precipitation reactions of
CaSO4 . 2H2 O and FePO4 . 2H2 O.

Ca+2 + SO−2
4 + 2H2 O =CaSO4 . 2H2 O (5.d)

Fe+3 + H2 PO−
4 + 2H2 O =FePO4 . 2H2 O+2H
+
(5.e)

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  Strengite

The concentration of H2 PO− 4 is given by Equation (5.15). The equilibrium

constant (K (5.e) ) is given in Table (5.5). Where m(H+) is the concentration of H + , m(Fe+3 )
is the concentration of Fe+3 and aw is water activity.

((m(H+ ) )2 ∗γ1 )
m(H2 PO−4 ) =K (5.e) *m 2)
(5.15)
(Fe+3 ) ∗γ3 ∗((aw )

 Soluble compounds

 Water

Predominate water soluble compound is H + . The concentration of H + (m(H+) ) is

given by Equation (5.16).

m(H+) =10(−pH) *(γ1 )(−1) (5.16)

 Sulfate

Predominate sulfate soluble compounds are SO−2 4 and HSO− 4 . Equilibrium

chemical reaction between sulfate soluble compounds is given by the chemical reaction
(5.f). m(SO−2
4 )
is the concentration of SO−2
4 and m(SO−2
4 )
is given by Equation (5.17). The
concentration of HSO−
4 (m(HSO−
4)
) is given by Equation (5.18). m(Ca+2 ) is concentration of
Ca+2 . K (5.d) and K (5.f) are in Table (5.5).

SO−2 + −
4 + H =HSO4 (5.f)

1
m(SO−2 =
4 ) K 2 2
(5.17)
(5.d) ∗m(Ca+2 ) ∗(γ2 ) ∗(aw )

m(HSO−4 ) =K (5.f) *m(SO−2

4 )
*m(H+ ) *γ2 (5.18)

 Phosphate

Predominate phosphate soluble compounds are H3 PO4 and H2 PO− 4 . Equilibrium

chemical reaction between phosphate soluble compounds is given by the chemical
reaction (5.g). m(H2 PO−4 ) is the concentration of H2 PO− 4 and the concentration of H3 PO4
(m(H3 PO4 ) ) is given by Equation (5.19). K (5.g) is in Table (5.5).

H2 PO− +
4 + H =H3 PO4 (5.g)

Joseph Kafumbila Page 15

 m(H3 PO4 ) =K (5.g) *m(H2 PO−4 ) *m(H+) *(γ1 )2 (5.19)

 Sulfite

−2
Predominate sulfite soluble compounds are SO2 , HSO− 3 and S2 O5 . Equilibrium
chemical reactions between sulfite soluble compounds are given by the chemical
reactions (5.h) and (5.i). m(HSO−3 ) is the concentration of HSO−
3 and m(SO2 ) and m(S2 O−2
5 )
are given by Equations (5.20) and (5.21). K (5.h) and K (5.i) are in Table (5.5).

HSO− +
3 +H =SO2 +H2 O (5.h)

−2
2HSO−
3 =S2 O5 +H2 O (5.i)

m(HSO− ) ∗m(H+ ) ∗(γ1 )2

3
m(SO2 ) =K (5.h)* (5.20)
aw

(m(HSO− ) )2 ∗(γ1 )2
m(S2 O−2
5 )
=K (5.i) * 3
(5.21)
γ2 ∗aw

 Calcium

Predominate Calcium soluble compounds are Ca+2 , CaSO4 , CaSO3 and CaH2 PO+ 4.
Equilibrium chemical reactions between Calcium soluble compounds are given by the
chemical reaction (5.j), (5.k) and (5.l). m(Ca+2 ) is the concentration of Ca+2 and the
concentration of CaSO4 (m(CaSO4 )), the concentration of CaSO3 (m(CaSO3 )) and the
concentration of CaH2 PO+
4 (m(CaH2 PO+
4 )
) are given by Equation (5.22), (5.23) and (5.24).
The total concentration of soluble Ca (m(CaT) ) is given by Equation (5.25). m(CaT) is in
Table (5.2). K (5.j) , K (5.k) and K (5.l) are in Table (5.5).

Ca+2 + SO−2
4 = CaSO4 (5.j)

Ca+2 + HSO−
3 = CaSO3 + H
+
(5.k)

Ca+2 + H2 PO− +
4 =CaH2 PO4 (5.l)

m(CaSO4 ) =K (5.j) *m(Ca+2 ) *m(SO−2

4 )
*(γ2 )(2) (5.22)

m(Ca+2 ) ∗m(HSO− ) ∗γ2

3
m(CaSO3 ) =K (5.k) (5.23)
m(H+ )

m(CaH2 PO+4 ) =K (5.l) *m(Ca+2 ) ∗ m(H2 PO−4 ) ∗ γ2 (5.24)

Joseph Kafumbila Page 16

 m(CaT) =m(Ca+2 ) +m(CaSO4) +m(CaSO3 ) +m(CaH2 PO+4 ) (5.25)

 Magnesium

Predominate Magnesium soluble compounds are Mg +2 , MgSO4 and MgH2 PO+ 4.

Equilibrium chemical reactions between Magnesium soluble compounds are given by
the chemical reaction (5.m) and (5.n). m(Mg+2 ) is the concentration of Mg +2 and the
concentration of MgSO4 (m(MgSO4 )) and the concentration of MgH2 PO+
4 (m(MgH2 PO+
4 )
)
are given by Equation (5.26) and (5.27). The total concentration of soluble Mg (m(MgT))
is given by Equation (5.28). m(MgT) is in Table (5.2). K (5.m) and K (5.n) are in Table (5.5).

Mg +2 + SO−2
4 = MgSO4 (5.m)

Mg +2 + H2 PO− +
4 =MgH2 PO4 (5.n)

m(MgSO4) =K (5.m) *m(Mg+2 ) *m(SO−2

4 )
*(γ2 )(2) (5.26)

m(MgH2 PO+4 ) =K (5.n)*m(Mg+2 ) ∗ m(H2 PO−4 ) ∗ γ2 (5.27)

m(MgT) =m(Mg+2 ) +m(MgSO4 ) +m(MgH2PO+4 ) (5.28)

 Aluminum

Predominate Aluminum soluble compounds are Al+3 , AlSO+ −

4 , Al(SO4 )2 and
AlH2 PO+2
4 . Equilibrium chemical reactions between Aluminum soluble compounds are
given by the chemical reactions (5.o), (5.p) and (5.q). m(Al+3 ) is the concentration of Al+3
and the concentrations of AlSO4+ (m(AlSO+4 ) ), Al(SO4 )−
2 (m(Al(SO4 )−
2 )
) and AlH2 PO+2
4
(m(AlH2PO+2
4 )
) are given by Equations (5.29), (5.30) and (5.31). The total concentration
of soluble Al (m(AlT)) is given by Equation (5.32). m(AlT) is in Table (5.2). K (5.o) , K (5.p)
and K (5.q) are in Table (5.5).

Al+3 + SO−2 +
4 = AlSO4 (5.o)

Al+3 +2SO−2 −
4 = Al(SO4 )2 (5.p)

Al+3 + H2 PO− +2
4 =AlH2 PO4 (5.q)

m(Al+3 ) ∗m(SO−2 ) ∗γ3 ∗γ2

m(AlSO+4 ) =K (5.o) * 4
(5.29)
γ1

Joseph Kafumbila Page 17

 m(Al+3 ) ∗(m(SO−2 ) )(2) ∗γ3 ∗(γ2 )(2)
m(Al(SO4 )−2 ) =K (5.o) * 4
(5.30)
γ1

m(Al+3 ) ∗m(H2 PO− ) ∗γ3 ∗γ1

4
m(AlH2 PO+2
4 )
=K (5.q) * (5.31)
γ2

m(AlT) =m(Al+3 )+m(AlSO+4 ) +m(Al(SO4 )−2 ) +m(AlH2PO+2

4 )
(5.32)

 Zinc

Predominate Zinc soluble compounds are Zn+2, ZnSO4 , Zn(SO4 )−2 2 and
+
ZnH2 PO4 . Equilibrium chemical reactions between Zinc soluble compounds are given by
the chemical reactions (5.r), (5.s) and (5.t). m(Zn+2 ) is the concentration of Zn+2 and the
concentrations of ZnSO4 (m(ZnSO4 ) ), Zn(SO4 )−2
2 (m(Zn(SO4)−2
2 )
) and ZnH2 PO+
4
(m(ZnH2PO+4 ) ) are given by Equations (5.33), (5.34) and (5.35). The total concentration
of soluble Zn (m(ZnT) ) is given by Equation (5.36). m(ZnT) is in Table (5.2). K (5.r) , K (5.s)
and K (5.t) are in Table (5.5).

Zn+2 + SO−2
4 = ZnSO4 (5.r)

Zn+2 + 2SO−2 −2
4 =Zn(SO4 )2 (5.s)

Zn+2 + H2 PO− +
4 =ZnH2 PO4 (5.t)

m(ZnSO4 ) =K (5.r) *m(Zn+2 ) *m(SO−2

4 )
*(γ2 )(2) (5.33)

m(Zn(SO4 )−2
2 )
=K (5.s) *m(Zn+2 ) *(m(SO−2
4 )
)2 *(γ2 )(2) (5.34)

m(ZnH2 PO+4 ) =K (5.t) *m(Zn+2 ) ∗ m(H2 PO−4 ) ∗ γ2 (5.35)

m(ZnT) =m(Zn+2 )+m(ZnSO4 ) + m(Zn(SO4 )−2

2 )
+m(ZnH2PO+4 ) (5.36)

 Manganese

Predominate Manganese soluble compounds are Mn+2, MnSO4 and MnH2 PO+ 4.
Equilibrium chemical reactions between Manganese soluble compounds are given by the
chemical reaction (5.u) and (5.v). m(Mn+2 ) is the concentration of Mn+2 and the
concentrations of MnSO4 (m(MnSO4 ) ) and MnH2 PO+
4 (m(MnH2 PO+
4)
) are given by Equation
(5.37) and (5.38). The total concentration of soluble Mn (m(MnT) ) is given by Equation
(5.39). m(MnT) is in Table (5.2). K (5.u) and K (5.v) are in Table (5.5).

Joseph Kafumbila Page 18

 Mn+2 + SO−2
4 = MnSO4 (5.u)

Mn+2 + H2 PO− +
4 =MnH2 PO4 (5.v)

m(MnSO4) =K (5.u) *m(Mn+2 ) *m(SO−2

4 )
*(γ2 )(2) (5.37)

m(MnH2 PO+4 ) =K (5.v) *m(Mn+2 ) ∗ m(H2 PO−4 ) ∗ γ2 (5.38)

m(MnT) =m(Mn+2 ) +m(MnSO4 ) +m(MnH2PO+4 ) (5.39)

 Copper

Predominate Copper soluble compounds are Cu+2 , CuSO4 and CuH2 PO+ 4.
Equilibrium chemical reactions between Copper soluble compounds are given by the
chemical reactions (5.w) and (5.x). m(Cu+2 ) is the concentration of Cu+2 and the
concentrations of CuSO4 (m(CuSO4 )) and CuH2 PO+
4 (m(CuH2 PO+
4)
) are given by Equations
(5.40) and (5.41). The total concentration of soluble Cu (m(CuT) ) is given by Equation
(5.42). m(CuT) is in Table (5.2). K (5.w) and K (5.x) are in Table (5.5).

Cu+2 + SO−2
4 = CuSO4 (5.w)

Cu+2 + H2 PO− +
4 =CuH2 PO4 (5.x)

m(CuSO4 ) =K (5.w) *m(Cu+2 ) *m(SO−2

4 )
*(γ2 )(2) (5.40)

m(CuH2 PO+4 ) =K (5.x) *m(Cu+2 ) ∗ m(H2 PO−4 ) ∗ γ2 (5.41)

m(CuT) =m(Cu+2 ) +m(CuSO4 ) +m(CuH2 PO+4 ) (5.42)

 Cobalt

Predominate Cobalt soluble compounds are Co+2 and CoSO4 . Equilibrium

chemical reaction between Cobalt soluble compounds is given by the chemical reaction
(5.y). m(Co+2 ) is the concentration of Co+2 and the concentration of CoSO4 (m(CoSO4 ) ) is
given by Equation (5.43). The total concentration of soluble Co (m(CoT) ) is given by
Equation (5.44). m(CoT) is in Table (5.2). K (5.y) is in Table (5.5).

Co+2 + SO−2
4 = CoSO4 (5.y)

m(CoSO4) =K (5.y)*m(Co+2 )*m(SO−2

4 )
*(γ2 )(2) (5.43)

Joseph Kafumbila Page 19

 m(CoT) =m(Co+2 )+m(CoSO4 ) (5.44)

 Iron

Predominate Fe(II) soluble compounds are Fe+2, FeSO4 and FeH2 PO+ 4.
Equilibrium chemical reactions between Fe(II) soluble compounds are given by the
chemical reactions (5.z) and (5.aa). m(Fe+2 ) is the concentration of Fe+2 and the
concentrations of FeSO4 (m(FeSO4 ) ) and FeH2 PO+
4 (m(FeH2 PO+
4 )
) are given by Equations
(5.45) and (5.46).

Fe+2 + SO−2
4 = FeSO4 (5.z)

Fe+2 + H2 PO− +
4 =FeH2 PO4 (5.aa)

m(FeSO4 ) =K (5.z)*m(Fe+2 ) *m(SO−2

4 )
*(γ2 )(2) (5.45)

m(FeH2 PO+4 ) =K (5.aa) *m(Fe+2 ) ∗ m(H2 PO−4 ) ∗ γ2 (5.46)

Predominate Fe(III) soluble compounds are Fe+3, FeSO+ − +2

4 , Fe(SO4 )2 , FeH2 PO4 ,
+
FeHPO+ − −2
4 , FeSO3 , Fe(SO3 )2 and FeH(SO3 )3 . Equilibrium chemical reactions between
Fe(III) soluble compounds are given by the chemical reactions (5.ab), (5.ac), (5.ad),
(5.ae), (5.af), (5.ag) and (5.ah). m(Fe+3 ) is the concentration of Fe+3 and the
concentrations of FeSO+
4 (m(FeSO+
4 )
), Fe(SO4 )−
2 (m(Fe(SO4 )−
2 )
), FeH2 PO+2
4 (m(FeH2 PO+2
4 )
),
FeHPO+
4 (m(FeHPO+
4)
), FeSO+
3 (m(FeSO+
3)
), Fe(SO3 )−
2 (m(Fe(SO3 )−
2)
), and FeH(SO3 )−2
3
(m(FeH(SO3 )−2
3 )
) are given by Equations (5.47), (5.45) and (5.46). K (5.z) , K (5.aa) , K (5.ab),
K (5.ac) , K (5.ad) , K (5.ae) , K (5.af) , K (5.ag) and K (5.ah) are in Table (5.5).

Fe+3 + SO−2 +
4 = FeSO4 (5.ab)

Fe+3 +2SO−2 −
4 = Fe(SO4 )2 (5.ac)

Fe+3 + H2 PO− +2
4 =FeH2 PO4 (5.ad)

Fe+3 + H2 PO− +
4 = FeHPO4 +H
+
(5.ae)

+
Fe+3 + HSO−
3 = FeSO3 +H
+
(5.af)

Fe+3 +2HSO− −
3 = Fe(SO3 )2 +2H
+
(5.ag)

Fe+3 +3HSO− −2
3 = FeH(SO3 )3 +2H
+
(5.ah)

Joseph Kafumbila Page 20

 m(Fe+3 ) ∗m(SO−2 ) ∗γ3 ∗γ2
m(FeSO+4 ) =K (5.ab)* 4
(5.47)
γ1

m(Fe+3 ) ∗(m(SO−2 ) )(2) ∗γ3 ∗(γ2 )(2)

m(Fe(SO4 )−2 ) =K (5.ac) * 4
(5.48)
γ1

m(Fe+3 ) ∗m(H2 PO− ) ∗γ3 ∗γ1

4
m(FeH2 PO+2
4 )
=K (5.ad) * (5.49)
γ2

m(Fe+3 ) ∗m(H2 PO− ) ∗γ3

4
m(FeHPO+4 ) =K (5.ae) * (5.50)
m(H+ ) ∗γ1

m(Fe+3 ) ∗m(HSO− ) ∗γ3

3
m(FeSO+3 ) =K (5.af)* (5.51)
m(H+ ) ∗γ1

m(Fe+3 ) ∗(m(HSO− ) )2 ∗γ3

3
m(Fe(SO3 )−2 ) =K (5.ag) * (5.52)
(m(H+ ) )2 ∗γ1

3
m(Fe+3 ) ∗(m(HSO− ) ) ∗γ1 ∗γ3
m(FeH(SO3 )−2
3 )
=K (5.ah)* 3
(5.53)
(m(H+ ) )2 ∗γ2

Equilibrium chemical reaction of Fe+3 and Fe+2 is given by the chemical

reaction (5.ai).

Fe+3+e− =Fe+2 (5.ai)

The concentration of Fe+3 (m(Fe+3 ) ) is given by Equation (5.54). µ(Fe+3 ) is given

by Equation (5.55). µ(Fe+2 ) is given by Equations (5.56). µ°(Fe+3 ) and µ°(Fe+2 ) are given in
Table (5.4)

µ −µ°
(Fe+3 ) (Fe+3 )
( )
m(Fe+3 ) =10 8.314∗298.15∗2.303 *(γ3 )(−1) (5.54)

µ(Fe+3 ) =µ(Fe+2 ) +96485*Eh (5.55)

µ(Fe+2 ) =µ°(Fe+2 ) +8.314*298.15*2.303*log(m(Fe+2 ) *γ2 ) (5.56)

The total concentration of soluble Fe (m(FeT) ) is given by Equation (5.57).

m(FeT) is in Table (5.2).

m(FeT) =m(Fe+2 )+m(FeSO4 ) +m(FeH2 PO+4 ) +m(Fe+3 ) +m(FeSO+4 ) +m(Fe(SO4 )−2 )

+m(FeH2 PO+2
4 )
+m(FeHPO+4 ) +m(FeSO+3 ) +m(Fe(SO3 )−2 ) +m(FeH(SO3 )−2
3 )
(5.57)

Joseph Kafumbila Page 21

 Table (5.4): Free Gibbs standard energy at 25°C

Compound ΔG (kj/mol) References

Fe+2 -78.9 NBS, Wagman et al, 1982
Fe+3 -4.7 NBS, Wagman et al, 1982

Table 5.5: Equilibrium constant of chemical reactions at 25°C

Chemical Log (k) Observations Reference

reaction
5.e -6.827 calculated MINTEQA2-V.4, 1999
5.d 4.61 MINTEQA2-V.4, 1999
5.f 1.99 MINTEQA2-V.4, 1999
5.g 2.147 calculated MINTEQA2-V.4, 1999
5.h 1.857 calculated R. N. Goldberg et al, 1985.4
5.i -1.495 calculated R. N. Goldberg et al, 1985
5.j 2.36 MINTEQA2-V.4, 1999
5.k -4.567 calculated D. Rai et al, 2002.5
5.l 1.350 calculated MINTEQA2-V.4, 1999
5.m 2.26 MINTEQA2-V.4, 1999
5.n 1.683 calculated MINTEQA2-V.4, 1999
5.o 3.89 MINTEQA2-V.4, 1999
5.p 4.92 MINTEQA2-V.4, 1999
5.q 3.10 calculated MINTEQA2-V.4, 1999
5.r 2.34 MINTEQA2-V.4, 1999
5.s 3.28 MINTEQA2-V.4, 1999
5.t 1.59 calculated MINTEQA2-V.4, 1999
5.u 2.25 MINTEQA2-V.4, 1999
5.v 1.34 calculated Thermoddem
5.w 2.36 MINTEQA2-V.4, 1999
5.x 1.76 calculated Thermoddem
5.y 2.30 MINTEQA2-V.4, 1999
5.z 2.39 MINTEQA2-V.4, 1999
5.aa 2.697 calculated MINTEQA2-V.4, 1999
5.ab 4.05 MINTEQA2-V.4, 1999
5.ac 5.38 MINTEQA2-V.4, 1999
5.ad 3.679 calculated MINTEQA2-V.4, 1999
5.ae 2.719 calculated MINTEQA2-V.4, 1999
5.af -0.717 calculated Gabor Lente, 2001.6
5.ag -0.860 calculated Peter Warneck, 2018.7
5.ah 1.417 calculated Peter Warneck, 2018

4 R.N. Goldberg et al, 1985, Thermodynamics of solution of SO2(g) in water and of aqueous sulfur
dioxide solution, Journal of Research of the National Bureau of Standards.
5 D. Rai et al, 1991, An Aqueous thermodynamic model for Ca(+2)-SO3(-2) ion interactions and the

solubility product of crystalline CaSO3.1/2H2O, Journal of solution chemistry.

6 Gabor Lente, 2001, Reactions of the Iron (III) hydroxo dimer with inorganic ligands, Thesis,

University of Debrecen.
7 Peter Warneck, 2018, The oxidation of sulfur (IV) by reactions with iron (III): A critical review

and data, Physical chemical-Chemical physics.

Joseph Kafumbila Page 22

  Electrical neutrality

The concentration m(HSO−3 ) is fixed by the Equation (5.58) giving the electrical
neutrality of solution.

m(SO−2
4 )
*2+m(HSO−4 ) +m(H2 PO−4 ) +m(HSO−3 ) +m(S2 O−2
5 )
*2+m(Al(SO4 )−2 ) +
m(Zn(SO4 )−2
2 )
*2+m(Fe(SO4 )−2 ) +m(Fe(SO3 )−2 ) +m(FeH(SO3 )−2
3 )
*2=m(Ca+2 ) *2+
m(CaH2 PO+4 ) +m(Mg+2 ) *2+m(MgH2PO+4 ) +m(Al+3 ) *3+m(AlSO+4 ) +m(AlH2 PO+2
4 )
*2+
m(Zn+2 ) *2+m(ZnH2 PO+4 ) +m(Mn+2 ) *2+m(MnH2 PO+4 ) +m(Cu+2 ) *2+m(CuH2 PO+4 ) +
m(Co+2 ) *2+m(Fe+2 ) *2+m(FeH2 PO+4 ) +m(Fe+3 )*3+m(FeSO+4 ) +m(FeH2 PO+2
4 )
*2+
m(FeHPO+4 ) +m(FeSO+3 ) +m(H+) (5.58)

 Ionic strength

The ionic strength of the system is given by Equation (5.59). Where “mi ” is the
molality of soluble compounds “i” and “Zi ” is electrical charge of the soluble compounds
“i”.
1
I = 2x∑ mi ∗ Zi2 (5.59)

 Water activity

The activity of water (solvent) (𝑎𝑤 ) is given by Equation (5.60). “ϕ” is the
osmotic coefficient, “W” is the molecular weight of water (18.016) and “𝑚𝑖 ” is the
concentration (mol/kg water) of soluble compounds (Charles E. Harvie et al, 1984).8

W
ln (aw ) = - 1000 *ϕ *∑i mi (5.60)

The calculations of osmotic coefficient have been approximated by Equation

(5.61) (H.C. Helgeson, 1969).9 The value of “u” is given by Equation (5.62). Table (5.6)
gives values of parameters “a”, “b”, “c” and “d” at 298.15 K. “A” comes from Debrye-
Huckel Equation for activity coefficient and is function of temperature. The value of “A”
is 0.5092 at 298.15K. “I” is the ionic strength (mol/kg of water).

2.303∗A 1 b∗I 2c∗I2 3d∗I3

ϕ=1- [u -2ln(u) - u] + + + (5.61)
a3 ∗I 2 3 4

8 Charles E. Harvie et al, 1984, The prediction of mineral solubilities in natural water: Na-K-Mg-
Ca-H-Cl-SO4-OH-HCO3-CO3-CO2-H2O system to high ionic strengths at 25°C, Geochimica et
Cosmochimica Acta
9 H.C. Helgeson, 1969, Thermodynamics of hydrothermal systems at elevated temperatures and

pressures, Ameraican Journal of Science 267.

Joseph Kafumbila Page 23

 u=1+a*√I (5.62)

Table 5.6: values of a, b, c and d parameter at 298.15K

a b c d
1.454 0.02236 9.38 x10−3 -5.362x10−4

 Activity coefficients

Activity of soluble compound “i” in water is given by Equation (5.63). “γi ” is

activity coefficient and mi is the concentration (mol/kg water) of soluble compound.

ai = γi * mi (5.63)

The calculations of individual ion activity coefficient have been approximated by

Equation (5.64) in concentrated as well as dilute electrolyte solutions involved in
geochemical processes at high temperatures and pressures (H.C. Helgeson et al, 1981)
and suitable for overall equilibrium diagram calculations. “γi ” is the activity coefficient of
soluble compound “i”, “Zi ” is the electrical charge of compound “i” and “I” is the ionic
strength (mol/kg of water). “A”, “B” and “b” are temperature-dependent parameters.
Table (5.7) gives values of parameters “A”, “B” and “b” at 298.15 K (B. Beverskog et al,
1998).10 “ä” is a distance of closest approach, which may be taken to be equal to that of
NaCl (3.72 10−10m).

Z2 A√I
Log(γi )= - (1+Bä√I)
i
– log(1+0.018015*I)+b*I (5.64)

Table 5.7: values of A, B and b parameter at 298.15K

A B x 10−10 b
0.509 0.328 0.064

For neutral aqueous species it is usually approximated that the activity

coefficients are unity at all values of ionic strength and temperature. The approximate
applicability is up to value of ionic strength around 5 (mol/kg of water) (H.C. Helgeson
et al, 1981).

10 Bjorn Beverskog, et al, 1998, Pourbaix diagrams for the system copper – chlorine at 5 – 100°C,
SKI Rapport 98:19.

Joseph Kafumbila Page 24

  Results of simulation

The new model of reductive leach of Copper and Cobalt ores is applied to pilot
plant data. Figure (5.3) gives the concentration of free SO2 gas versus ionic strength of
leach solution in the range of pH from 1.40 to 1.55 and the range of Eh from 0.572 to
.575V. The results show that the concentration of free SO2 gas increases with the
increase of the ionic strength of the solution. In the saturation condition of leach solution
with free SO2 gas, the concentration of free SO2 gas must decreases with the increase of
ionic strength of solution (Colin L. Young at al, 1983).11 This means that the solution is
not saturated in free SO2 gas.

Figure 5.3: Concentration of free SO2 gas versus ionic strength of leach solution

Figures (5.4) and (5.5) give respectively the molar fractions of total ferric and
ferrous compounds and molar fractions of iron compounds versus pH in the range of Eh
from 0.570 to 0.578V. In the pilot plant reductive leach condition, the molar fraction of
total ferric compounds increases with the increase of pH due to complexation of ferric
by sulfite compounds. In these range of Eh, the soluble complex of ferric with sulfite is
the major ferric compound in the leach solution. These results seem to be uncomfortable
in our eyes.

11 Colin L. Young et al, 1983, Sulfur dioxide, chlorine, fluorine and chlorine oxides – Solubility
data series V.12, International Union of Pure and Applied chemistry.

Joseph Kafumbila Page 25

Figure 5.4: Molar fractions of total ferric and ferrous compounds versus pH

Figure 5.5: Molar fractions of iron compounds versus pH

Joseph Kafumbila Page 26

5.3.2.6. New model of reductive leach of Copper and Cobalt ores with dithionate

 Concept

The mechanism of oxidation of sulfite to sulfate is complex. The oxidation of

sulfite compounds in the reductive leach of Copper and Cobalt ores produce dithionate,
peroxymonosulfate, sulfate compounds (J. Kafumbila, 2020a).12

The mechanisms of dithionate production are the following:

Firstly it has been observed that the transition metal ions form sulfite
complexes in their higher oxidation states form soluble complexes with sulfite
compounds. The chemical reactions (5.aj), (5.ak) and (5.al) give the complexation
reaction of cobalt, manganese and iron respectively at low pH.

+
Co+3 +HSO−
3 =CoSO3 +H
+
(5.aj)

+
Mn+3 +HSO−
3 =MnSO3 +H
+
(5.ak)

+
Fe+3+HSO−
3 =FeSO3 +H
+
(5.al)

Some sulfite complexes decompose to produce reduced metal ion and the sulfite
free radical (SÖ−
3 ). The chemical reactions (5.am), (5.an) and (5.ao) give respectively the
decomposition reactions of cobalt, manganese and iron complexes. For strong oxidants
like Co(III) and Mn(III), the reactions (5.am) and (5.an) are fast and apparently
irreversible. For weaker oxidants like Fe(III), the reaction (5.ao) is much slow and
reversible.

CoSO+ +2 −
3 =Co +SÖ3 (5.am)

MnSO+ +2 −
3 =Mn +SÖ3 (5.an)

FeSO+ +2 −
3 =Fe +SÖ3 (5.ao)

Sulfite radical reacts with sulfite complexes to produce dithionate according to

the chemical reactions (5.ap), (5.aq) and (5.ar). Sulfite radicals produce also dithionate
according to the chemical reaction (5.as)

12 J. Kafumbila, 2020a, Utilization efficiency of sulfur dioxide during reductive leaching of Copper
– Cobalt ores, technical report, researchgate. (PDF) Utilization efficiency of sulfur dioxide
during reductive leaching of Copper -Cobalt ores (researchgate.net)

Joseph Kafumbila Page 27

 CoSO+ − +2 −2
3 +SÖ3 =Co +S2 O6 (5.ap)

MnSO+ − +2 −2
3 +SÖ3 =Mn +S2 O6 (5.aq)

FeSO+ − +2 −2
3 +SÖ3 =Fe +S2 O6 (5.ar)

2SÖ− −2
3 =S2 O6 (5.as)

Secondly the proposal rate-determining step in the mechanism of dissolved SO2

gas oxidation on platinum electrode is given by reaction (5.at) which is followed by a
disproportionation step (5.au) (A.J. Appleby et al, 1979).13

2SO2 +2H2 O =S2 O−2 +

6 +4H +2e
−
(5.at)

S2 O−2 −2
6 =SO2 +SO4 (5.au)

The mechanisms of peroxymonosulfate production are the following:

Sulfite radical (SÖ−

3 ) adds rapidly soluble oxygen or oxygen from the mineral
surface to form peroxysulfate radical (SÖ−5 ) according to the addition chemical reaction
(5.av).

−
SÖ−
3 +O2 =SÖ5 (5.av)

Peroxysulfate radical (SÖ−5 ) is a strong oxidant and the product is

peroxymonosulfate (caro’s acid). The chemical reaction (5.aw) gives the oxidation
reaction at low pH.

SÖ− + − −
5 +H +e =HSO5 (5.aw)

Peroxymonosulfate (caro’s acid) is also a strong oxidant and the product is

sulfate compound. The chemical reaction (5.ax) gives the oxidation reaction at low pH.

HSO− + − −
5 +2H +2e =HSO4 +H2 O (5.ax)

In the condition of reductive leach of Copper and Cobalt ores, the peroxysulfate
radical and peroxymonosulfate react with sulfite compounds to produce sulfate
compounds according to the chemical reactions (5.ay) and (5.az).

13 A. J. Appleby et al, 1979, The mechanism of the electrochemical oxidation of sulfur dioxide in
sulfuric acid solution, Journal of Eletro-analytical Chemistry and Interfacial Electrochemistry.

Joseph Kafumbila Page 28

 2SÖ− − −
5 +3HSO3 +H2 O=5HSO4 (5.ay)

HSO− − −
5 +HSO3 =2HSO4 (5.az)

Observations are such that S2 O−2

6 must be the soluble compound whose
presence in the leach solution decreases the concentration of sulfate anions to have
electrical neutrality.

The study of the sulfur water system classifies sulfur compounds as stable or
unstable. Only elementary sulfur (S), sulfate compounds and sulfide compounds are
stables. The compounds classed as unstable can undergo further oxidation or reduction
depending on thermodynamic condition (G. Valensi et al, 1966).14 The dithionate is
relatively stable in acid solution (Hanne Crossland et al, 1961).15

The simulation model of reductive leach of Copper and Cobalt ores is reviewed
by introducing dithionate anions in place of sulfite compounds.

 Soluble compounds

 Dithionate

The concentration m(S2 O−2

6 )
is fixed by the Equation (5.65) giving the neutrality
of solution.

m(SO−2
4 )
*2+m(HSO−4 ) +m(H2 PO−4 ) +m(S2 O−2
6 )
*2+m(Al(SO4)−2 ) + m(Zn(SO4)−2
2 )
*2
+m(Fe(SO4 )−2 ) =m(Ca+2 ) *2+m(CaH2 PO+4 )+m(Mg+2 ) *2+m(MgH2PO+4 ) +m(Al+3 ) *3+
m(AlSO+4 ) +m(AlH2PO+2
4 )
*2+m(Zn+2 )*2+m(ZnH2PO+4 ) +m(Mn+2 ) *2+m(MnH2PO+4 ) +
m(Cu+2 ) *2+m(CuH2 PO+4 )+m(Co+2 ) *2+m(Fe+2 ) *2+m(FeH2 PO+4 ) +m(Fe+3 )*3+m(FeSO+4 )
+m(FeH2 PO+2
4 )
*2+m(FeHPO+4 ) +m(H+) (5.65)

 Results of simulation

Figures (5.6), (5.7), (5.8), (5.9), and (5.10) give respectively the activity of
dithionate versus activity of Co+2, activity of Mn+2, activity of Fe+2, activity of Fe+3 , and
activity of Cu+2. Figures (5.11) and (5.12) give respectively the saturation concentration
of phosphorous versus leach Eh and leach pH.

14 G. Valensi at al, 1966. Atlas of Electrochemical Equilibria in Aqueous Solutions, Pourbaix, M.

(Ed.). Vol II. Pergamon Press.
15 Hanne Crossland et al, 1961, Estimation of dithionate, Acta Chemica Scandinavica.

Joseph Kafumbila Page 29

 Figure 5.6: Activity of dithionate versus activity of Co+2

Figure 5.7: Activity of dithionate versus activity of Mn+2

Joseph Kafumbila Page 30

 Figure 5.8: Activity of dithionate versus activity of Fe+2

Figure 5.9: Activity of dithionate versus activity of Fe+3

Joseph Kafumbila Page 31

 Figure 5.10: Activity of dithionate versus activity of Cu+2

Figure 5.11: Saturation concentration of phosphorous versus leach pH

Joseph Kafumbila Page 32

 Figure 5.12: Saturation concentration of phosphorous versus leach Eh

The results show that:

 The activity of dithionate in solution increases with the increase of activities

of Co+2 and Mn+2 principally.
 There is not relationship between activity of dithionate and the activity of
Cu+2 and Fe+3.

 Empirical Equation

Equation (5.66) gives empirical Equation giving activity of Ca+2 as function of

ionic strength of solution, pH and Eh obtained from pilot plant data. Equation (5.67)
gives the difference (%) between the Ca+2 activity (a(Ca+2 ) ) and simulated Ca+2 activity
(sa(Ca+2 ) ).

(m(Ca+2) *γ2 )=3.669*10(−3) -9.547*10(−5) *I-3.669*10(−5) *pH-

3.433*10(−3) *Eh (5.66)

sa(Ca+2 )
D=absolute value of (1- )*100 (5.67)
a(Ca+2 )

Joseph Kafumbila Page 33

 Figure (5.13) gives simulated Ca+2 activity with Equation (5.66) versus Ca+2
activity from reductive leach. Figure (5.66) gives the points where the difference (D) is
less than 5%, between 5 and 10%, between 10 and 20% and high than 20%.

Figure 5.13: Simulated Ca+2 activity with Equation (5.66) versus Ca+2 activity from
reductive leach solution

5.3.2.7. Saturation concentration of iron

The relationship between the Ca+2 activity and leach solution parameters is
found. Into the modelling of reductive leach of Copper and Cobalt used to simulated the
concentration of calcium, the constraint given by Equation (5.25) (total concentration of
calcium is given by pilot plant data) is removed and replaced by Equation (5.66).

Equation (5.68) gives the concentration of Fe+2. µ(Fe+2 ) is given by Equation

(5.69) coming from equilibrium condition of Copiapite precipitation reaction (5.ba).
Equations (5.70), (5.71) and (5.72) give chemical potential of H + , SO−2 4 and H2 O
respectively. Table (5.8) gives the standard chemical potential of substances at 25°C.

µ −µ°
(Fe+2 ) (Fe+2 )
( )
m(Fe+2 ) =10 8.314∗298.15∗2.303 *(γ2 )(−1) (5.68)

µ(Fe+2 ) =µ°(Copiapite) +2µ(H+ ) -6µ(SO−2

4 )
-22µ(H2 O) -4.96485*Eh (5.69)

Joseph Kafumbila Page 34

 µ(H+) =8.314*298.15*2.303*log(m(H+ ) *γ1 ) (5.70)

µ(SO−2
4 )
=µ°(SO−2 ) +8.314*298.15*2.303*log(m(SO−2
4 )
*γ2 ) (5.71)
4

µ(H2 O) =µ°(H2 O) +8.314*298.15*2.303*log(a𝑤 ) (5.72)

Fe+2+4Fe+3 +6SO−2
4 + 22H2 O = Fe5 (SO4 )6 (OH)2 . 20H2 O + 2H
+
(5.ba)

Table (5.8): Log(k) and Free Gibbs energy at 25°C

Substance Reference
Copiapite ΔG=-9971 Kj/mol Bruce S. Hemigway et al16
SO−2
4 -744.53 NBS, Wagman et al, 1982
H2 O -237.129 NBS, Wagman et al, 1982

Figure (5.14) gives the total saturation concentration of Iron versus total
concentration of Iron into pilot plant solution.

Figure 5.14: Iron saturation concentration and Iron concentration into pilot plant
solution versus Date

16Bruce S. Hemigway et al, Thermodynamic data for modelling acid drainage problems:
compilation and estimation of data for selected soluble Iron Sulfate minerals, U.S. Geological
Survey, Report 0.2-164.

Joseph Kafumbila Page 35

 The results show that the iron concentration in the pilot plant leach solution has
a saturation concentration controlled by Copiapite precipitation.

5.3.3. Copiapite precipitation

There is precipitation of Iron as Copiapite when the inlet quantity of Iron in the
leach tanks gives high Iron concentration than the saturation concentration. The inlet
quantity of Iron contains the quantity of iron in the raffinate pumped to leach tanks and
the quantity of Iron dissolved from solid feed.

Copiapite precipitation follows the chemical reaction (5.b). Table (5.9) gives
masses of acid and precipitate.

FeSO4 +2Fe2 (SO4 )3+22H2 O=Fe5 (SO4 )6 (OH)2 . 20H2 O+H2 SO4 (5.b)

Table 5.9: Masses of acid and precipitate

Designation Reaction Element FeT FeT

MMA MMP
t/t t/t
FeT 5.b FeT 0.351 4.476

𝐹𝑒𝑇
Where “𝑀𝑀𝐴 ” is the mass of produced acid per mass of total precipitated Fe,
𝐹𝑒𝑇
and “𝑀𝑀𝑃 ” is the mass of precipitate per mass of total precipitated Fe.

5.3.4. Strengite precipitation

There is precipitation of Iron as Strengite when the inlet quantity of phosphoric

acid in the leach tanks gives high phosphoric acid concentration than the saturation
concentration. The inlet quantity of phosphoric contains the quantity of phosphoric acid
in the raffinate pumped to leach tanks and the quantity of phosphoric acid dissolved
from solid feed.

Strengite precipitation follows the chemical reaction (5.c). Table (5.10) gives
masses of acid and precipitate.

Fe2 (SO4 )3 +2H3 PO4 =2FePO4 . 2H2 O+3H2 SO4 (5.c)

Table 5.10: Masses of acid and precipitate

Designation Reaction Element PA PA PA

MMA MMP MFe
t/t t/t t/t
PA 5.c PA 1.501 1.907 0.570

Joseph Kafumbila Page 36

 𝑃𝐴 𝑃𝐴
Where “𝑀𝑀𝐴 ” is the mass of produced acid per mass of phosphoric acid, “𝑀𝑀𝑃 ”
is the mass of precipitate per mass of phosphoric acid, and “
PA
MFe ” is mass of precipitated Fe par mass of phosphoric acid.

5.3.5. Liquid specific gravity

Equation (5.73) gives the approximate value of specific gravity of liquid in as

function of liquid chemical composition (J. Kafumbila, 2017a).17

SGL = -6.139 * 10−7 x [CT ]2 + 9.742 * 10−4 * CT + 1 (5.73)

Where “ 𝑆𝐺𝐿 ” is liquid specific gravity (t/m3).

Equation (5.75) gives the value of “CT ”.

CT = ∑k1 αk ∗ Ck (5.75)

Where “𝐶𝑘 ” is the concentration of element in liquid (g/L) and “𝛼𝑘 ” is constant
(Table 5.11 gives value of 𝛼𝑘 for elements)

Table 5.11: value of constant 𝛼𝑘

Element αk
H2SO4 1.000
Cu 2.511
Co 2.629
Fe 2.719
Zn 2.468
Ni 2.635
Mn 2.747
Mg 4.949
Al 6.337
Ca 3.395
Na 3.088
K 2.234
Cr 3.769
Cd 1.854

17 J. Kafumbila, 2017a, Design of counter current decantation in copper hydrometallurgy -

(PDF) DESIGN OF COUNTER CURRENT DECANTATION IN COPPER METALLURGY
(researchgate.net)

Joseph Kafumbila Page 37

5.3.6. Leach circuit layout

5.3.6.1. Dissolution of cobalt (III)

 Dissolution of cobalt (III) with SO2

It has been observed that Cobalt (III) reacts with sulfite species in absence of
iron (R.C. Hubli et al, 1997).18 The studies on the kinetic model of the dissolution of
cobalt (III) are carried out when soluble SO2 is used as the reducing reagents. By using
the mathematical modelling of the shrinking core model; the studies show that the
kinetic model of the dissolution of cobalt (III) is the shrinking core model and the rate
controlling step is the diffusion of the reducing reagent in the unreacted core. The rate of
the dissolution of cobalt (III) increases with increasing the concentration of sulfite
species up to 0.025M.

 Dissolution of cobalt (III) with ferrous

It has been observed that Cobalt (III) reacts with ferrous species in absence of
sulfite species (M. Rajaie et al, 2015).19

 Dissolution of cobalt (III) with ferrous and SO2

 Batch test

The sample of copper-cobalt ore other than pilot plant feed is collected from an
exploration site in Haut-Katanga province of the Democratic Republic of Congo. The
sample of copper-cobalt ore is pulverized to 80% passing 150 micron. Cobalt grade of
the sample is 0.6%. Batch agitation leaching tests are performed using a 3 L glass reactor
in which 1.0 kg of the sample, pulped with synthetic raffinate solution at 20% (w/w),
was continuously agitated by means of an overhead stirrer. The stirrer speed is set so
that adequate suspension of the solids is achieved throughout each experiment. The
synthetic raffinate contained 15 g/L of sulfuric acid and desired concentration of
ferrous. The pH and the Eh of slurry are monitored and controlled continuously using a
standard pH probe and redox potential probe (Ag/AgCl). Each solid sample is analyzed
for cobalt. Samples are taken after 1, 2, 3, 4, 5 and 6 hours. These samples are
immediately filtered and washed with water. The solids are analyzed for cobalt.

18 R.C. Hubli et Al, 1997, Reduction of cobalt oxide in acid media: a kinetic study,
Hydrometallurgy.
19 M. Rajaie Najafabadiv et al, 2015, Optimization of the leaching conditions of cobalt and

Manganese with ferrous sulfate from Filter-cake of Zinc Plants, hydrometallurgical Processes.

Joseph Kafumbila Page 38

 The batch leaching test is conducted (pH of 1.5, the redox potential of 350 mV
(Ag/AgCl), ambient temperature and leach time of 6 hours). In the reactor of the batch
leach test, Na2S2O5 is used to maintain the redox potential value. The ferrous
concentration in the synthetic raffinate is varied from 0.5 to 3 g/L by adding ferrous
sulfate. Figure (5.15) gives grade of cobalt in the leach residue versus leach residence
time.

Figure 5.15: Co grade in the leach residue versus leach residence time (pH 1.5,
temperature 25°C and redox potential 350 mV (Ag/AgCl) at different iron
concentration in solution

The results show that the grade of cobalt in the leach residue decreases with
increasing of the leaching residence time. Below cobalt grade in the leach residue of
0.053%; the rate of the dissolution of cobalt is negligible (iron concentration of 2.5 and
3g/L). The rate of the dissolution of cobalt increases with increasing iron concentration
in the leach solution.

 Pilot plant result

Figure (5.16) gives the Cobalt grade in leach residue versus Iron concentration
in the leach solution in four zones:

- Redox potential (RP) (Ag/AgCl) less than 370mV and pH less than 1.6.

Joseph Kafumbila Page 39

 - Redox potential (RP) (Ag/AgCl) less than 370mV and pH high than 1.6.
- Redox potential (RP) (Ag/AgCl) high than 370mV and pH less than 1.6.
- Redox potential (RP) (Ag/AgCl) high than 370mV and pH high than 1.6.

Figure 5.16: Cobalt grade in leach residue versus Iron concentration in leach solution

The results show that Cobalt grade is low in leach residue when Iron
concentration in leach solution is high, the redox potential is less than 370mV (Ag/AgCl)
and pH is less than 1.6.

 Mechanism of Cobalt (III) dissolution with SO2 and ferrous

The mechanism of reductive dissolution of Heterogenite in presence of soluble

SO2 and Iron is the following:

 Co3 O4 and CoOOH rich rocks are good electrical conductors. (Jian Wen Wang
et al, 2013).20 Reductive dissolution is corrosion process.

 The anodic electrode is located at one face and cathodic electrode is located
at different face; there is a potential gradient between the two electrodes.

20 Jian Wen Wang et al, 2013, Synthesis of nanosized zinc-doped cobalt oxyhydroxide parties by
a dropping method and their carbon monoxide gas sensing properties, Hindawi, Journal of
nanomaterials.

Joseph Kafumbila Page 40

 The electron transport between the two electrodes takes place inside of
Heterogenite.

 On the cathodic electrode, there are two consecutive reactions: the first
reaction is the reduction of cobaltic ion into the Heterogenite structure and
this process breaks the first Co-O bond (chemical reaction (5.bb)). The
second reaction is the protonation of oxygen surface atoms and process
breaks the second Co-O bond and cobalt ion is released into the solution
(chemical reaction (5.bc)).

≣CoOOH+e− =≣CoO+OH − (5.bb)

≣CoO+2H + =Co+2+H2 O (5.bc)

 On the anodic electrodes, the first step is the migration of reactants to the
Heterogenite surface and adsorption of the reactants on the Heterogenite
surface. The migration rate of HSO− 3 into the pores of Heterogenite is very
slow comparatively to the migration rate of Fe+2. In consequence Fe+2is a
predominate reactant on the Heterogenite surface. The adsorption of Fe+2 is
facilitated by neutralization process of free electric charge on the
Heterogenite surface (chemical reaction (5.bd)). The second step is the
reaction of oxidation of ferrous to ferric compounds on the surface of
Heterogenite and the electrons are transferred into the Heterogenite
structure (chemical reaction (5.be)). The third step is desorption of reaction
products from Heterogenite surface (chemical reaction (5.bf)) and the
migration of reaction products into the solution. The facility of Fe+3
compound to form strong complexes with anions (sulfate, phosphate and
silicate) presented in solution promoting detachment of ferric compounds
into solution (Ikram Boukerche et al, 2010).21 The fourth step is the reaction
of reduction ferric to ferrous by HSO− 3 into the solution (chemical reaction
(5.bg)).

≣XO− +Fe+2=≣XOFe+ (5.bd)

≣XOFe+ =≣XOFe+2+e− (5.be)

≣XOFe+2+SO−2 − +
4 =≣XO +FeSO4 (5bf)

2FeSO+ − +2 −2
4 +HSO3 +H2 O =2Fe +3SO4 +3H
+
(5.bg)

21Ikram Boukerche et al, 2010, Dissolution of cobalt from CoO/Al2O3 catalyst with mineral acid,
Ind. Eng. Chem. Res.

Joseph Kafumbila Page 41

5.3.6.2. Leach circuit layout

In the case when Copper and Cobalt are leached from the ore, there are two
leach circuit layouts:

 The gangue acid consumption is high: the leach circuit has one single leach step
and leach pH ranges between 1.7 and 2.0. In the industrial practice, the value of
leach redox potential is ranged from 370 to 400 mV (Ag/AgCl) when SO2 gas is
injected under the impeller. The impeller is designed to pump up the solid
particles and not to disperse gas into the pulp. At the level of the leach redox
potential and leach pH, the saturation concentration of Iron is less than 1g/L. In
these conditions, the recommendation is to use filblast technology. The filblast is
device which atomizes the pulp in a gaseous atmosphere. In the case of cobalt
(III) leach, the pulp is atomized in a SO2 atmosphere. Under these conditions, the
solubility of SO2 will increase and the migration rate of SO2 to Heterogenite
surface will increase also. Figure (5.17) shows a filblast installation (B. Scenesini,
1997).22 The filblast can be installed at the outlet of pulp recirculation pump or at
the end of pulp recirculation pipe in submersion above the agitated open leach
tank. The filblast installation can be placed on the first leach tank or the first and
second leach tanks. The pulp flow rate in the recirculation filblast pipe can reach
1,000m3/h. The main advantageous of filblast technology is that the recycle
pump takes big particles of cobalt (III) minerals residing in the bottom of the
leach tank, which will be processing in the filblast advice. In this condition the
increase in the cobalt dissolution kinetic will be more significant because the
kinetic leaching model of cobalt (III) dissolution is shrinking core model. With
the filblast technology the excepted residual cobalt grade in the solid will be less
than 0.05% after 4 hours.

 The gangue acid consumption is low: the leach circuit has two leach steps. The
first leach step works at pH 1.8 to increase copper solvent extraction efficiency
and the second leach step works at pH 1.5 to increase cobalt leach efficiency by
increasing the saturation concentration of Iron. The residence time of the first
leach step is 2 hours. The leach tests must be done in both conditions: the first
step on the feed and the second step on the residue of the first step. Figure (5.18)
gives the layout of leach circuit having two leach steps.

22 Scenesini B., 1997, The filblast cynidation process – a maturing technology, Word Gold.

Joseph Kafumbila Page 42

 Figure 5.17: Typical End-of-pipe submersed filblast installation

Figure 5.18: Layout of leach circuit having two leach steps

Joseph Kafumbila Page 43

5.3.7. Flow diagram

Figure (5.19) gives a flow diagram of a leach circuit.

Figure 5.19: Flow diagram of leach circuit

5.3.8. Preliminary flow diagram mass balance Table

Table (5.12) gives Table of preliminary flow diagram mass balance of leach
circuit as it appears on Microsoft Excel spreadsheets. Table (A) is simulation Table with
numbers in red color that are design criteria, Table (B) gives the additional design
criteria (red color), Table (C) gives additional calculation and Table (D) gives Excel
solver constraints.

Abbreviation in Tables (A) means:

 AS: Acid solution

 LP: Leach pulp
 Floc: Flocculants
 OF: Overflow of thickener
 UF: Underflow of thickener

Joseph Kafumbila Page 44

 Table 5.12- A: Flow diagram mass balance Table

A B C D E F G H I J K L
1
2 Table A Flow diagram mass balance for leach circuit
3
4 1 2 3 4 5 6 7 8
5 Feed Acid SO2 AS CO2 LP Floc UF
6 Solid
7 Mass t/h 900.00
8 Volume m3/h
9 SGS t/m3 2.7 2.5 2.65 2.5
10 Pulp
11 Mass t/h
12 Volume m3/h
13 SGP t/m3
14 %solid 58 30 58
15 %W/V 0.25
16 Liquid
17 Mass t/h
18 Volume m3/h
19 SGL t/m3 1.000 1.84 1.000
20 CT
21 H3 PO4 g/L
22 Cu g/L
23 Acid g/L
24 Fe(II) g/L
25 Fe(III) g/L
26 Al g/L
27 Co g/L
28 Zn g/L
29 Ni g/L
30 Mn g/L
31 Mg g/L
32 Ca g/L

Joseph Kafumbila Page 45

 Table 5.12- B: Flow diagram mass balance Table

A B C D E F G H I J K L
33
34 Table A Flow diagram mass balance for leach circuit
35
36 9 10 11 12 13 14 15 16
37 OF Raff Bleed
38 Solid
39 Mass t/h
40 Volume m3/h
41 SGS t/m3
42 Pulp
43 Mass t/h
44 Volume m3/h
45 SGP t/m3
46 %solid
47 %W/V
48 Liquid
49 Mass t/h
50 Volume m3/h
51 SGL t/m3
52 CT
53 H3 PO4 g/L
54 Cu g/L 0.300
55 Acid g/L
56 Fe(II) g/L
57 Fe(III) g/L
58 Al g/L
59 Co g/L
60 Zn g/L
61 Ni g/L
62 Mn g/L
63 Mg g/L
64 Ca g/L

Joseph Kafumbila Page 46

 Table 5.12- C: Flow diagram mass balance Table

A B C D E F G H I J K L
65
66 Table B Additional design criteria Table C Additional Calculation
67 pH 1.7 % Eh
68 Leach redox potential (Ag/AgCl) 370 mV H+
69 Gangue acid consumption (GAC) 43.26 Kg/t SO−2
4
70 SO2 consumption (SO2C) 14.85 Kg/t HSO4−
71 Pure acid concentration in strong acid 98 % S2 O−2
6
72 Leach weight loss (LWL) 32.5 Kg/t H2 PO− 4
73 CO2 production (CO2P) 7.51 Kg/t H3 PO4
74 Flocculants dosage 40 g/t Cu+2
75 SolPA 0.45 Kg/t CuSO4
76 SolCu 14.041 Kg/t CuH2 PO+ 4
77 SolFe 0.861 Kg/t Fe+2
78 SolAl 0.688 Kg/t FeSO4
79 SolCo 2.860 Kg/t FeH2 PO+ 4
80 SolZn 0.023 Kg/t Fe+3
81 SolNi 0.068 Kg/t FeSO+ 4
82 SolMn 0.688 Kg/t Fe(SO4 )− 2
83 SolMg 1.002 Kg/t FeH2 PO+2 4
84 αPA 1.000 FeHPO+ 4
85 αCu 2.511 Al+3
86 αAc 1.000 AlSO+ 4
87 αFe(II) 2.719 Al(SO4 )− 2
88 αFe(III) 3.580 AlH2 PO+2 4
89 αAl 6.337 Co+2
90 αCo 2.629 CoSO4
91 αZn 2.468 Zn+2
92 αNi 2.635 ZnSO4
93 αMn 2.747 Zn(SO4 )−2 2
94 αMg 4.949 ZnH2 PO+ 4
95 αCa 3.395 Ni+2
96 NiSO4
97 MMAEl
MMPEl PA
MFe Mn+2
98 t/t t/t t/t MnSO4
99 Stren 1.501 1.907 0.570 MnH2 PO+ 4
100 Copiap 0.351 4.476 Mg +2
101 MgSO4
102 Table C MgH2 PO+ 4
103 Fe(II) g/L Ca+2
104 Fe(III) g/L CaSO4
105 Fe(II)/FeT CaH2 PO+ 4
106 .b1
107 Total acid consumption (TAC) Kg/t Ch+
108 Qty of Fe precipitated as Copiapite Kg/h Ch-
109 Qty of P precipitated as Strengite Kg/h
110

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 Table 5.12- D: Flow diagram mass balance Table

A B C D E F G H I J K L
110
111 Table D Excel solver constraints Table C
112 Const 1 Ia
113 Const 2 Ib
114 Const 3
115 Const 4 γ1
116 Const 5 γ2
117 Const 6 γ3
118 Const 7 aw
119 Const 8
120 Const 9 u
121 Const 10 ϕ
122 Const 11 Na
123 Const 12 Nb
124 Const 13
125 Const 14 Standard Chemical potential
126 Const 15 Copiapite -9.971.000 j/mol
127 Const 16 Fe+2 -78.900 j/mol
128 Const 17 Fe+3 -4.600 j/mol
129 Const 18 SO−2
4 -744.530 j/mol
130 Const 19 H2 O -237.129 j/mol
131 Const 20
132 Const 21 Chemical potential
133 Const 22 SO−2
4 j/mol
134 Const 23 H2 O j/mol
135 Const 24 H+ j/mol
136 Const 25 Fe+2 j/mol
137 Const 26 Fe+3 j/mol
138 Const 27
139 Const 28

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5.3.9. Procedure of flow diagram mass balance

Procedure of flow diagram mass balance is the following:

1. Feed flow

- In the Excel cell “D8” (solid volume flowrate), type “=D7/D9”.

- In the Excel cell “D11” (pulp mass flowrate), type “=D7/D14*100”.
- In the Excel cell “D17” (liquid mass flowrate), type “=D11-D7”.
- In the Excel cell “D18” (Liquid volume flowrate), type “=D17/D19”.
- In the Excel cell “D12” (pulp volume flowrate), type “=D8+D18”.
- In the Excel cell “D13” (pulp specific gravity), type “=D11/D12”.

2. Acid flow

- In the Excel cell “E17” (liquid mass flowrate), type “40” (blue color because it is
an Excel Solver variable).
- In the Excel cell “E18” (Liquid volume flowrate), type “=E17/E19”.

3. SO2 flow

- In the Excel cell “F7” (gas mass flowrate), type “=D7*F70/1000”.

4. CO2 flow

- In the Excel cell “H7” (gas mass flowrate), type “=D7*F73/1000”.

5. Leach pulp flow

- In the Excel cell “I7” (solid mass flowrate), type “=D7*(1-F72/1000)”.

- In the Excel cell “I8” (solid volume flowrate), type “=I7/I9”.
- In the Excel cell “I11” (pulp mass flowrate), type “=I7/I14*100”.
- In the Excel cell “I17” (liquid mass flowrate), type “=I11-I7”.
- In the Excel cell “I22” (Cu concentration), type “5.000”. (Blue color because it is
an Excel Solver variable).
- In the Excel cell “I24” (Fe(II) concentration), type “1.000”. (Blue color because it
is an Excel Solver variable).
- In the Excel cell “I26” (Al concentration), type “0.500”. (Blue color because it is an
Excel Solver variable).
- In the Excel cell “I27” (Co concentration), type “0.500”. (Blue color because it is
an Excel Solver variable).

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 - In the Excel cell “I28” (Zn concentration), type “0.500”. (Blue color because it is
an Excel Solver variable).
- In the Excel cell “I29” (Ni concentration), type “0.500”. (Blue color because it is an
Excel Solver variable).
- In the Excel cell “I30” (Mn concentration), type “0.500”. (Blue color because it is
an Excel Solver variable).
- In the Excel cell “I31” (Mg concentration), type “0.500”. (Blue color because it is
an Excel Solver variable).
- In the Excel cell “I32” (Ca concentration), type “0.500”. (Blue color because it is
an Excel Solver variable).

6. Additional calculation

- In the Excel cell “J67” (Eh leach solution), type “=F68/1000+0.22”.

- In the Excel cell “K113” (Ionic strength Ib – exponent of 10), type “1.000”. (Blue
color because it is an Excel Solver variable).
- In the Excel cell “J113” (Ionic strength Ib value), type “=10^(-K113)”.
- In The Excel cell “J115” (activity coefficient- 𝛾1),
type “=10^(-0.509*1*J113^(0.5)/(1+1.22*J113^(0.5)) +0.064*J113-
log(1+0.018015*J113))”.
- In The Excel cell “J116” (activity coefficient -𝛾2),
type “=10^(-0.509*4*J113^(0.5)/(1+1.22*J113^(0.5)) +0.064*J113-
log(1+0.018015*J113))”.
- In The Excel cell “J117” (activity coefficient -𝛾3),
type “=10^(-0.509*9*J113^(0.5)/(1+1.22*J113^(0.5)) +0.064*J113-
log(1+0.018015*J113))”.
- In the Excel cell “J120” (value of “u”), type “=1+1.454*J113^(0.5)”.
- In the Excel Cell “J121” (value of “ϕ”), type “=1-0.3815/J113*(J120-2*Ln(J120)-
1/J120)+1.118*10^(-2)*J113+6.253*10^(-3)*J113^(2)-
4.022*10^(-4)*J113^(3)”.
- In the Excel cell “K123” (Number Nb – exponent of 10), type “1.000”. (Blue color
because it is an Excel Solver variable).
- In the Excel cell “J123” (Number Nb value), type “=10^(-K123)”.
- In the Excel cell “J118” (water activity - 𝑎𝑤 ),
type “=EXP(-18.016/1000*J121*J123)
- In the Excel cell “J68” (Molality of H + ), type “=10^(-F67)/J115”.
- In the Excel cell “K103” (Molality of Ca+2 – exponent of 10), type “1.000”. (Blue
color because it is an Excel Solver variable).
- In the Excel cell “J103” (Molality of Ca+2 ), type “=10^(-K103)”.
- In the Excel cell “J69” (Molality of SO−2
4 ),
type “=10^(-4.61)/(J103*J118^(2)*J116^(2))”.
- In the Excel cell “J70” (Molality of HSO− 4 ),
type “=10^(1.99)/(J69*J688*J116)”.

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- In the Excel cell “K71” (Molality of S2 O−2
6 – exponent of 10), type “1.000”. (Blue
color because it is an Excel Solver variable).
- In the Excel cell “J71” (Molality of S2 O−2
6 ), type “=10^(-K71)”.
- In the Excel cell “J133” (Chemical potential of SO−2 4 ),
type “=J129+8.314*298.15*2.303*log(J69*J116)”.
- In the Excel cell “J134” (Chemical potential of H2 O),
type “=J130+8.314*298.15*2.303*log(J118)”.
- In the Excel cell “J135” (Chemical potential of H + ),
type “=8.314*298.15*2.303*log(J68*J115)”.
- In the Excel cell “J136” (Chemical potential of Fe+2),
type “=(J126+2*J135-4*96485*J67-6*J133-22*J134)/5”.
- In the Excel cell “J137” (Chemical potential of Fe+3),
type “=J136+96485*J67”.
- In the Excel cell “J77” (Molality of Fe+2),
type “=10^((J136-J127)/(8.314*298.15*2.303))/J116”.
- In the Excel cell “J80” (Molality of Fe+3),
type “=10^((J137-J128)/(8.314*298.15*2.303))/J117”.
- In the Excel cell “J72” (Molality of H2 PO−4 ),
type “=10^(-6.827)*J68^(2)*J115/(J80*J117*J118^(2))”.
- In the Excel cell “J73” (Molality of H3 PO4 ),
type “=10^(2.148)*J72*J68*J115^(2))”.
- In the Excel cell “K74” (Molality of Cu+2– exponent of 10), type “1.000”. (Blue
color because it is an Excel Solver variable).
- In the Excel cell “J74” (Molality of Cu+2 ), type “=10^(-K74)”.
- In the Excel cell “J75” (Molality of CuSO4 ),
type “=10^(2.36)*J74*J69*J116^2”.
- In the Excel cell “J76” (Molality of CuH2 PO+ 4 ),
type “=10^(1.76)*J74*J72*J116”.
- In the Excel cell “J78” (Molality of FeSO4 ),
type “=10^(2.39)*J77*J69*J116^2”.
- In the Excel cell “J79” (Concentration of FeH2 PO+ 4 ),
type “=10^(2.697)*J77*J72*J116”.
- In the Excel cell “J81” (Molality of FeSO+ 4 ),
type “=10^(4.05)*J80*J69*J117*J116/J115”.
- In the Excel cell “J82” (Molality of Fe(SO4 )− 2 ),
type “=10^(5.38)*J80*J69^(2)*J117*J116^(2)/J115”.
- In the Excel cell “J83” (Molality of FeH2 PO+2 4 ),
type “=10^(3.679)*J80*J72*J117*J115/J116”.
- In the Excel cell “J84” (Molality of FeHPO+ 4 ),
type “=10^(2.719)*J80*J72*J117/(J68*J115)”.
- In the Excel cell “K85” (Molality of Al+3– exponent of 10), type “1.000”. (Blue
color because it is an Excel Solver variable).

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- In the Excel cell “J85” (Molality of Al+3 ), type “=10^(-K85)”.
- In the Excel cell “J86” (Molality of AlSO+4 ),
type “=10^(3.59)*J85*J69*J117*J116/J115”.
- In the Excel cell “J87” (Molality of Al(SO4 )− 2 ),
type “=10^(4.92)*J85*J69^(2)*J117*J116^(2)/J115”.
- In the Excel cell “J88” (Molality of AlH2 PO+2 4 ),
type “=10^(3.1)*J85*J72*J117*J115/J116”.
- In the Excel cell “K89” (Molality of Co+2– exponent of 10), type “1.000”. (Blue
color because it is an Excel Solver variable).
- In the Excel cell “J89” (Molality of Co+2 ), type “=10^(-K89)”.
- In the Excel cell “J90” (Molality of CoSO4 ),
type “=10^(2.3)*J89*J69*J116^2”.
- In the Excel cell “K91” (Molality of Zn+2– exponent of 10), type “1.000”. (Blue
color because it is an Excel Solver variable).
- In the Excel cell “J91” (Molality of Zn+2), type “=10^(-K91)”.
- In the Excel cell “J92” (Molality of ZnSO4 ),
type “=10^(2.34)*J91*J69*J116^2”.
- In the Excel cell “J93” (Molality of Zn(SO4 )−2 2 ),
type “=10^(4.92)*J91*J69^(2)*J116^(2)”.
- In the Excel cell “J94” (Molality of ZnH2 PO+ 4 ),
type “=10^(1.59)*J91*J72*J116”.
- In the Excel cell “K95” (Molality of Ni+2 – exponent of 10), type “1.000”. (Blue
color because it is an Excel Solver variable).
- In the Excel cell “J95” (Molality of Ni+2 ), type “=10^(-K95)”.
- In the Excel cell “J96” (Molality of NiSO4 ),
type “=10^(2.3)*J95*J69*J116^2”.
- In the Excel cell “K97” (Molality of Mn+2– exponent of 10), type “1.000”. (Blue
color because it is an Excel Solver variable).
- In the Excel cell “J97” (Molality of Mn+2), type “=10^(-K97)”.
- In the Excel cell “J98” (Molality of MnSO4),
type “=10^(2.25)*J97*J69*J116^2”.
- In the Excel cell “J99” (Molality of MnH2 PO+ 4 ),
type “=10^(1.34)*J97*J72*J116”.
- In the Excel cell “K100” (Molality of Mg +2 – exponent of 10), type “1.000”. (Blue
color because it is an Excel Solver variable).
- In the Excel cell “J100” (Molality of Mg +2 ), type “=10^(-K100)”.
- In the Excel cell “J101” (Molality of MgSO4 ),
type “=10^(2.26)*J100*J69*J116^2”.
- In the Excel cell “J102” (Molality of MgH2 PO+ 4 ),
type “=10^(1.683)*J100*J72*J116”.
- In the Excel cell “J104” (Molality of CaSO4 ),
type “=10^(2.36)*J103*J69*J116^2”.
- In the Excel cell “J105” (Molality of CaH2 PO+ 4 ),

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 type “=10^(1.35)*J103*J72*J116”.
- In the Excel cell “J107” (Sum of positive charge – Ch+), type “=J68+J74*2+
J76+J77*2+J79+J80*2+J81+J83*2+J84+J85*3+J86+J88*2+J89*2+J94+J95*2+
J97*2+J100*2+J102+J103*2+J105”.
- In the Excel cell “J108” (Sum of negative charge – Ch-), type “=J69*2+J70
+J82+J87+J93*2+J72+J71*2”.
- In the Excel cell “J112” (Ionic strength Ia), type “=1/2*(J68+J69*4+J70
+J71*4+J72+J74*4+J76+J77*4+J79+J80*9+J81+J82+J83*4+J84+J85*9+J86
+J87+J88*4+J89*4+J91*4+J93*4+J94+J95*4+J97*4+J99+J100*4+J102
+J103*4+J105)”.
- In the Excel cell “J122” (Sum of concentration Na), type “=sum(J68:J105)”.
- In the Excel cell “F103” (Concentration of Fe(II)), type “=(J77+J78+J79)*55.85”.
- In the Excel cell “F104” (Concentration of Fe(III)), type “=(J80+J81+J82+
J83+J84)*55.85”.
- In the Excel cell “F105” (Ratio Fe(II)/FeT), type “=F103/(F103+F104)”.

7. Leach pulp flow

- In the Excel cell “I21” (Concentration of phosphoric acid), type “=(J73+J72+J76

+J79+J83+J84+J88+J94+J99+J102+J105)*97.99”. (assumption all phosphorous
in solution is as phosphoric acid)
- In the Excel cell “I23” (Concentration of acid), type “=98.08*J68”. (assumption
HSO− 4 neutralizes the positive charge of H )
+

- In the Excel cell “I25” (Concentration of Fe(III)), type “=I24*(1-F105)/F105”.

- In the Excel cell “I20” (CT ), type “=I21*F84+I22*F85+I23*F86 +I24*F87
+I25*F88+I26*F89+I27*F90+I28*F91+I29*F92+I30*F93+I31*F94 +I32*F95”.
- In the Excel cell “I19” (liquid specific gravity), type “=-6.139*10(−7) *(𝐈𝟐𝟎)(𝟐)
+9.742*10(−4) *I20+1”.
- In the Excel cell “I18” (liquid volume flowrate), type “=I17/I19”.
- In the Excel cell “I12” (pulp volume flowrate), type “=I8+I18”.
- In the Excel cell “I13” (pulp specific gravity), type “=I11/I12”.

8. Flocculants flow

- In the Excel cell “J7” (solid mass flowrate), type “=I7*F74*10^-6”.

- In the Excel cell “J8” (solid volume flowrate), type “=J7/J9”.
- In the Excel cell “J18” (liquid volume flowrate), type “=J7/J15*100”.
- In the Excel cell “J17” (liquid mass flowrate), type “=J18*J19”.

9. Additional calculation Table

- In the Excel cell “F106” (“b” dilution factor), type “0.9” (blue color because it is an
Excel Solver variable).

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10. UF flow

- In the Excel cell “K7” (solid mass flowrate), type “=I7+J7”.

- In the Excel cell “K8” (solid volume flowrate), type “=K7/K9”.
- In the Excel cell “K11” (pulp mass flowrate), type “=K7/K14*100”.
- In the Excel cell “K17” (liquid mass flowrate), type “=K11-K7”.
- In the Excel cell “K21” (PA concentration), type “=I21*F106”.
- In the Excel cell “K22” (Cu concentration), type “=I22* F106”.
- In the Excel cell “K23” (Ac concentration), type “=I23* F106”.
- In the Excel cell “K24” (Fe(II) concentration), type “=I24* F106”.
- In the Excel cell “K25” (Fe(III) concentration), type “=I25* F106”.
- In the Excel cell “K26” (Al concentration), type “=I26* F106”.
- In the Excel cell “K27” (Co concentration), type “=I27* F106”.
- In the Excel cell “K28” (Zn concentration), type “=I28* F106”.
- In the Excel cell “K29” (Ni concentration), type “=I29* F106”.
- In the Excel cell “K30” (Mn concentration), type “=I30* F106”.
- In the Excel cell “K31” (Mg concentration), type “=I31* F106”.
- In the Excel cell “K32” (Ca concentration), type “=I32* F106”.
- In the Excel cell “K20” (CT ), type “=K21*F84+K22*F85+K23*F86 +K24*F87
+K25*F88+K26*F89+K27*F90+K28*F91+K29*F92+K30*F93+K31*F94
+K32*F95”.
- In the Excel cell “K19” (liquid specific gravity), type “=-6.139*10(−7) *(𝐊𝟐𝟎)(𝟐)
+9.742*10(−4) *K20+1”.
- In the Excel cell “K18” (liquid volume flowrate), type “=K17/K19”.
- In the Excel cell “K12” (pulp volume flowrate), type “=K8+K18”.
- In the Excel cell “K13” (pulp specific gravity), type “=K11/K12”.

11. OF flow

- In the Excel cell “D49” (liquid mass flowrate), type “=I17+J17-K17”.

- In the Excel cell “D50” (liquid SG), type “=K19”.
- In the Excel cell “D48” (liquid volume flowrate), type “=D49/D51”.
- In the Excel cell “D53” (PA concentration), type “=K21”.
- In the Excel cell “D54” (Cu concentration), type “=K22”.
- In the Excel cell “D55” (Ac concentration), type “=K23”.
- In the Excel cell “D56” (Fe(II) concentration), type “=K24”.
- In the Excel cell “D57” (Fe(III) concentration), type “=K25”.
- In the Excel cell “D58” (Al concentration), type “=K26”.
- In the Excel cell “D59” (Co concentration), type “=K27”.
- In the Excel cell “D60” (Zn concentration), type “=K28”.
- In the Excel cell “D61” (Ni concentration), type “=K29”.

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 - In the Excel cell “D62” (Mn concentration), type “=K30”.
- In the Excel cell “D63” (Mg concentration), type “=K31”.
- In the Excel cell “D64” (Ca concentration), type “=K32”.

12. Raffinate flow

- In the Excel cell “E48” (liquid volume flowrate), type “1375” (blue color because
it is an Excel Solver variable).
- In the Excel cell “E47” (liquid mass flowrate), type “=D47-(D48*D52-
E48*E52)*0.969/1000”.
- In the Excel cell “E51” (PA concentration), type “=D48*D51/E48”.
- In the Excel cell “E53” (Ac concentration), type “=(D48*D53+(D48*D52-
E48*E52)*1.54)/E48”.
- In the Excel cell “E54” (Fe(II) concentration), type “=D48*D54/E48”.
- In the Excel cell “E55” (Fe(III) concentration), type “=D48*D55/E48”.
- In the Excel cell “E56” (Al concentration), type “=D48*D56/E48”.
- In the Excel cell “E57” (Co concentration), type “=D48*D57/E48”.
- In the Excel cell “E58” (Zn concentration), type “=D48*D58/E48”.
- In the Excel cell “E59” (Ni concentration), type “=D48*D59/E48”.
- In the Excel cell “E60” (Mn concentration), type “=D48*D60/E48”.
- In the Excel cell “E61” (Mg concentration), type “=D48*D61/E48”.
- In the Excel cell “E62” (Ca concentration), type “=D48*D62/E48”.
- In the Excel cell “E52” (CT ), type “=E53*F84+E54*F85+E55*F86 +E56*F87
+E57*F88+E58*F89+E59*F90+E60*F91+E61*F92+E62*F93+E63*F94
+E64*F95”.
- In the Excel cell “E51” (liquid specific gravity), type “=-6.139*10(−7) *(𝐄𝟓𝟐)(𝟐)
+9.742*10(−4) *E52+1”.

13. Acid solution flow

- In the Excel cell “G21” (PA concentration), type “=E53”.

- In the Excel cell “G22” (Cu concentration), type “=E54”.
- In the Excel cell “G23” (Ac concentration), type “=E55”.
- In the Excel cell “G24” (Fe(II) concentration), type “=E56”.
- In the Excel cell “G25” (Fe(III) concentration), type “=E57”.
- In the Excel cell “G26” (Al concentration), type “=E58”.
- In the Excel cell “G27” (Co concentration), type “=E59”.
- In the Excel cell “G28” (Zn concentration), type “=E60”.
- In the Excel cell “G29” (Ni concentration), type “=E61”.
- In the Excel cell “G30” (Mn concentration), type “=E62”.
- In the Excel cell “G31” (Mg concentration), type “=E63”.
- In the Excel cell “G32” (Ca concentration), type “=E64”.
- In the Excel cell “G19” (liquid specific gravity), type “=E51”.

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 - In the Excel cell “G17” (liquid mass flowrate), type “=I7+I17+H7-F7-E17-D7-
D17”.
- In the Excel cell “G18” (liquid volume flowrate), type “=G17/G19”.

14. Bleed flow

- In the Excel cell “F53” (PA concentration), type “=E53”.

- In the Excel cell “F54” (Cu concentration), type “=E54”.
- In the Excel cell “F55” (Ac concentration), type “=E55”.
- In the Excel cell “F56” (Fe(II) concentration), type “=E56”.
- In the Excel cell “F57” (Fe(III) concentration), type “=E57”.
- In the Excel cell “F58” (Al concentration), type “=E58”.
- In the Excel cell “F59” (Co concentration), type “=E59”.
- In the Excel cell “F60” (Zn concentration), type “=E60”.
- In the Excel cell “F61” (Ni concentration), type “=E61”.
- In the Excel cell “F62” (Mn concentration), type “=E62”.
- In the Excel cell “F63” (Mg concentration), type “=E63”.
- In the Excel cell “F64” (Ca concentration), type “=E64”.
- In the Excel cell “F51” (liquid specific gravity), type “=E51”.
- In the Excel cell “F49” (liquid mass flowrate), type “=E49-G17”.
- In the Excel cell “F50” (liquid volume flowrate), type “=F49/F51”.

15. Additional calculation Table

- In the Excel cell “F107” (TAC total acid consumption), type “=F69+F76*1.54”.
- In the Excel cell “F108” (Quantity of Fe precipitated as Copiapite), type
“=D7*F77+G18*(G24+G25)-I18*(I24+I25)”.
- In the Excel cell “F109” (Quantity of phosphoric acid precipitated as Strengite),
type “=D7*F75+G18*G21-I18*I21”.

16. Solver constraints (green color)

- In the Excel cell “C112” (solver constraint 1), type “= J107/J108”. (ratio of
electrical charge)
- In the Excel cell “C113” (solver constraint 2), type “=I22/((J74+J75
+J76)*63.54)”.
- In the Excel cell “C114” (solver constraint 3), type “=I24/((J77+J78
+J79)*55.85)”.
- In the Excel cell “C115” (solver constraint 4), type “=I26/((J85+J86
+J87+J88)*26.98)”.
- In the Excel cell “C116” (solver constraint 5), type “=I27/((J89+J90)*58.93)”.
- In the Excel cell “C117” (solver constraint 6), type “=I28/((J91+J92
+J93+J94)*65.38)”.

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 - In the Excel cell “C118” (solver constraint 7), type “=I29/((J95+J96)*58.69)”.
- In the Excel cell “C119” (solver constraint 8), type “=I30/((J97+J98
+J99)*54.94)”.
- In the Excel cell “C120” (solver constraint 9), type “=I31/((J100+J101
+J102)*24.31)”.
- In the Excel cell “C121” (solver constraint 10), type “=I32/((J103+J104
+J105)*40.08)”.
- In the Excel cell “C122” (solver constraint 11), type “=I18*I22/(K18*K22+
D50*D54)”.
- In the Excel cell “C123” (solver constraint 12), type “=E50*E51/E49.
- In the Excel cell “C124” (solver constraint 13), type “=E17*1000/(I18*I23+
D7*F107-G18*G23).
- In the Excel cell “C125” (solver constraint 14), type “=I18*I22/(G18*G22
+D7*F76).
- In the Excel cell “C126” (solver constraint 15), type “=I18*I26/(G18*G26
+D7*F78).
- In the Excel cell “C127” (solver constraint 16), type “=I18*I27/(G18*G27
+D7*F79).
- In the Excel cell “C128” (solver constraint 17), type “=I18*I28/(G18*G28
+D7*F80).
- In the Excel cell “C129” (solver constraint 18), type “=I18*I29/(G18*G29
+D7*F81).
- In the Excel cell “C130” (solver constraint 19), type “=I18*I30/(G18*G30
+D7*F82).
- In the Excel cell “C131” (solver constraint 20), type “=I18*I31/(G18*G31
+D7*F83).
- In the Excel cell “C132” (solver constraint 21), type “=J112/J113”.
- In the Excel cell “C133” (solver constraint 22), type “=J122/J123”.
- In the Excel cell “C134” (solver constraint 23), type “=(J103*J116)/(-
9.547*10^(5)*J113-3.669*10^(-5)*F67-3.433*10^(-3)*J67+3.669*10^(-3))”.

17. Optimization of variables

Optimization procedure which uses Microsoft Excel solver is as follows:

 On the ‘Data’, in the ‘Analysis group’ click solver (if the solver command is not
available, you must activate the solver add-in).
 In the ‘Set objective’ box, enter the cell reference “C112”.
 Click ‘Value of’ and then type the number ‘1’ in the box.
 In the “By Changing Variable Cells” box, enter the references (E17, I22, I24, I26,
I27, I28, I29, I30, I31, I32, E50, F106, K71, K85, K89, K91, K95, K97, K100, K103,
K113 and K123).
o In the ‘Solver Parameters’ dialog box, click ‘Add’.

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 o In the ‘Cell Reference’ box, enter the cell reference “C113”.
o Click the ‘relationship’ ‘=‘, in the ‘Constraint’ box, type the number ‘1’.
o Click ‘OK’ to return to ‘Solver Parameters’ dialog box.
……………………………………………………………………………………………..
o In the ‘Solver Parameters’ dialog box, click ‘Add’.
o In the ‘Cell Reference’ box, enter the cell reference “C134”.
o Click the ‘relationship’ ‘=‘, in the ‘Constraint’ box, type the number ‘1’.
o Click ‘OK’ to return to ‘Solver Parameters’ dialog box.

 Click ‘Solve’. To keep the solution values on the worksheet, in the ‘Solver Results’
dialog box, click ‘Keep solver solution’.

Table (5.13) gives the results of mass balance of leach circuit. In the Excel cell
“F108” (quantity of Fe precipitated as Copiapite is negative. This means that the Fe
concentration is under the saturation concentration. In the Excel cell “F109” (quantity of
phosphoric acid precipitated as Strengite) is positive. This means that there is
precipitation of phosphoric acid as Strengite). The procedure is repeated taking into
account the above observations.

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 Table 5.13- A: Flow diagram mass balance Table

A B C D E F G H I J K L
1
2 Table A Flow diagram mass balance for leach circuit
3
4 1 2 3 4 5 6 7 8
5 Feed Acid SO2 AS CO2 LP Floc UF
6 Solid
7 Mass t/h 900.00 13.37 6.76 870.75 0.035 870.78
8 Volume m3/h 333.33 348.30 0.013 348.31
9 SGS t/m3 2.7 2.5 2.65 2.5
10 Pulp
11 Mass t/h 1551.72 2902.50 1501.35
12 Volume m3/h 985.06 2288.36 950.61
13 SGP t/m3 1.58 1.27 1.58
14 %solid 58 30 58
15 %W/V 0.25
16 Liquid
17 Mass t/h 651.72 48.25 1295.92 2031.75 13.93 630.57
18 Volume m3/h 651.72 26.22 1244.53 1940.06 13.93 602.30
19 SGL t/m3 1.000 1.84 1.041 1.047 1.000 1.047
20 CT 50.096 49.740
21 H3 PO4 g/L 0.030 0.030 0.030
22 Cu g/L 0.300 6.706 6.658
23 Acid g/L 12.693 2.916 2.895
24 Fe(II) g/L 1.118 1.125 1.117
25 Fe(III) g/L 0.043 0.043 0.043
26 Al g/L 0.873 0.879 0.873
27 Co g/L 3.881 3.907 3.879
28 Zn g/L 0.030 0.030 0.030
29 Ni g/L 0.086 0.086 0.086
30 Mn g/L 0.874 0.880 0.874
31 Mg g/L 1.273 1.281 1.272
32 Ca g/L 0.642 0.646 0.641

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 Table 5.13- B: Flow diagram mass balance Table

A B C D E F G H I J K L
33
34 Table A Flow diagram mass balance for leach circuit
35
36 9 10 11 12 13 14 15 16
37 OF Raff Bleed
38 Solid
39 Mass t/h
40 Volume m3/h
41 SGS t/m3
42 Pulp
43 Mass t/h
44 Volume m3/h
45 SGP t/m3
46 %solid
47 %W/V
48 Liquid
49 Mass t/h 1451.11 1406.79 110.86
50 Volume m3/h 1351.67 1350.99 106.47
51 SGL t/m3 1.047 1.041 1.041
52 CT 43.587
53 H3 PO4 g/L 0.030 0.030 0.030
54 Cu g/L 6.658 0.300 0.300
55 Acid g/L 2.895 12.693 12.693
56 Fe(II) g/L 1.117 1.117 1.117
57 Fe(III) g/L 0.043 0.043 0.043
58 Al g/L 0.873 0.873 0.873
59 Co g/L 3.879 3.879 3.879
60 Zn g/L 0.030 0.030 0.030
61 Ni g/L 0.086 0.086 0.086
62 Mn g/L 0.874 0.874 0.874
63 Mg g/L 1.272 1.272 1.272
64 Ca g/L 0.641 0.641 0.641

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 Table 5.13- C: Flow diagram mass balance Table

A B C D E F G H I J K L
65
66 Table B Additional design criteria Table C Additional Calculation
67 pH 1.7 % Eh 0.590
68 Leach redox potential (Ag/AgCl) 370 mV H+ 2.973E-02
69 Gangue acid consumption (GAC) 43.26 Kg/t SO−2
4 1.160E-01
70 SO2 consumption (SO2C) 14.85 Kg/t HSO4− 4.857E-02
71 Pure acid concentration in strong acid 98 % S2 O−2
6 8.415E-02 1.075
72 Leach weight loss (LWL) 32.5 Kg/t H2 PO− 4 5.468E-05
73 CO2 production (CO2P) 7.51 Kg/t H3 PO4 1.030E-04
74 Flocculants dosage 40 g/t Cu+2 6.754E-02 1.168
75 SolPA 0.45 Kg/t CuSO4 3.754E-02
76 SolCu 14.041 Kg/t CuH2 PO+ 4 3.084E-05
77 SolFe 0.861 Kg/t Fe+2 1.263E-02
78 SolAl 0.688 Kg/t FeSO4 7.472E-03
79 SolCo 2.860 Kg/t FeH2 PO+ 4 4.955E-05
80 SolZn 0.023 Kg/t Fe+3 1.483E-04
81 SolNi 0.068 Kg/t FeSO+ 4 4.605E-04
82 SolMn 0.688 Kg/t Fe(SO4 )− 2 1.646E-04
83 SolMg 1.002 Kg/t FeH2 PO+2 4 2.000E-06
84 αPA 1.000 FeHPO+ 4 2.364E-05
85 αCu 2.511 Al+3 1.322-02 1.879
86 αAc 1.000 AlSO+ 4 1.424E-02
87 αFe(II) 2.719 Al(SO4 )− 2 5.089E-03
88 αFe(III) 3.580 AlH2 PO+2 4 4.707E-05
89 αAl 6.337 Co+2 4.476E-02 1.349
90 αCo 2.629 CoSO4 2.153E-02
91 αZn 2.468 Zn+2 2.221E-04 3.653
92 αNi 2.635 ZnSO4 1.172E-04
93 αMn 2.747 Zn(SO4 )−2 2 1.183E-04
94 αMg 4.949 ZnH2 PO+ 4 6.815E-08
95 αCa 3.395 Ni+2 9.931E-04 3.003
96 NiSO4 4.777E-04
97 MMAEl
MMPEl PA
MFe Mn+2 1.121E-02 1.950
98 t/t t/t t/t MnSO4 4.805E-03
99 Stren 1.501 1.907 0.570 MnH2 PO+ 4 1.933E-06
100 Copiap 0.351 4.476 Mg +2 3.663E-02 1.436
101 MgSO4 1.607E-02
102 Table C MgH2 PO+ 4 1.392E-05
103 Fe(II) 1.125 g/L Ca+2 1.038E-02 1.984
104 Fe(III) 0.043 g/L CaSO4 5.734E-03
105 Fe(II)/FeT 0.963 CaH2 PO+ 4 1.833E-06
106 .b1 0.993
107 Total acid consumption (TAC) 64.880 Kg/t Ch+ 4.543E-01
108 Qty of Fe precipitated as Copiapite -47.54 Kg/h Ch- 4.543E-01
109 Qty of P precipitated as Strengite 383.81 Kg/h
110

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 Table 5.13- D: Flow diagram mass balance Table

A B C D E F G H I J K L
110
111 Table D Excel solver constraints Table C
112 Const 1 1.000 Ia 8.795E-01
113 Const 2 1.000 Ib 8.795E-01 0.056
114 Const 3 1.000
115 Const 4 1.000 γ1 6.712E-01
116 Const 5 1.000 γ2 1.442E-01
117 Const 6 1.000 γ3 1.111E-02
118 Const 7 1.000 aw 9.903E-01
119 Const 8 1.000
120 Const 9 1.000 u 2.364
121 Const 10 1.000 ϕ 9.189E-01
122 Const 11 1.000 Na 5.907E-01
123 Const 12 1.000 Nb 5.907E-01 0.220
124 Const 13 1.000
125 Const 14 1.000 Standard Chemical potential
126 Const 15 1.000 Copiapite -9.971.000 j/mol
127 Const 16 1.000 Fe+2 -78.900 j/mol
128 Const 17 1.000 Fe+3 -4.600 j/mol
129 Const 18 1.000 SO−2
4 -744.530 j/mol
130 Const 19 1.000 H2 O -237.129 j/mol
131 Const 20 1.000
132 Const 21 1.000 Chemical potential
133 Const 22 1.000 SO−2
4 -754673 j/mol
134 Const 23 1.000 H2 O -237153 j/mol
135 H+ -9705 j/mol
136 Fe+2 -94541 j/mol
137 Fe+3 -37615 j/mol
138
139

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5.3.10. Procedure of flow diagram mass balance

Procedure of flow diagram mass balance is the following:

18. Feed flow

- In the Excel cell “D8” (solid volume flowrate), type “=D7/D9”.

- In the Excel cell “D11” (pulp mass flowrate), type “=D7/D14*100”.
- In the Excel cell “D17” (liquid mass flowrate), type “=D11-D7”.
- In the Excel cell “D18” (Liquid volume flowrate), type “=D17/D19”.
- In the Excel cell “D12” (pulp volume flowrate), type “=D8+D18”.
- In the Excel cell “D13” (pulp specific gravity), type “=D11/D12”.

19. Acid flow

- In the Excel cell “E17” (liquid mass flowrate), type “40” (blue color because it is
an Excel Solver variable).
- In the Excel cell “E18” (Liquid volume flowrate), type “=E17/E19”.

20. SO2 flow

- In the Excel cell “F7” (gas mass flowrate), type “=D7*F70/1000”.

21. CO2 flow

- In the Excel cell “H7” (gas mass flowrate), type “=D7*F73/1000”.

22. Leach pulp flow

- In the Excel cell “I7” (solid mass flowrate), type “870”. (Blue color because it is an
Excel Solver variable).
- In the Excel cell “I8” (solid volume flowrate), type “=I7/I9”.
- In the Excel cell “I11” (pulp mass flowrate), type “=I7/I14*100”.
- In the Excel cell “I17” (liquid mass flowrate), type “=I11-I7”.
- In the Excel cell “I22” (Cu concentration), type “5.000”. (Blue color because it is
an Excel Solver variable).
- In the Excel cell “I24” (Fe(II) concentration), type “1.000”. (Blue color because it
is an Excel Solver variable).
- In the Excel cell “I26” (Al concentration), type “0.500”. (Blue color because it is an
Excel Solver variable).

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 - In the Excel cell “I27” (Co concentration), type “0.500”. (Blue color because it is
an Excel Solver variable).
- In the Excel cell “I28” (Zn concentration), type “0.500”. (Blue color because it is
an Excel Solver variable).
- In the Excel cell “I29” (Ni concentration), type “0.500”. (Blue color because it is an
Excel Solver variable).
- In the Excel cell “I30” (Mn concentration), type “0.500”. (Blue color because it is
an Excel Solver variable).
- In the Excel cell “I31” (Mg concentration), type “0.500”. (Blue color because it is
an Excel Solver variable).
- In the Excel cell “I32” (Ca concentration), type “0.500”. (Blue color because it is
an Excel Solver variable).

23. Additional calculation

- In the Excel cell “J67” (Eh leach solution), type “=F68/1000+0.22”.

- In the Excel cell “K113” (Ionic strength Ib – exponent of 10), type “1.000”. (Blue
color because it is an Excel Solver variable).
- In the Excel cell “J113” (Ionic strength Ib value), type “=10^(-K113)”.
- In The Excel cell “J115” (activity coefficient- 𝛾1),
type “=10^(-0.509*1*J113^(0.5)/(1+1.22*J113^(0.5)) +0.064*J113-
log(1+0.018015*J113))”.
- In The Excel cell “J116” (activity coefficient -𝛾2),
type “=10^(-0.509*4*J113^(0.5)/(1+1.22*J113^(0.5)) +0.064*J113-
log(1+0.018015*J113))”.
- In The Excel cell “J117” (activity coefficient -𝛾3),
type “=10^(-0.509*9*J113^(0.5)/(1+1.22*J113^(0.5)) +0.064*J113-
log(1+0.018015*J113))”.
- In the Excel cell “J120” (value of “u”), type “=1+1.454*J113^(0.5)”.
- In the Excel Cell “J121” (value of “ϕ”), type “=1-0.3815/J113*(J120-2*Ln(J120)-
1/J120)+1.118*10^(-2)*J113+6.253*10^(-3)*J113^(2)-
4.022*10^(-4)*J113^(3)”.
- In the Excel cell “K123” (Number Nb – exponent of 10), type “1.000”. (Blue color
because it is an Excel Solver variable).
- In the Excel cell “J123” (Number Nb value), type “=10^(-K123)”.
- In the Excel cell “J118” (water activity - 𝑎𝑤 ),
type “=EXP(-18.016/1000*J121*J123)
- In the Excel cell “J68” (Molality of H + ), type “=10^(-F67)/J115”.
- In the Excel cell “K103” (Molality of Ca+2 – exponent of 10), type “1.000”. (Blue
color because it is an Excel Solver variable).
- In the Excel cell “J103” (Molality of Ca+2 ), type “=10^(-K103)”.
- In the Excel cell “J69” (Molality of SO−2
4 ),
type “=10^(-4.61)/(J103*J118^(2)*J116^(2))”.

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- In the Excel cell “J70” (Molality of HSO− 4 ),
type “=10^(1.99)/(J69*J688*J116)”.
- In the Excel cell “K71” (Molality of S2 O−2
6 – exponent of 10), type “1.000”. (Blue
color because it is an Excel Solver variable).
- In the Excel cell “J71” (Molality of S2 O−2
6 ), type “=10^(-K71)”.
- In the Excel cell “J133” (Chemical potential of SO−2 4 ),
type “=J129+8.314*298.15*2.303*log(J69*J116)”.
- In the Excel cell “J134” (Chemical potential of H2 O),
type “=J130+8.314*298.15*2.303*log(J118)”.
- In the Excel cell “J135” (Chemical potential of H + ),
type “=8.314*298.15*2.303*log(J68*J115)”.
- In the Excel cell “K77” (Molality of Fe+2 – exponent of 10), type “1.000”. (Blue
color because it is an Excel Solver variable).
- In the Excel cell “J77” (Molality of Fe+2), type “=10^(-K77)”.
- In the Excel cell “J136” (Chemical potential of Fe+2),
type “=J127+8.314*298.15*2.303*log(J77*J116)”.
- In the Excel cell “J137” (Chemical potential of Fe+3),
type “=J136+96485*J67”.
- In the Excel cell “J80” (Molality of Fe+3),
type “=10^((J137-J128)/(8.314*298.15*2.303))/J117”.
- In the Excel cell “J72” (Molality of H2 PO− 4 ),
type “=10^(-6.827)*J68^(2)*J115/(J80*J117*J118^(2))”.
- In the Excel cell “J73” (Molality of H3 PO4 ),
type “=10^(2.148)*J72*J68*J115^(2))”.
- In the Excel cell “K74” (Molality of Cu+2– exponent of 10), type “1.000”. (Blue
color because it is an Excel Solver variable).
- In the Excel cell “J74” (Molality of Cu+2 ), type “=10^(-K74)”.
- In the Excel cell “J75” (Molality of CuSO4 ),
type “=10^(2.36)*J74*J69*J116^2”.
- In the Excel cell “J76” (Molality of CuH2 PO+ 4 ),
type “=10^(1.76)*J74*J72*J116”.
- In the Excel cell “J78” (Molality of FeSO4 ),
type “=10^(2.39)*J77*J69*J116^2”.
- In the Excel cell “J79” (Concentration of FeH2 PO+ 4 ),
type “=10^(2.697)*J77*J72*J116”.
- In the Excel cell “J81” (Molality of FeSO+ 4 ),
type “=10^(4.05)*J80*J69*J117*J116/J115”.
- In the Excel cell “J82” (Molality of Fe(SO4 )− 2 ),
type “=10^(5.38)*J80*J69^(2)*J117*J116^(2)/J115”.
- In the Excel cell “J83” (Molality of FeH2 PO+2 4 ),
type “=10^(3.679)*J80*J72*J117*J115/J116”.
- In the Excel cell “J84” (Molality of FeHPO+ 4 ),
type “=10^(2.719)*J80*J72*J117/(J68*J115)”.

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- In the Excel cell “K85” (Molality of Al+3– exponent of 10), type “1.000”. (Blue
color because it is an Excel Solver variable).
- In the Excel cell “J85” (Molality of Al+3 ), type “=10^(-K85)”.
- In the Excel cell “J86” (Molality of AlSO+4 ),
type “=10^(3.59)*J85*J69*J117*J116/J115”.
- In the Excel cell “J87” (Molality of Al(SO4 )− 2 ),
type “=10^(4.92)*J85*J69^(2)*J117*J116^(2)/J115”.
- In the Excel cell “J88” (Molality of AlH2 PO+2 4 ),
type “=10^(3.1)*J85*J72*J117*J115/J116”.
- In the Excel cell “K89” (Molality of Co+2– exponent of 10), type “1.000”. (Blue
color because it is an Excel Solver variable).
- In the Excel cell “J89” (Molality of Co+2 ), type “=10^(-K89)”.
- In the Excel cell “J90” (Molality of CoSO4 ),
type “=10^(2.3)*J89*J69*J116^2”.
- In the Excel cell “K91” (Molality of Zn+2– exponent of 10), type “1.000”. (Blue
color because it is an Excel Solver variable).
- In the Excel cell “J91” (Molality of Zn+2), type “=10^(-K91)”.
- In the Excel cell “J92” (Molality of ZnSO4 ),
type “=10^(2.34)*J91*J69*J116^2”.
- In the Excel cell “J93” (Molality of Zn(SO4 )−2 2 ),
type “=10^(4.92)*J91*J69^(2)*J116^(2)”.
- In the Excel cell “J94” (Molality of ZnH2 PO+ 4 ),
type “=10^(1.59)*J91*J72*J116”.
- In the Excel cell “K95” (Molality of Ni+2 – exponent of 10), type “1.000”. (Blue
color because it is an Excel Solver variable).
- In the Excel cell “J95” (Molality of Ni+2 ), type “=10^(-K95)”.
- In the Excel cell “J96” (Molality of NiSO4 ),
type “=10^(2.3)*J95*J69*J116^2”.
- In the Excel cell “K97” (Molality of Mn+2– exponent of 10), type “1.000”. (Blue
color because it is an Excel Solver variable).
- In the Excel cell “J97” (Molality of Mn+2), type “=10^(-K97)”.
- In the Excel cell “J98” (Molality of MnSO4),
type “=10^(2.25)*J97*J69*J116^2”.
- In the Excel cell “J99” (Molality of MnH2 PO+ 4 ),
type “=10^(1.34)*J97*J72*J116”.
- In the Excel cell “K100” (Molality of Mg +2 – exponent of 10), type “1.000”. (Blue
color because it is an Excel Solver variable).
- In the Excel cell “J100” (Molality of Mg +2 ), type “=10^(-K100)”.
- In the Excel cell “J101” (Molality of MgSO4 ),
type “=10^(2.26)*J100*J69*J116^2”.
- In the Excel cell “J102” (Molality of MgH2 PO+ 4 ),
type “=10^(1.683)*J100*J72*J116”.
- In the Excel cell “J104” (Molality of CaSO4 ),

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 type “=10^(2.36)*J103*J69*J116^2”.
- In the Excel cell “J105” (Molality of CaH2 PO+ 4 ),
type “=10^(1.35)*J103*J72*J116”.
- In the Excel cell “J107” (Sum of positive charge – Ch+), type “=J68+J74*2+
J76+J77*2+J79+J80*2+J81+J83*2+J84+J85*3+J86+J88*2+J89*2+J94+J95*2+
J97*2+J100*2+J102+J103*2+J105”.
- In the Excel cell “J108” (Sum of negative charge – Ch-), type “=J69*2+J70
+J82+J87+J93*2+J72+J71*2”.
- In the Excel cell “J112” (Ionic strength Ia), type “=1/2*(J68+J69*4+J70
+J71*4+J72+J74*4+J76+J77*4+J79+J80*9+J81+J82+J83*4+J84+J85*9+J86
+J87+J88*4+J89*4+J91*4+J93*4+J94+J95*4+J97*4+J99+J100*4+J102
+J103*4+J105)”.
- In the Excel cell “J122” (Sum of concentration Na), type “=sum(J68:J105)”.
- In the Excel cell “F103” (Concentration of Fe(II)), type “=(J77+J78+J79)*55.85”.
- In the Excel cell “F104” (Concentration of Fe(III)), type “=(J80+J81+J82+
J83+J84)*55.85”.
- In the Excel cell “F105” (Ratio Fe(II)/FeT), type “=F103/(F103+F104)”.

24. Leach pulp flow

- In the Excel cell “I21” (Concentration of phosphoric acid), type “=(J73+J72+J76

+J79+J83+J84+J88+J94+J99+J102+J105)*97.99”. (assumption all phosphorous
in solution is as phosphoric acid)
- In the Excel cell “I23” (Concentration of acid), type “=98.08*J68”. (assumption
HSO− 4 neutralizes the positive charge of H )
+

- In the Excel cell “I25” (Concentration of Fe(III)), type “=I24*(1-F105)/F105”.

- In the Excel cell “I20” (CT ), type “=I21*F84+I22*F85+I23*F86 +I24*F87
+I25*F88+I26*F89+I27*F90+I28*F91+I29*F92+I30*F93+I31*F94 +I32*F95”.
- In the Excel cell “I19” (liquid specific gravity), type “=-6.139*10(−7) *(𝐈𝟐𝟎)(𝟐)
+9.742*10(−4) *I20+1”.
- In the Excel cell “I18” (liquid volume flowrate), type “=I17/I19”.
- In the Excel cell “I12” (pulp volume flowrate), type “=I8+I18”.
- In the Excel cell “I13” (pulp specific gravity), type “=I11/I12”.

25. Flocculants flow

- In the Excel cell “J7” (solid mass flowrate), type “=I7*F74*10^-6”.

- In the Excel cell “J8” (solid volume flowrate), type “=J7/J9”.
- In the Excel cell “J18” (liquid volume flowrate), type “=J7/J15*100”.
- In the Excel cell “J17” (liquid mass flowrate), type “=J18*J19”.

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26. Additional calculation Table

- In the Excel cell “F106” (“b” dilution factor), type “0.9” (blue color because it is an
Excel Solver variable).

27. UF flow

- In the Excel cell “K7” (solid mass flowrate), type “=I7+J7”.

- In the Excel cell “K8” (solid volume flowrate), type “=K7/K9”.
- In the Excel cell “K11” (pulp mass flowrate), type “=K7/K14*100”.
- In the Excel cell “K17” (liquid mass flowrate), type “=K11-K7”.
- In the Excel cell “K21” (PA concentration), type “=I21*F106”.
- In the Excel cell “K22” (Cu concentration), type “=I22* F106”.
- In the Excel cell “K23” (Ac concentration), type “=I23* F106”.
- In the Excel cell “K24” (Fe(II) concentration), type “=I24* F106”.
- In the Excel cell “K25” (Fe(III) concentration), type “=I25* F106”.
- In the Excel cell “K26” (Al concentration), type “=I26* F106”.
- In the Excel cell “K27” (Co concentration), type “=I27* F106”.
- In the Excel cell “K28” (Zn concentration), type “=I28* F106”.
- In the Excel cell “K29” (Ni concentration), type “=I29* F106”.
- In the Excel cell “K30” (Mn concentration), type “=I30* F106”.
- In the Excel cell “K31” (Mg concentration), type “=I31* F106”.
- In the Excel cell “K32” (Ca concentration), type “=I32* F106”.
- In the Excel cell “K20” (CT ), type “=K21*F84+K22*F85+K23*F86 +K24*F87
+K25*F88+K26*F89+K27*F90+K28*F91+K29*F92+K30*F93+K31*F94
+K32*F95”.
- In the Excel cell “K19” (liquid specific gravity), type “=-6.139*10(−7) *(𝐊𝟐𝟎)(𝟐)
+9.742*10(−4) *K20+1”.
- In the Excel cell “K18” (liquid volume flowrate), type “=K17/K19”.
- In the Excel cell “K12” (pulp volume flowrate), type “=K8+K18”.
- In the Excel cell “K13” (pulp specific gravity), type “=K11/K12”.

28. OF flow

- In the Excel cell “D49” (liquid mass flowrate), type “=I17+J17-K17”.

- In the Excel cell “D50” (liquid SG), type “=K19”.
- In the Excel cell “D48” (liquid volume flowrate), type “=D49/D51”.
- In the Excel cell “D53” (PA concentration), type “=K21”.
- In the Excel cell “D54” (Cu concentration), type “=K22”.
- In the Excel cell “D55” (Ac concentration), type “=K23”.
- In the Excel cell “D56” (Fe(II) concentration), type “=K24”.
- In the Excel cell “D57” (Fe(III) concentration), type “=K25”.
- In the Excel cell “D58” (Al concentration), type “=K26”.

Joseph Kafumbila Page 68

 - In the Excel cell “D59” (Co concentration), type “=K27”.
- In the Excel cell “D60” (Zn concentration), type “=K28”.
- In the Excel cell “D61” (Ni concentration), type “=K29”.
- In the Excel cell “D62” (Mn concentration), type “=K30”.
- In the Excel cell “D63” (Mg concentration), type “=K31”.
- In the Excel cell “D64” (Ca concentration), type “=K32”.

29. Raffinate flow

- In the Excel cell “E48” (liquid volume flowrate), type “1375” (blue color because
it is an Excel Solver variable).
- In the Excel cell “E47” (liquid mass flowrate), type “=D47-(D48*D52-
E48*E52)*0.969/1000”.
- In the Excel cell “E51” (PA concentration), type “=D48*D51/E48”.
- In the Excel cell “E53” (Ac concentration), type “=(D48*D53+(D48*D52-
E48*E52)*1.54)/E48”.
- In the Excel cell “E54” (Fe(II) concentration), type “=D48*D54/E48”.
- In the Excel cell “E55” (Fe(III) concentration), type “=D48*D55/E48”.
- In the Excel cell “E56” (Al concentration), type “=D48*D56/E48”.
- In the Excel cell “E57” (Co concentration), type “=D48*D57/E48”.
- In the Excel cell “E58” (Zn concentration), type “=D48*D58/E48”.
- In the Excel cell “E59” (Ni concentration), type “=D48*D59/E48”.
- In the Excel cell “E60” (Mn concentration), type “=D48*D60/E48”.
- In the Excel cell “E61” (Mg concentration), type “=D48*D61/E48”.
- In the Excel cell “E62” (Ca concentration), type “=D48*D62/E48”.
- In the Excel cell “E52” (CT ), type “=E53*F84+E54*F85+E55*F86 +E56*F87
+E57*F88+E58*F89+E59*F90+E60*F91+E61*F92+E62*F93+E63*F94
+E64*F95”.
- In the Excel cell “E51” (liquid specific gravity), type “=-6.139*10(−7) *(𝐄𝟓𝟐)(𝟐)
+9.742*10(−4) *E52+1”.

30. Acid solution flow

- In the Excel cell “G21” (PA concentration), type “=E53”.

- In the Excel cell “G22” (Cu concentration), type “=E54”.
- In the Excel cell “G23” (Ac concentration), type “=E55”.
- In the Excel cell “G24” (Fe(II) concentration), type “=E56”.
- In the Excel cell “G25” (Fe(III) concentration), type “=E57”.
- In the Excel cell “G26” (Al concentration), type “=E58”.
- In the Excel cell “G27” (Co concentration), type “=E59”.
- In the Excel cell “G28” (Zn concentration), type “=E60”.
- In the Excel cell “G29” (Ni concentration), type “=E61”.
- In the Excel cell “G30” (Mn concentration), type “=E62”.

Joseph Kafumbila Page 69

 - In the Excel cell “G31” (Mg concentration), type “=E63”.
- In the Excel cell “G32” (Ca concentration), type “=E64”.
- In the Excel cell “G19” (liquid specific gravity), type “=E51”.
- In the Excel cell “G17” (liquid mass flowrate), type “=I7+I17+H7-F7-E17-D7-
D17”.
- In the Excel cell “G18” (liquid volume flowrate), type “=G17/G19”.

31. Bleed flow

- In the Excel cell “F53” (PA concentration), type “=E53”.

- In the Excel cell “F54” (Cu concentration), type “=E54”.
- In the Excel cell “F55” (Ac concentration), type “=E55”.
- In the Excel cell “F56” (Fe(II) concentration), type “=E56”.
- In the Excel cell “F57” (Fe(III) concentration), type “=E57”.
- In the Excel cell “F58” (Al concentration), type “=E58”.
- In the Excel cell “F59” (Co concentration), type “=E59”.
- In the Excel cell “F60” (Zn concentration), type “=E60”.
- In the Excel cell “F61” (Ni concentration), type “=E61”.
- In the Excel cell “F62” (Mn concentration), type “=E62”.
- In the Excel cell “F63” (Mg concentration), type “=E63”.
- In the Excel cell “F64” (Ca concentration), type “=E64”.
- In the Excel cell “F51” (liquid specific gravity), type “=E51”.
- In the Excel cell “F49” (liquid mass flowrate), type “=E49-G17”.
- In the Excel cell “F50” (liquid volume flowrate), type “=F49/F51”.

32. Additional calculation Table

- In the Excel cell “F107” (TAC total acid consumption), type “=F69+F76*1.54”.
- In the Excel cell “F108” (Quantity of Fe precipitated as Copiapite), type
“=D7*F77+G18*(G24+G25)-I18*(I24+I25)-F109*E99”.
- In the Excel cell “F109” (Quantity of phosphoric acid precipitated as Strengite),
type “=D7*F75+G18*G21-I18*I21”.

33. Solver constraints (green color)

- In the Excel cell “C112” (solver constraint 1), type “= J107/J108”. (ratio of
electrical charge)
- In the Excel cell “C113” (solver constraint 2), type “=I22/((J74+J75
+J76)*63.54)”.
- In the Excel cell “C114” (solver constraint 3), type “=I24/((J77+J78
+J79)*55.85)”.
- In the Excel cell “C115” (solver constraint 4), type “=I26/((J85+J86
+J87+J88)*26.98)”.

Joseph Kafumbila Page 70

- In the Excel cell “C116” (solver constraint 5), type “=I27/((J89+J90)*58.93)”.
- In the Excel cell “C117” (solver constraint 6), type “=I28/((J91+J92
+J93+J94)*65.38)”.
- In the Excel cell “C118” (solver constraint 7), type “=I29/((J95+J96)*58.69)”.
- In the Excel cell “C119” (solver constraint 8), type “=I30/((J97+J98
+J99)*54.94)”.
- In the Excel cell “C120” (solver constraint 9), type “=I31/((J100+J101
+J102)*24.31)”.
- In the Excel cell “C121” (solver constraint 10), type “=I32/((J103+J104
+J105)*40.08)”.
- In the Excel cell “C122” (solver constraint 11), type “=I18*I22/(K18*K22+
D50*D54)”.
- In the Excel cell “C123” (solver constraint 12), type “=E50*E51/E49.
- In the Excel cell “C124” (solver constraint 13), type “=E17*1000/(I18*I23+
D7*F107-G18*G23-F109*C99).
- In the Excel cell “C125” (solver constraint 14), type “=I18*I22/(G18*G22
+D7*F76).
- In the Excel cell “C126” (solver constraint 15), type
“=I18*(I24+I25)/(G18*(G24+G25) +D7*F77-F109*E99).
- In the Excel cell “C127” (solver constraint 16), type “=I18*I26/(G18*G26
+D7*F78).
- In the Excel cell “C128” (solver constraint 17), type “=I18*I27/(G18*G27
+D7*F79).
- In the Excel cell “C129” (solver constraint 18), type “=I18*I28/(G18*G28
+D7*F80).
- In the Excel cell “C130” (solver constraint 19), type “=I18*I29/(G18*G29
+D7*F81).
- In the Excel cell “C131” (solver constraint 20), type “=I18*I30/(G18*G30
+D7*F82).
- In the Excel cell “C132” (solver constraint 21), type “=I18*I31/(G18*G31
+D7*F83).
- In the Excel cell “C133” (solver constraint 22), type “=J112/J113”.
- In the Excel cell “C134” (solver constraint 23), type “=J122/J123”.
- In the Excel cell “C135” (solver constraint 24), type “=(J103*J116)/(-
9.547*10^(5)*J113-3.669*10^(-5)*F67-3.433*10^(-3)*J67+3.669*10^(-3))”.
- In the Excel cell “C136” (solver constraint 25), type “=I7/(D7*(1-
F72/1000)+F109*D99/1000)”.

Joseph Kafumbila Page 71

34. Optimization of variables

Optimization procedure which uses Microsoft Excel solver is as follows:

 On the ‘Data’, in the ‘Analysis group’ click solver (if the solver command is not
available, you must activate the solver add-in).
 In the ‘Set objective’ box, enter the cell reference “C112”.
 Click ‘Value of’ and then type the number ‘1’ in the box.
 In the “By Changing Variable Cells” box, enter the references (E17, I7, I22, I24, I26,
I27, I28, I29, I30, I31, I32, E50, F106, K71, K77, K85, K89, K91, K95, K97, K100,
K103, K113 and K123).
o In the ‘Solver Parameters’ dialog box, click ‘Add’.
o In the ‘Cell Reference’ box, enter the cell reference “C113”.
o Click the ‘relationship’ ‘=‘, in the ‘Constraint’ box, type the number ‘1’.
o Click ‘OK’ to return to ‘Solver Parameters’ dialog box.
……………………………………………………………………………………………..
o In the ‘Solver Parameters’ dialog box, click ‘Add’.
o In the ‘Cell Reference’ box, enter the cell reference “C136”.
o Click the ‘relationship’ ‘=‘, in the ‘Constraint’ box, type the number ‘1’.
o Click ‘OK’ to return to ‘Solver Parameters’ dialog box.

 Click ‘Solve’. To keep the solution values on the worksheet, in the ‘Solver Results’
dialog box, click ‘Keep solver solution’.

Table (5.14) gives the results of mass balance of leach circuit

Joseph Kafumbila Page 72

 Table 5.14- A: Flow diagram mass balance Table

A B C D E F G H I J K L
1
2 Table A Flow diagram mass balance for leach circuit
3
4 1 2 3 4 5 6 7 8
5 Feed Acid SO2 AS CO2 LP Floc UF
6 Solid
7 Mass t/h 900.00 13.37 6.76 871.47 0.035 871.50
8 Volume m3/h 333.33 348.59 0.013 348.60
9 SGS t/m3 2.7 2.5 2.65 2.5
10 Pulp
11 Mass t/h 1551.72 2904.89 1502.59
12 Volume m3/h 985.06 2291.98 951.93
13 SGP t/m3 1.58 1.27 1.58
14 %solid 58 30 58
15 %W/V 0.25
16 Liquid
17 Mass t/h 651.72 47.67 1298.90 2033.42 13.94 631.09
18 Volume m3/h 651.72 25.91 1248.50 1943.39 13.94 603.33
19 SGL t/m3 1.000 1.84 1.040 1.046 1.000 1.046
20 CT 49.070 48.721
21 H3 PO4 g/L 0.041 0.042 0.041
22 Cu g/L 0.300 6.695 6.648
23 Acid g/L 12.676 2.915 2.895
24 Fe(II) g/L 0.763 0.768 0.762
25 Fe(III) g/L 0.029 0.030 0.029
26 Al g/L 0.874 0.880 0.874
27 Co g/L 3.884 3.910 3.882
28 Zn g/L 0.030 0.030 0.030
29 Ni g/L 0.086 0.086 0.086
30 Mn g/L 0.875 0.881 0.874
31 Mg g/L 1.274 1.282 1.273
32 Ca g/L 0.639 0.643 0.639

Joseph Kafumbila Page 73

 Table 5.14- B: Flow diagram mass balance Table

A B C D E F G H I J K L
33
34 Table A Flow diagram mass balance for leach circuit
35
36 9 10 11 12 13 14 15 16
37 OF Raff Bleed
38 Solid
39 Mass t/h
40 Volume m3/h
41 SGS t/m3
42 Pulp
43 Mass t/h
44 Volume m3/h
45 SGP t/m3
46 %solid
47 %W/V
48 Liquid
49 Mass t/h 1416.28 1407.95 109.05
50 Volume m3/h 1353.99 1353.32 104.82
51 SGL t/m3 1.046 1.040 1.040
52 CT 42.578
53 H3 PO4 g/L 0.041 0.041 0.041
54 Cu g/L 6.648 0.300 0.300
55 Acid g/L 2.895 12.676 12.676
56 Fe(II) g/L 0.762 0.763 0.763
57 Fe(III) g/L 0.029 0.029 0.029
58 Al g/L 0.874 0.874 0.874
59 Co g/L 3.882 3.884 3.884
60 Zn g/L 0.030 0.030 0.030
61 Ni g/L 0.086 0.086 0.086
62 Mn g/L 0.874 0.875 0.875
63 Mg g/L 1.273 1.274 1.274
64 Ca g/L 0.639 0.639 0.639

Joseph Kafumbila Page 74

 Table 5.14- C: Flow diagram mass balance Table

A B C D E F G H I J K L
65
66 Table B Additional design criteria Table C Additional Calculation
67 pH 1.7 % Eh 0.590 V
68 Leach redox potential (Ag/AgCl) 370 mV H+ 2.972E-02
69 Gangue acid consumption (GAC) 43.26 Kg/t SO−2
4 1.148E-01
70 SO2 consumption (SO2C) 14.85 Kg/t HSO4− 4.849E-02
71 Pure acid concentration in strong acid 98 % S2 O−2
6 8.053E-02 1.094
72 Leach weight loss (LWL) 32.5 Kg/t H2 PO− 4 7.974E-05
73 CO2 production (CO2P) 7.51 Kg/t H3 PO4 1.502E-04
74 Flocculants dosage 40 g/t Cu+2 6.769E-02 1.169
75 SolPA 0.45 Kg/t CuSO4 3.763E-02
76 SolCu 14.041 Kg/t CuH2 PO+ 4 4.515E-05
77 SolFe 0.861 Kg/t Fe+2 8.584E-03 2.066
78 SolAl 0.688 Kg/t FeSO4 5.113E-03
79 SolCo 2.860 Kg/t FeH2 PO+ 4 4.952E-05
80 SolZn 0.023 Kg/t Fe+3 9.946E-05
81 SolNi 0.068 Kg/t FeSO+ 4 3.150E-04
82 SolMn 0.688 Kg/t Fe(SO4 )− 2 1.124E-04
83 SolMg 1.002 Kg/t FeH2 PO+2 4 1.983E-06
84 αPA 1.000 FeHPO+ 4 2.363E-06
85 αCu 2.511 Al+3 1.307E-02 1.884
86 αAc 1.000 AlSO+ 4 1.436E-02
87 αFe(II) 2.719 Al(SO4 )− 2 5.123E-03
88 αFe(III) 3.580 AlH2 PO+2 4 6.879E-05
89 αAl 6.337 Co+2 4.471E-02 1.350
90 αCo 2.629 CoSO4 2.165E-02
91 αZn 2.468 Zn+2 2.221E-04 3.653
92 αNi 2.635 ZnSO4 1.179E-04
93 αMn 2.747 Zn(SO4 )−2 2 1.179E-04
94 αMg 4.949 ZnH2 PO+ 4 1.002E-07
95 αCa 3.395 Ni+2 9.918E-04 3.004
96 NiSO4 4.802E-04
97 MMAEl
MMPEl PA
MFe Mn+2 1.119E-02 1.951
98 t/t t/t t/t MnSO4 4.831E-03
99 Stren 1.501 1.907 0.570 MnH2 PO+ 4 2.839E-06
100 Copiap 0.351 4.476 Mg +2 3.658E-02 1.437
101 MgSO4 1.615E-02
102 Table C MgH2 PO+ 4 2.044E-05
103 Fe(II) 0.768 g/L Ca+2 1.031E-02 1.987
104 Fe(III) 0.030 g/L CaSO4 5.732E-03
105 Fe(II)/FeT 0.963 CaH2 PO+ 4 2.676E-06
106 .b1 0.993
107 Total acid consumption (TAC) 64.880 Kg/t Ch+ 4.447E-01
108 Qty of Fe precipitated as Copiapite 0.000 Kg/h Ch- 4.447E-01
109 Qty of P precipitated as Strengite 375.80 Kg/h
110

Joseph Kafumbila Page 75

 Table 5.14- D: Flow diagram mass balance Table

A B C D E F G H I J K L
110
111 Table D Excel solver constraints Table C
112 Const 1 1.000 Ia 8.601E-01
113 Const 2 1.000 Ib 8.601E-01 0.065
114 Const 3 1.000
115 Const 4 1.000 γ1 6.713E-01
116 Const 5 1.000 γ2 1.454E-01
117 Const 6 1.000 γ3 1.135E-02
118 Const 7 1.000 aw 9.905E-01
119 Const 8 1.000
120 Const 9 1.000 u 2.348
121 Const 10 1.000 ϕ 9.186E-01
122 Const 11 1.000 Na 5.792E-01
123 Const 12 1.000 Nb 5.792E-01 0.237
124 Const 13 1.000
125 Const 14 1.000 Standard Chemical potential
126 Const 15 1.000 Copiapite -9.971.000 j/mol
127 Const 16 1.000 Fe+2 -78.900 j/mol
128 Const 17 1.000 Fe+3 -4.600 j/mol
129 Const 18 1.000 SO−2
4 -744.530 j/mol
130 Const 19 1.000 H2 O -237.129 j/mol
131 Const 20 1.000
132 Const 21 1.000 Chemical potential
133 Const 22 1.000 SO−2
4 -754677 j/mol
134 Const 23 1.000 H2 O -237153 j/mol
135 Const 24 1.000 H+ -9705 j/mol
136 Const 25 1.000 Fe+2 -95477 j/mol
137 Fe+3 -38551 j/mol
138
139

Joseph Kafumbila Page 76

 Other publications

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Joseph Kafumbila Page 78
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Joseph Kafumbila Page 79