Thermochemical database and copper mineral

solubilities in process waters using PHREEQC

Authors:
- Fuentes, Aldo, Univ. Técnica Federico Santa María, Chile.
- Ojeda, Sergio, Univ. Técnica Federico Santa María, Chile.
- Justel, Francisca, Univ. Técnica Federico Santa María, Chile.
- Contreras, José, Univ. Técnica Federico Santa María, Chile. Presenter: Casas, Jesús M.
- Hernández, Pía, Univ. de Antofagasta, Chile. Univ. Técnica Federico Santa María, Chile.
- Jiménez, Yecid, Univ. de Antofagasta, Chile.
- Casas, Jesús M., Univ. Técnica Federico Santa María, Chile.

Symposium: Hydrometallurgy
Introduction
CuSO4-H2SO4 aqueous solutions are the basis of the hydrometallurgical processes for production of Cu cathodes
via EW and CuSO4:5H2O via crystallization

Table 1: Typical concentration of Cu and H2SO4 in solutions of industrial processes for

Cu cathode production via EW and CuSO4:5H2O via crystallization.
Raffinate Rich Spent
Solute PLS Electrolyte Electrolyte
Solution
Cu, total, g/L 2-6 0.2 - 0.5 40 - 50 35 - 45
H2SO4, total, g/L 1-2 8 - 15 170 - 180 180 - 200

A literature review shows few data on thermochemical modeling for aqueous Cu electrolyte systems applied to
the hydrometallurgical processes, where solutions present high ionic strength values.

In this work, a parameterization of the SIT model applied to the CuSO4 - H2SO4 -H2O ternary system in the
temperature range 10 - 50 °C was carried out, which allowed estimating the thermodynamic properties, the
binary interaction parameters (virial coefficients) and simulating speciation and solubility of copper electrolytic
systems.
In addition, simulations of solubility at 25 °C in CuSO4 solutions containing Ca or Mg, and copper chloride present
in NaCl solutions are presented.
Model Formulation H2O NaCl0
H
+
CuCl0
Especiation and Ionic interactions
in copper electrolytes CuCl+ CuCl20
Cu+
Cl- MgCl+
CaCl+
CuSO40
Cu 2+

HSO4-
SO42- H2SO40
Na+ NaHSO40 NaSO4-
Ca2+ MgHSO4+

Mg2+ CaHSO4+

(1)
Chemical reactions in the general from:
where νi, zi and r stand for stoichiometric coefficient, charge of a reaction species (reactant or product) Bi, and the number of moles of water participating in the reaction, respectively.

Equilibrium relationships for each defined component are:

(2)

where and stand for the conditional and standard thermodynamic equilibrium constants of the reaction, respectively.
represents the water activity and is the activity coefficient for the -th aqueous species.
Model Formulation

Mass Balances:

where, mi is the molal concentration and TOT Xj is the total molal concentration of the j-th component.

The specific interaction (SIT) model was used to evaluate the activity coefficients () of dissolved ions.
This model is based on Bröonsted-Guggenheim-Scatchard theory adapted by Ciavatta, (1980, 1990):
(4)

where, is the Debye-Hückel’s slop ( 0.51 (kg/mol) 0.5 at 25 °C), is the ion strength of solution in mol/kg, is the molality, and
is the interaction parameter between the counter ions and , in kg/mol. and 0 for ions of same charge sign.

Ionic strength of the solution (I) is defined by:

(5)
 Methodology
The equilibrium speciation model consists of an algebraic non-linear system, previous equations 1 to 5.
Solution through PHREEQC software (Parkhurst and Appelo, 2013), using multi-variable Newton-Raphson numerical
algorithm and allows the calculation of the aqueous speciation in the presence of ions, complexes, minerals, and
dissolved gaseous species for a wide range of pH, temperature, and concentration values.
The electrolyte systems studied were: System System
• H2SO4 - H2O • CuSO4 - MgSO4 - H2O
• CuSO4 - H2O • CuCl2 - NaCl - H2O
• CuSO4 - H2SO4 - H2O • CuCl - NaCl - H2O
• CuSO4 - CaSO4 - H2O
The standard equilibrium constants (K0) were correlated with the temperature (T) as:
(6)

The binary interaction parameters between anions and cations were correlated with the temperature as:
(7)
Methodology

The binary interaction parameters, were regressed with the application of software PHREEQC coupled with the
software PEST (Doherty 2018), minimizing an objective function (OF) defined by :

(8)

The parameters of the models developed in this work are compiled in the following database compatible with
Phreeqc software: “Copper_Thermochemical_Database.dat”
Results and Discussion System CuSO4 - H2SO4 - H2O

10

Species Concentration, (mol/kg H2O)

HSO4-
Chemical model :
H2O H+ + OH- (9) SO42-
H+
1
H+ + SO42- HSO4- (10)
CuSO40
H + HSO H2SO4
+
4
- 0
(11) CuSO40
Cu2+ + SO42- CuSO40 (12) 0.1
Cu2+

CuSO4·5H2O(s) Cu2+ + SO42- + 5H2O (13)

Cu2+
0.01
[H+], [HSO4-] & [CuSO40] species increases
SO42-
its stability with the increase of total
HSO4-
dissolved sulphate. 0.001
H+

0.5 1 1.5 2 2.5 3 3.5 4

The relative stabilities of both [Cu 2+] &
[SO42-] decrease with the addition of Total Sulphate Concentration, (mol/kg H2O)

sulphuric acid. Figure 1: Species distribution in the ternary system CuSO4 - H2SO4 - H2O,
at 50 °C, [CuSO4] = 0.8 molal, as a function of total sulphate added as H2SO4.
Results and Discussion System CuSO4 - H2SO4 - H2O
160

140

120
Chalcanthite solubility increases markedly CuSO4 + H2O
100
in the range 0 - 60 °C and decreases by the

[Cu], (g/L)
presence on sulphuric acid due to the 80

common effect of sulphate ions. 60

CuSO4 + H2SO4 + H2O
40

These results are important to fix the 20

optimum operating conditions for copper 0

0 10 20 30 40 50 60
electrowinning at high temperature (50 - Temperature, (°C)
60 °C), and for chalcanthite crystallization
Figure 2: Chalcanthite (CuSO4·5H2O) solubility in water and aqueous
at low temperature (0 - 10 °C).
sulphuric acid solution (150 - 200 g/L) as a function of temperature.
Calculated values with SIT-model and experimental data from
Milligan & Moyer (1975), and Höffler & Steiger (2018).
Results and Discussion System CuSO4 - H2SO4 - H2O
2.2

2.0

1.8

1.6

[Cu], (mol/kg H2O)

1.4
The chalcanthite solubility decreases
1.2
markedly with increasing sulphuric acid
1.0
concentration due to the common effect of
0.8
sulphate ions. 0.6

0.4
These results are important to fix the 0.2
optimum operating conditions for 0.0 0.5 1.0 1.5 2.0 2.5 3.0

chalcanthite reactive crystallization using [H2SO4], (mol/kg H2O)

sulphuric acid as saturating agent of the Exp. 10°C Exp. 25°C Exp. 50 °C
electrolyte solution.
Figure 3: Chalcanthite (CuSO4·5H2O) solubility in aqueous solutions of
sulphuric acid, at three temperatures. Calculated values with SIT-model
and experimental data from Agde & Barkhot (1927) (10 and 50 °C),
Linke (1958) (25 °C), Milligan & Moyer (1975) (10, 25 and 50 °C), de
Juan et al. (1999) (25 °C), and Justel et al. (2015) (25 °C).
 0.017
Results and Discussion
[CaSO4] , (mol/kg H2O) 0.016 3.5

[MgSO4], (mol/kg H2O)

MgSO4·7H O
0.015 3 2

0.014 2.5
0.013 Cu
2 SO
0.012 4 ·5H
1.5 O
0.011 2

0.010 1
0.009 0.5
0.008 0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 -0.6 0.4 1.4
[CuSO4], (mol/kg H2O)
[CuSO4], (mol/kg H2O)

Figure 4: Gypsum solubility (CaSO4:2H2O) in aqueous solutions Figure 5: Chalcanthite (CuSO 4·5H2O) and epsomite (MgSO4·7H2O) solubilities in aqueous
of copper sulphate at 25 °C. Calculated values with SIT-model solutions of copper and magnesium sulphates at 25 °C. Calculated values with SIT-model and
and experimental data from Wollmann & Voigt, (2008). experimental data from Averina & Shevchuk, (1967).
6.4
6.2 2.5
[CuCl2], (mol/kg H2O)

[CuCl], (mol/kg H2O)

6.0
2
5.8
CuCl
5.6 2 ·2H O 1.5 )
(cr
2
5.4 uCl 2
1 C
5.2
5.0
0.5
4.8
4.6 0
0 0.5 1 1.5 2 2.5 3 3.5 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6
[NaCl], (mol/kg H2O) [NaCl], (mol/kg H2O)
Calculated Exp. (Fritz 1982) Exp. (Berger & Winand 1984)
 Conclusions

• The speciation of copper electrolytes and estimations of copper mineral solubilities can be effectively simulated at
different temperatures (10 - 50 °C) and solution concentrations (0 - 6 molal), using a thermochemical model based on
the specific ion interaction theory (SIT model) and the use of PHREEQC software with improved database and
properties.

• The results indicated that metal solubilities were strongly dependent on the temperatures and salinities or
concentrations of the solution for the cases studied.

• The modeling of ionic speciation and the estimation of mineral solubilities and physicochemical properties of copper
electrolytes allows us to develop a thermochemical database.
Thermochemical simulations could contribute to obtain operational improvements of hydrometallurgical processes
to produce copper cathodes via EW and the crystallization of CuSO4:5H2O.
 Thermochemical database and copper mineral
solubilities in process waters using PHREEQC

Acknowledgements:
The authors thank the Universidad Técnica Federico Santa María (project: PI_LII_2022_05)
and the Universidad de Antofagasta for their supports in this research.