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Hydrometallurgy
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A R T I C LE I N FO A B S T R A C T
Keywords: The dissolution of liberated chrysocolla particles in dilute (0.033 to 0.15 mol L−1) sulfuric acid solutions has
Chrysocolla been shown to be relatively rapid and the kinetics of dissolution are consistent with rate-determining diffusion of
Leach acid through the silica layer that is formed around the particles from which the copper has been dissolved. The
Acid rate is inversely proportional to the square of the particle size and increases linearly with increasing acidity. The
Ash-layer
effect of the addition of chloride ions on the rate is negligible at concentrations below 70 g/L chloride. Addition
Diffusion
of sulphate ions results in reduced rates of dissolution due to complexation of the proton by sulphate ions. The
effect of temperature is relatively small as expected for a process for which the rate is controlled by diffusion.
The rate of dissolution in dilute acid is slower than malachite but faster than tenorite under the same con-
ditions. These results suggest that heap leaching of chrysocolla in dilute acid may be slow relative to malachite
but should present no chemical problems and that there is no advantage to be gained from the addition of
chloride ions. High sulphate concentrations (100 g/L) in the raffinate solution to the heap could reduce the rate
by up to one-half.
⁎
Corresponding author.
E-mail address: m.nicol@murdoch.edu.au (M.J. Nicol).
https://doi.org/10.1016/j.hydromet.2018.04.001
Received 9 January 2018; Received in revised form 22 March 2018; Accepted 1 April 2018
Available online 04 April 2018
0304-386X/ © 2018 Elsevier B.V. All rights reserved.
M.J. Nicol, C. Akilan Hydrometallurgy 178 (2018) 7–11
4. Results
Fig. 1. Species distribution for chrysocolla in acidic sulfate solutions at 25 °C. in which b is a stoichiometric factor (in this case 1 mol copper dis-
solved/mol sulfuric acid consumed), C is the concentration
(mole cm−3) of the species diffusing into or out of the product layer and
D is the diffusion coefficient (cm2 s−1) in the product layer.
Fig. 3 shows the dissolution curves for various size fractions in
0.1 mol L−1 sulfuric acid.
It is obvious that the initial dissolution rate is rapid but it slows
noticeably after about 60% dissolution and that the rate decreases as
the particle size increases. Also shown (as square points and right axis)
are the corresponding plots according to Eq. (2). The good linearity of
the plots up to 80% extraction suggests that the data is consistent with
the assumed rate-determining step.
As a further test of the rate equation, the values of 3 x slope (=1/τ)
of these lines are plotted in Fig. 4 as a function of the reciprocal of the
square of the geometric mean diameter (d) of the screen sizes defining
each size fraction as per Eq. (3).
Fig. 2. Photograph of a group of particles from the +500–710 μm size fraction
Again, the adequate linearity (except for the point for the smallest
before and after leaching.
size) confirms the applicability of the leaching model. From the slope of
the line in Fig. 4, the diffusion coefficient of the proton in the hydrated
published scan in Appendix A. The only impurity detected by XRD was silica layer (density 2.21 g cm−3) can be estimated as
quartz. The lumps were hand-crushed in a pestle and mortar and sev- 7.8 × 10−6 cm2 s−1 that is remarkably similar to the measured diffu-
eral size fractions from 180 μm to 850 μm obtained by dry screening the sion coefficient of HCl in silica gel of 8.5 × 10−6 cm2 s−1 (Patrick and
crushed material. Fig. 2 shows a number of such particles from the Allan, 1934). These values are about an order of magnitude lower than
+500 to 710 μm size fraction. the value in the solution phase (9.3 × 10−5 cm2 s−1 at infinite dilution)
Examination of the particles shows that the chrysocolla (pale blue/ (Cussler, 2011), confirming that diffusion in the product layer is rate-
green) is generally liberated from the quartz (colourless) and other determining.
minor dark gangue minerals. The composition in terms of chrysocolla The results (in terms of the time for complete dissolution) as ob-
content increased with decreasing particle size due to preferential tained from plots similar to those shown in Fig. 3 for experiments on the
crushing of the softer copper mineral. The copper content decreased effect of the acid concentration on the rate of dissolution of the
from 17.8% to 11.7% from the finest to coarsest fraction. +250–355 μm size fraction at 25 °C are summarized in Fig. 5.
After leaching, the converted chrysocolla appears as amorphous It can be seen that the rate increases linearly with increasing acidity
cloudy, white particles easily distinguished visually from the original as would be required for diffusion (a first-order process) as the rate
crystalline quartz. There does not appear to be a noticeable size change controlling step.
during dissolution. The effect of the addition of chloride (as sodium chloride) on the
The leach tests were conducted in a stirred, temperature-controlled rate was studied using the +355–500 μm size fraction in a solution of
baffled reactor as described previously (L Velásquez-Yévenes et al., 0.1 mol L−1 acid at 25 °C. The results are summarized in Table 1.
2010). A small glass tube heat exchanger was fitted to the reactor It is apparent that the rate is independent of the chloride con-
through which chilled water from a low-temperature water bath was centration in the range studied as could be expected if the rate is con-
circulated. Most experiments were conducted at 25 °C at a stirring rate trolled by the diffusion of acid within the silica product layer.
of 580 rev min−1. Agitation at 400 rev min−1 was found to be required Addition of excess sulfate ions (as magnesium sulfate) could be
to maintain the particles in suspension. Unless stated otherwise, 600 mL expected to reduce the rate due to the formation of hydrogen sulfate
of a leach solution of the appropriate composition was added to the ions thereby reducing the proton concentration. The results of such
reactor and, after the temperature had stabilized, 1 g of the desired size experiments with the +250–355 μm size fraction in 0.1 mol L−1 acid at
fraction was added to the reactor. 2 mL samples were periodically re- 25 °C are shown in Table 2.
moved after allowing the suspension to settle for 20 s before sampling These results confirm the above expectation and also shown in
the solution. Table 2 are the calculated proton concentrations using thermodynamic
The solution samples were added to 5 mL of 2 M ammonium data (Martell and Smith, 2004) for the protonation of sulfate and the
chloride.ammonium hydroxide at pH 10 and the volume made up to formation of magesium sulfate ion-pairs at various ionic strengths. The
10 mL. The absorbance of the solution at 615 nm was measure in a approximate correlation between the rate of dissolution and the proton
20 mm quartz cell using a Shimadzu spectrophotometer. A standard concentration is consistent with the rate-determining step being the
solution of copper was used for calibration. This method is more rapid diffusion of protons through the product layer. It is likely that
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M.J. Nicol, C. Akilan Hydrometallurgy 178 (2018) 7–11
Fig. 3. Effect of particle size on the dissolution of chrysocolla in 0.1 mol L−1 acid at 25 °C.
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M.J. Nicol, C. Akilan Hydrometallurgy 178 (2018) 7–11
Table 1
Effect of chloride on the rate of dissolution.
[NaCl] M 1/τ min−1
0 0.0049
0.2 0.0055
0.5 0.0051
2 0.0051
Table 2
Effect of sulfate on the rate of dissolution.
[Sulfate] mol L−1 1/τ min−1 [H+] calc mol L−1
Table 4
Table 3 Initial rates of dissolution in 0.1 mol L−1 H2SO4 at 25 °C.
Effect of temperature on the rate of dissolution. Mineral Initial rate mol cm−2 min−1
° −1
Temp C 1/τ min
Malachite 2.4 × 10−6
20 0.0042 Chrysocolla 1.3 × 10−6
25 0.0049 Tenoritea 2.5 × 10−7
30 0.0056
35 0.0068
a
0.2 M H2SO4 – rotating disk.
Appendix A. Appendix
A published (University of Arizona, 2018) XRD scan of chrysocolla (Fig. A.1) is compared to that obtained with the sample used in this study (Fig.
A.2). The former was characterized as having broad, low peaks with weak lines often diffuse. The pattern is fairly characteristic. The similarity in
terms of very broad lines for the present sample provides confirmatory identification of the present sample as chrysocolla. Note the sharp peaks in the
present sample (Fig. A.2) due to quartz as an impurity.
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M.J. Nicol, C. Akilan Hydrometallurgy 178 (2018) 7–11
Fig. A.1. XRD scan of chrysocolla courtesy of RRUFF project at University of Arizona (2018)
Fig. A.2. XRD scan for the sample of chrysocolla used in the present study.
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