1

September 21 to 24, 2014 San Luis Potosi, Mexico

Leaching Of Sub-Grade Copper-Zinc Ore Based On The
Application Of Electrochemically Treated Waste-Dump
Acid Water
Chanturiya .L.
1
, Samusev .L.
2

1
Russia, Moscow, Leninskiy prospect, 6, 119991
Mining Institute of National University of Science and Technology "MISIS"
E-mail: elenachan@mail.ru
2
Russia, Moscow, Krjukovsky tupik, 4, 111020
Institute of Comprehensive Exploitation of Mineral Resources, Russian Academy of Sciences
E-mail: Andrey63vzm@mail.ru
Abstract
Feasibility of use of electrochemically treated waste-dump acid waters for the
intensification (2.8 - 6.0-fold) of leaching of sub-standard sulphidic copper-zinc ores is
experimentally determined. The technology provides the usage of a product of the
electrochemically treated waste-dump acid waters with high concentration of oxidants.
The mechanism of the intensification of the leaching process consists in the
acidification of sulphides by hypochlorite ions, MnO4 -, Fe3 + and the dissolved oxygen
with formation of easily dissoluble compounds and micro defects on the surface and in
the bulk of sulphidic minerals that results in the intensive infiltration of the leaching
solution into its volume and the accelerated desorption of newly formed chemical
products. The laboratory and full-scale tests with sub-grade copper-zinc ores proved
the efficiency of application of electrochemically treated waste-dump water. Copper
and zinc concentration of 1.5 - 3.0 g/dm3 in productive solutions required for the
subsequent processing by cementation method were provided with 20.2% increase of
copper and 14.4% increase of zinc recovery as compared with a standard flow sheet of
sulphuric acid leaching. The use of electrochemically treated waste-dump acid waters
for leaching of copper-zinc ores allows to receive the additional production and to
improve environmental ecological conditions.
Keywords leaching, copper-zinc ore, hypochlorite, waste-dump water,
electrochemical treatment
1. Introduction

Long-year development of solid mineral deposit by traditional physical and engineering
methods has resulted in significant depletion of ore balance-sheet reserves,
deterioration of their quality, accumulation of great tonnage of mineral mining and
smelting wastes as well as industrial waste water. In many cases metal concentration
in industrial waste water (from mines and waste dumps, etc.) is similar to that of
conventional hydro mineral feedstock, namely mineralized water and brines. At the
same time, sub-grade ore dumps and industrial waste waters form a long-term source
of environmental contamination (Chanturiya, V. A., 2008).
Arrangement and intensification of forced leaching is one of the methods minimizing
the harmful environmental effect of such sources.
Presently, leaching methods are mainly used for the processing of oxidized copper-zinc
ores containing 0.1 to 3% of copper and zinc. In this case, sulphuric acid solutions are


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September 21 to 24, 2014 San Luis Potosi, Mexico
used as a basic solvent (Chanturiya, V. A., Minenko, V.G., Koporulina, E.V., Samusev,
A.L., Chanturiya E.L., 2011).
However, the basis of mineral reserves and resources of the copper-zinc industry is
formed by pyrite deposits with main minerals are pyrite, chalcopyrite and sphalerite.
Application of sulphuric acid solutions for leaching of such mineral feedstock is not
efficient, as sulphuric acid is not able to oxidize it in the absence of extra oxidizers.
Such agents as Fe3+, hydrogen peroxide, sodium hypochlorite, oxygen, etc., are used
as oxidizers, as their application results in sulphide sulphur oxidation to SO42- ions and
conversion of non-ferrous metals into liquid phase. One of the most promising methods
of liquid phase saturation with oxidizers is electrochemical technology of water
conditioning, which is able to specifically regulate physical-chemical properties and gas
composition of liquid media without application of any agents (Fazlullin, M.I., 2001;
Tikhonov, V.I., Volkov, A.A. 2002).
For the investigation of the mechanism of intensifying the process of copper-zinc ore
leaching with the application of electrochemically treated waste-dump water with high
concentration of oxidizers some specially designed experiments were carried out to
estimate the effect on the variation of the structure and chemical composition of the
mineral surface.
2. Experimental Work

Sulphide minerals (pyrite, chalcopyrite, sphalerite), sub-grade Cu-Zn ores and waste
dumps (Table 1), waste-dump water (Table 2), man-made model solutions formed the
subject matter of the research.

Table 1 Chemical composition of copper-zinc ore from Uchalinskoe deposit
Component Fe SiO
2
S
total
Al
2
O
3
CaO Zn Cu
Content, % 22.6 23.2 31.2 7.3 5.3 2.8 0.7

Table 2 Chemical composition of waste-dump water
Component Fe
total
Ca
2+
S
total
Mn
2+
Zn
2+
Cu
2+
Na
+

Concentration, mg/dm
3
66 440 1.1 370 56 56 48

Research was performed with the use of optical and analytical electronic microscopy,
sorption method of measurement of sulphide material specific surface. Research into
leaching was performed with a modular test bench set (Figure 1). The test bench set is
helpful for the investigation of the process of useful components leaching for a broad
range of ore size on a continuous basis.

Research of electrochemically treated of waste-dump water was performed with the
laboratory diaphragmless cell at 250 A/m2 current density, with addition of NaCl salt.


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September 21 to 24, 2014 San Luis Potosi, Mexico

Figure 1 Modular test bench set for ore leaching on the continuous basis

As a result of the following cell reactions:
at the anode: 2Cl
-
- 2e Cl
2

at the cathode: 2
2
+2
2
+ 2
-

in the volume Cl
2
+ H
2
O HCl + HClO 2H
+
+ ClO
-
+ Cl
-

the concentration of available chlorine ions in waste-dump water increases to 1.5
g/dm
3
.

3. Results and Discussions

It has been found that application of modified electrochemically treated waste-dump
water results in sulphide oxidation by available chlorine ions, MnO4-, Fe3+ ions and
oxygen, with the formation of readily soluble copper and zinc complexes, sulphates,
hydroxides and oxides, etc. (Figure 2). It also results in the intensive defect and pore
formation in near-surface layers of the mineral material.
Data on the formation of pores and microcracks on the surface of copper-zinc ore are
proved by the investigation of the specific surface of sulphide minerals.
As a result of interaction of sulphide minerals with electrochemically treated waste-
dump water the specific surface of pyrite, sphalerite and chalcopyrite increased 1.4 -,
3.3- and 5.6- time accordingly, as compared with the treatment by sulphuric acid
solution (Figure 3).

Data on the expansion of the specific surface of sulphides are proved by optical
analysis of the mineral surface. After the contact with electrochemically treated waste-
dump water the formation of new phases of easily soluble complexes and the element
sulphur layer on the surface of sulphide minerals were found (Figures 4-5).

This mechanism implies intensive oxidation of sulphide by available chlorine ions,
MnO4- and Fe3+ ions and oxygen accompanied by the destruction of mineral matrix
with the formation of defects and microcracks that results in the intensive penetration of


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September 21 to 24, 2014 San Luis Potosi, Mexico
the leaching solution into the mineral volume and accelerated desorption of newly
formed chemical products.

Figure 2 Iron, copper and zinc mineral film formed on the surface of Cu-Zn ore, oxidized
manganese complexes after the contact with electrochemically treated waste-dump water

The effect of electrochemically treated waste-dump water characterized by high
concentration of oxidizers on the rate of dissolution was studied with monomineral
samples of pyrite, chalcopyrite and sphalerite. To compare the results some
experiments were carried out with the application of original waste-dump water and
sulphuric acid solutions. The experiments (Figure 6) showed that in case of waste-
dump water electrolysis product application the rate of chalcopyrite, sphalerite and
pyrite dissolution is 2.8 7.3-time higher as compared with the application of sulphuric
acid solution.
Research of the effect of current density, duration of treatment and NaCl original
concentration on the efficiency of hypochlorite solution production has identified the
most reasonable parameters of electrochemical treatment as follows: Is=250 A/m2, t
treat = 10 minutes, NaCl = 20 g/dm3.
Bench tests have proved high efficiency of the proposed conditions of waste-dump
water electrochemical treatment, which intensify the process of leaching of sub-grade
copper-zinc ores from Uchalinsky GOK.
The desired 1.53.0 g/dm3 copper and zinc concentrations for the subsequent
processing of productive solutions by cementation method were provided after 100-day
leaching.
In this case copper and zinc recovery was 86.4% and 43.0% accordingly. At the same
time, copper and zinc recovery with the application of sulphuric acid solution was of
66.2% and of 28.6% respectively. The technological scheme of leaching copper-zinc
ores using electrochemical water treatment technologies and the main technological
equipment are shown on the Figure 7.


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September 21 to 24, 2014 San Luis Potosi, Mexico

Figure 3 Variation of the specific surface of sulphide minerals (1 pyrite; 2 chalcopyrite; 3
sphalerite) in the interaction with different solvents



Figure 4 Newly formed phases on the
surface of chalcopyrite
Figure 5 Element sulphur layer on the
surface of sphalerite

Figure 6 Monomineral samples dissolution rate (1 Chalcopyrite, 2 Pyrite, 3 Sphalerite)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
1 2 3
s
p
e
c
i
f
i
c

s
u
r
f
a
c
e

m
2
/
g

Original
Sulfuric acid
Electrochemically
0
2
4
6
8
10
12
14
16
1 2 3
m
g
/
g
*
d
a
y
s
waste-dump water
sulphuric acid solution
electrochemically treated waste-dump water


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September 21 to 24, 2014 San Luis Potosi, Mexico


Figure 7 The technological scheme of heap leaching copper-zinc ores

4. Conclusions

Thus, on the basis of modern research methods findings the mechanism of intensifying
the process of copper-zinc ore heap leaching is determined, which implies the
formation of readily soluble copper and zinc complexes on sulphide surface and
accompanied by the destruction of mineral matrix with the formation of defects and
microcracks under the effect of modified chlorine ions of electrochemically treated
waste-dump water. This has let the authors propose the efficient method of integrated
processing of sub-grade copper-zinc ore and mineralized water, which is rather helpful
for the enhancement of leaching rate, end-to-end non-ferrous metal recovery and
utilization of industrial waste water that is important for the industry and facilitates the
improvement of environmental situation in the region.
The decision on the patent grant for invention named "The way the heap leaching of
oxidized and mixed copper-zinc ore" has been obtained (authors: V.A. Chanturya, E.L.
Chanturya, V.G. Minenko, A.L. Samusev, A.I. Kaplin). Order 2010147041/03 (067
950).

5. Acknowledgments

Authors express thanks to the school of thought of Academician of Russian Academy
of science V. Chanturiya for the support and scientific guidance.

References
Chanturiya, V. A., (2008) Innovation Processes in Technologies for the Processing of
Refractory Mineral Raw Materials. ISSN 1075 7015 Geologiya Rudnykh
Mestorozhdeniy, 50 (6) 491501.

Chanturiya, V. A., Minenko, V.G., Koporulina, E.V., Samusev, A.L., Chanturiya E.L.
(2011) Grounding the efficiency of application of electrochemical technology of water
treatment for the processes of ore heap leaching. Fiziko-tekhnicheskiye problemy
razrabotki poleznykh iskopaemykh. 5 115-124.

Fazlullin, M.I. (2001) Heap leaching of noble metals. M.: Academy of Mining Sciences.
Tikhonov, V.I., Volkov, A.A. (2002). Science 296, 2363.