J. Cent. South Univ.

(2017) 24: 2799−2804

DOI: https://doi.org/10.1007/s11771-017-3694-3

Copper smelter slag treatment by ammonia solution:

Leaching process optimization

R. Nadirov1, L. Syzdykova2, A. Zhussupova2

1. Department of General and Inorganic Chemistry, al-Farabi Kazakh National University, Almaty, 050040, Kazakhstan;
2. Department of Physical Chemistry, Catalysis and Petrochemistry, al-Farabi Kazakh National University,
Almaty, 050040, Kazakhstan
© Central South University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2017

Abstract: The feasibility of copper smelter slag processing by ammonia solution treatment was investigated. The central composite
rotatable design (CCRD) and approximation method were used to determine the optimum conditions of zinc and copper recovery to a
solution. The experimental design was done at five levels of the four operating parameters which were the initial concentration of
NH3, the initial Cl– ions concentration, leaching time and solid/liquid ratio. Two mathematical models describing dependence of
metal recovery on the operating parameters were obtained. The models are successful in predicting the responses. It was found that
optimal parameters for zinc and copper recovery are as follows (values for copper are given in brackets): initial CNH3 17.1% (19.9%),
initial CCl– 160 g/L (160 g/L), leaching process duration 4.56 h (4.13 h), solid/liquid ratio 0.39 (0.53). The maximum Zn and Cu
recoveries to solution, obtained experimentally under the conditions, are 81.16% and 56.48%, respectively.

Key words: copper slag; ammonia solution; metal recovery; central composite design; optimization

described by the following schemes:

1 Introduction
Copper smelter slag is a by-product of the
pyrometallurgical stages in the copper recovery process
from sulfide materials, and mainly consists of oxides of
metals and silicone, as well as considerable amounts of
metallic values besides copper [1]. Pyrometallurgical,
hydrometallurgical and bio-hydrometallurgical methods
are the ways that can be used for non-ferrous metals
recovery from copper smelter slag [2]. Today attention is
focusing on hydrometallurgical methods for raw
materials treatment in non-ferrous metallurgy because of
relatively low environmental and operational concerns.
Numerous publications have studied the leaching of base
metals from metallurgical slag [3–10].
Recently, it was found that ammonia solutions
containing ammonium chloride are effective for the
extraction of zinc and copper from technogenic raw
materials, containing zinc and copper oxides [11, 12].
Physico-chemical basis and technological principles of
zinc and copper recovery by ammonia–ammonium
extraction are based on the properties of the system
H2O–NH3–NH4Cl containing zinc and copper amines,
and the phase equilibria liquid–solid, liquid – vapor. Zinc
and copper dissolution in aqueous solution of NH4OH in
the absence (1) and presence (2) of Cl – ions can be
MО+4NH3(sol)+nH2O→[M(NH3)4](OH)2+(n–1)H2O (1)
2+ –
МО+хNH3(sol)+2NH4Cl(sol)→[M(NH3)n] 2Cl +H2O
(2)
where М=Cu, Zn; n=x+2.
Previously we have reported the investigation of
zinc and copper recovery process from copper smelter
slag of Balkhash copper plant (Kazakhstan) by
ammonium chloride treatment [13]. In the present study,
to avoid the using of high-temperature processes we
focused on investigating the copper and zinc recovery
process by ammonia solution treatment of copper smelter
slag. The work is undertaken to investigate the
effectiveness of four process variables, namely; an initial
concentration of NH3, an initial concentration of Cl– ions,
treatment process duration and solid/liquid ratio on the
copper and zinc recovery to a solution from copper
smelter slag.
Experimental design is widely used for regulation of
the effects of parameters in many processes. The
experiments in the present work are planned using
central composite rotatable design to investigate the main
effects of each operating factor and the interactions of
these variables and to find out the factors combination
that gives the maximum values of copper and zinc
recovery, separately.

Received date: 2016−07−01; Accepted date: 2017−03−13

Corresponding author: R. Nadirov, PhD; Tel: +7–747–4520525; E-mail: nadirov.rashid@gmail.com
2800 J. Cent. South Univ. (2017) 24: 2799–2804
experimental design: statistical design experiments,
2 Materials and methods estimation of coefficient through a mathematical model
and analysis of the model workability (Montgomery,
2.1 Materials 2001). In the present study, four operating parameters
Mineralogical analysis of slag sample, performed were selected as independent variables: initial
using DRON-3M model diffractometer, is presented in concentration of NH3 (x1), initial Cl– ions concentration
Table 1. (x2), leaching duration (x3) and solid/liquid ratio (x4). The
levels and ranges of operating parameters are shown in
Table 1 Mineralogical analysis of slag sample (mass Table 3. The dependent output response variables were
fraction, %) copper and zinc recovery (%).
Fe2SiO4 FeSiO3 Fe3O4 ZnFe2O4 CaSiO3 MgSiO3
Table 3 Independent variables and their levels used for central
29.4 26.7 9.3 15.1 2.5 0.7
composite rotatable design
Cu2S Cu5FeS4 CuFeS2 ZnS Al2SiO5
Range and level
0.5 0.7 1.0 1.2 4.6 Variable Symbol
–2 –1 0 1 2
Initial
Chemical analysis of slag sample, performed using concentration x1 2 10 15 20 25
optical emission spectroscopy with inductively coupled of NH3/%
plasma (OPTIMA 8000, Perkin Elmer), is presented in Initial
Table 2. concentration of x2 0 40 80 120 160
Cl– ions/(g·L–1)
Table 2 Chemical analysis of slag sample (mass fraction, %) Leaching
x3 1 2 3 4 5
duration/h
Si Fe Zn Cu Ca Mg S Al Solid-to-liquid
x4 0.2 0.3 0.4 0.5 0.6
13.95 39.70 4.57 1.18 0.77 0.18 1.06 1.54 ratio

2.2 Slag leaching The matrix of CCRD is given in Table 3. According

2.2.1 Experimental procedures
The slag sample produced by Balkhash copper plant
(Kazakhstan) was used for the experiments. A sample of
slag (10 g; –200 mesh) was placed into a glass-stopper
150-mL flask. An ammonia solution with desired
concentration of NH4OH and Cl– ions was prepared by
mixing distilled water and NH4Cl to the concentrated
to this table, the design is composed of 24 factorial
design (runs 1–16), 8 star-points (runs 17–24) and 12
replicates (runs 25–36).
The least square method was used to estimate the
correlation of the independent variables and the response
as a second-order polynomial equation:
k k k

ammonia solution. The contents of the flask were well y  b0   bi xi   buj xu x j  b jj x 2j   (4)
j 1 u , j 1 j 1,u  j
stirred using horizontal shaker at an agitation speed
200 r/min for a certain time and then were filtered. The where b0 is the value for the fixed response at the central
concentration of metal ions in solution was determined point of the experiment; bi, bj and bij are the linear,
by atomic adsorption spectrometer (Shimadzu AA-6200). quadratic and cross-product coefficients, respectively;
Solid residues were analyzed by X-ray fluorescence and ε is the residual error, estimated by the difference
(Spectroscan). The amount of metal recovered was between the predicted and the observed value of
estimated using Eq. (3). response (y).
 m  The dimensionless xj variables are related to the
  1  1   100% (3) standardized forms as shown below [14]:
 m 0 
z j  z 0j z j max  z j min
where η is the recovery; m0 and m1 correspond to metal xi  , j=1, 2, 3, …, k, z 0j  ,
contents of sample before and after being leaching, z j 2
respectively. z j max  z j min
2.2.2 Experimental design z j 
2
Central composite rotatable design (CCRD) helps to
optimize the process, affected by a number of operating where zjmax and zjmin represent the maximum and the
parameters with the minimum numbers of experiments as minimum levels of factor j in natural unit. The
well as to determine the relationship between response, coefficients of the fitted equation were obtained from
namely, copper and zinc recovery to a solution, and data of Eq. (4) as follows:
operating factors. The three steps were used in B=[XTX]–1[X]TY (5)
J. Cent. South Univ. (2017) 24: 2799–2804
where B is the column matrix of estimated coefficients;
[XTX]–1 is the dispersion matrix; [X]T is the transpose
matrix [X] and Y is the column matrix of observed values.
Three known tests were used to evaluate the adequacy of
the mathematical model, including Student’s t-test,
R-square test and Fisher test [15]. Excel software was
used for model coefficients estimation (Eq. (4)).
2801
3 Results and discussion
3.1 Leaching process modeling
The model coefficients for copper and zinc recovery,
separately, obtained from mathematical processing of
data presented in Table 4, were tested for significance

Table 4 Experimental design and results for zinc and copper recovery to solution
Coded value of parameters Zinc recovery/% Copper recovery/%
Run No.
x0 x1 x2 x3 x4 Observed Predicted Observed Predicted
1 1 –1 –1 –1 –1 37.42 37.34 22.42 23.20
2 1 1 –1 –1 –1 62.14 63.64 35.49 36.11
3 1 –1 1 –1 –1 37.87 38.47 30.11 30.81
4 1 1 1 –1 –1 62.42 62.37 48.53 48.14
5 1 –1 –1 1 –1 60.86 61.51 34.48 33.82
6 1 1 –1 1 –1 78.23 77.04 44.57 44.64
7 1 –1 1 1 –1 61.14 62.64 37.03 37.79
8 1 1 1 1 –1 76.83 75.77 53.21 53.04
9 1 –1 –1 –1 1 20.61 21.21 14.56 14.54
10 1 1 –1 –1 1 45.79 43.95 20.44 19.90
11 1 –1 1 –1 1 22.77 24.25 30.67 30.81
12 1 1 1 –1 1 45.05 44.58 40.12 40.59
13 1 –1 –1 1 1 57.11 57.45 31.63 32.23
14 1 1 -1 1 1 69.86 69.43 36.39 35.50
15 1 –1 1 1 1 62.45 60.49 45.67 44.86
16 1 1 1 1 1 70.33 70.06 53.12 52.55
17 1 –2 0 0 0 35.80 34.22 27.64 26.95
18 1 2 0 0 0 68.19 68.27 46.81 47.56
19 1 0 –2 0 0 67.38 68.71 20.17 20.24
20 1 0 2 0 0 69.24 69.15 44.91 44.90
21 1 0 0 –2 0 29.58 28.69 22.46 21.63
22 1 0 0 2 0 77.13 78.33 43.32 44.21
23 1 0 0 0 –2 55.48 54.53 47.38 46.46
24 1 0 0 0 2 31.42 32.69 36.58 37.32
25 1 0 0 0 0 67.44 68.22 42.40 41.89
26 1 0 0 0 0 70.03 68.22 41.78 41.89
27 1 0 0 0 0 67.81 68.22 41.32 41.89
28 1 0 0 0 0 68.20 68.22 42.11 41.89
29 1 0 0 0 0 67.31 68.22 41.91 41.89
30 1 0 0 0 0 67.89 68.22 41.62 41.89
31 1 0 0 0 0 68.68 68.22 42.68 41.89
32 1 0 0 0 0 69.11 68.22 42.30 41.89
33 1 0 0 0 0 68.20 68.22 41.78 41.89
34 1 0 0 0 0 67.69 68.22 40.89 41.89
35 1 0 0 0 0 67.91 68.22 42.13 41.89
36 1 0 0 0 0 68.42 68.22 41.50 41.89
2802
(t-test), at 5% of significance level and 11 degrees of
freedom.
Test results showed that all individual effects for
copper and zinc recovery are significant at 5% of
significance level. Only the interaction (x4×x4) for copper
recovery and the interactions (x2×x2), (x2×x3) for zinc
recovery are not significant. Therefore, mentioned
interactions were excluded from the appropriate final
equations.
The second-order response function representing
copper and zinc recovery to solution obtained after
realizing 36 experiments and discarding the insignificant
effects can be shown in coded variables as follows:
Cu recovery=41.895+5.152x1+6.165x2+5.645x3–
2.285x4+1.106x1x2–0.521x1x3–1.889x1x4–
0.910x2x3+2.165x2x4+1.768x3x4–1.159x12–
2.331x22–2.243x32
Zn recovery=68.271+8.967x1+0.44x2+12.410x3–5.461x4–
0.601x1x2–2.690x1x3–0.890x1x4+0.476x2x4+
3.020x3x4–4.030x12–3.690x32–6.166x42 (7)
The Fisher’s variance ratio test, i.e., F-test, was
used for testing of equation reliability; the calculated
values of F-test are presented in Table 5. The upper
degree of freedom for models of copper and zinc
recovery are 22 and 23, respectively. The lower degree of
freedom for both models is 11. The tabulated F values
for 5% of significance in the case of copper and zinc
recoveries are 2.640 and 2.625, respectively. Comparison
of calculated and tabulated F values for both models,
separately, enables to assume the statistical significance
of both models.
J. Cent. South Univ. (2017) 24: 2799–2804
(Eqs. (6), (7)), show that initial concentration of NH3,
initial Cl– ions concentration, leaching time and solid-to-
liquid ratio all have an individual effect on the zinc and
copper recovery from copper slag to a solution during the
ammonia–ammonium leaching. It was of interest to
compare the effect of the factors significance for the zinc
and copper recovery to a solution, separately. Relatively
low value of the coefficient x2 in Eq. (7) indicates that
Cl– ions concentration does not significantly impact zinc
recovery to a solution, in comparison with copper
recovery. This fact indicates the prevalence of Eq. (1)
above Eq. (2) during the zinc recovery to a solution.
In turn, reaction (2) requires significant recovery of
copper to solution during leaching. Overall, the values
of regression coefficients, excluding the factor x2,
indicate that the process of zinc recovery is more
(6) sensitive to the leaching parameters than to the ones for
copper recovery.
To demonstrate the effect of pairwise interactions
having the most impact on metal recovery, the
three-dimensional response surfaces for Zn and Cu
recovery are presented in Figs. 1–4.
Each figure shows the dependence of metal
recovery on two variables; while, the other two variables
have been fixed at the zero level.
The value of x1x3 has a significant negative impact
on the zinc recovery into solution. Opposite, the value of

Table 5 Fisher test for model of copper and zinc recovery

Item Copper recovery Zinc recovery
2
Residual variance,  res 0.545 1.271
2
Replication variance,  rep 0.248 0.583
Estimated F value 2.198 2.180
Fig. 1 Response surface for Zn-recovery at constant values of
2
The R values for Eqs. (6) and (7) were found to be initial concentration of Cl– ions and solid-to-liquid ratio
99.6%, indicating the good agreement between the
experimental and the predicted values of copper and zinc
recovery.
The observed values of zinc and copper recovery
clearly indicate that Eqs. (6) and (7) adequately describe
the leaching process.

3.2 Impact of experimental factors on zinc and copper

recovery into solution
As is known, the value and signs of the regression
equations coefficients provide insights the impact of the
factors and their interactions on the value of the output Fig. 2 Response surface for Zn-recovery at constant values of
parameter. The coefficients of regression obtained above initial concentrations of both NH3 and Cl– ions
J. Cent. South Univ. (2017) 24: 2799–2804
Fig. 3 Response surface for Cu-recovery at constant values of
initial concentration of NH3 and leaching duration
Fig. 4 Response surface for Cu-recovery at constant values of
initial concentration of Cl– ions and leaching duration
x3x4 has a significant impact on the process considered.
The most positive impact on copper recovery has an x2x4
interaction with 2.165 of value. In its turn, the most
negative impact on the mentioned metal recovery has an
x1x4 interaction with –1.889 of value.
3.3 Obtaining optimal parameters of leaching process
Approximation method was used to leaching
process optimization [16]. The Excel software was
applied at calculation process. The corresponding
conditions of the best metal recovery are follows:
For zinc recovery,
x1=0.42, corresponding to initial CNH3=17.1%;
x2=2.00, corresponding to initial CCl–=160 g/L;
x3=1.59, corresponding to leaching time=4.56 h;
x4=–0.01, corresponding to solid-to-liquid ratio=0.39.
For copper recovery,
x1=1.98, corresponding to initial CNH3=19.9%;
x2=2.00, corresponding to initial CCl–=160 g/L;
x3=1.13, corresponding to leaching time=4.13 h;
x4=1.29, corresponding to solid-to-liquid =0.53.
To test the validity of the conditions found as
2803
optimal from the model, a leaching experiment was
carried out.
At these optimal parameters, 80.31% of total zinc
recovery and 55.62% of total copper recovery were
predicted using Eqs. (6) and (7). Actually, 81.16% of
zinc recovery and 56.48% of copper recovery were
observed during the experiments. The results indicate
that the model is successful in predicting the responses.
4 Conclusions
The present work was aimed at finding possibilities
of zinc and copper concentrates obtained via copper slag
treatment by ammonia solution. The statistical method
called central composite rotatable design (CCRD) and
approximation method were used to determine the
optimum conditions of zinc and copper recovery to a
solution. The experimental design was done at five levels
of the operating parameters, namely the initial
concentration of NH3, the initial Cl– ions concentration,
leaching time and solid/liquid ratio.
The regression equations describing the effect of
factors on the zinc and copper recovery to a solution
were obtained. The validity of regression equation has
been controlled by statistical approaches.
It was found that optimum parameters for zinc
recovery are follows: initial CNH3 17.1%, initial CCl–
160 g/L, leaching time 4.56 h, solid-to-liquid ratio 0.39.
For copper recovery, the optimum parameters are follows:
initial CNH3 19.9%, initial CCl– 160 g/L, leaching time
4.13 h, solid-to-liquid 0.53. The maximum zinc and
copper recoveries to a solution obtained experimentally
at the conditions were 81.16% and 56.48%, respectively.
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(Edited by YANG Hua)

Cite this article as: R. Nadirov, L. Syzdykova, A. Zhussupova. Copper smelter slag treatment by ammonia solution:
Leaching process optimization [J]. Journal of Central South University, 2017, 24(12): 2799–2804. DOI:
https://doi.org/10.1007/s11771-017-3694-3.