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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet
Modeling and optimization of surface quality of copper deposits recovered from brass
scrap by direct electrowinning
M. Aghazadeh, A. Zakeri , M.Sh. Bafghi
School of Metallurgy and Materials Engineering, Iran University of Science and Technology, Tehran 16846-13114, I.R. Iran
a r t i c l e
i n f o
Article history:
Received 8 April 2011
Received in revised form 21 August 2011
Accepted 3 November 2011
Available online 11 November 2011
Keywords:
Scrap recycling
Copper recovery
Anodic dissolution
Electrodeposition
Cathode quality
Statistical design of experiments
Response surface methodology
a b s t r a c t
A research study has been undertaken to develop the fundamentals of a method for the direct recovery of
copper from brass (Cu30 wt.% Zn) scrap based on simultaneous electrolytic dissolution of the scrap at the
anode and electrodeposition of copper at the cathode in an acidied sulfate electrolyte. In the present
paper, effects of the concentrations of Cu 2+ (1050 g/L), Zn2+ (040 g/L) and free H2SO4 (15 N) in the electrolyte as well as cathodic current density (50350 A/m 2) and bath temperature (3070 C) have been
studied on the macroscopic surface quality of copper deposits dened by their visual morphological characteristics as expressed by an innovative Deposit Morphology Index (DMI). A Central Composite Design of experiments has been used to develop a quadratic model correlating the key operating parameters to the DMI.
Statistical analysis of the experimental results showed that the concentration of Cu 2+ in the electrolyte
and the cathodic current density are the most inuential factors on the quality of the deposits. It was also
found that these two parameters have statistically signicant interaction on each other. A smooth and compact copper deposit could be obtained at high Cu2+ concentrations and high current densities (above 40 g/L
and 250 A/m 2, respectively) regardless of the level of other factors. However, when the electrolyte temperature is relatively high (60 C), the optimum condition extends to low current densities (down to 50 A/m2)
and mid Cu 2+ concentrations (3040 g/L).
2011 Elsevier B.V. All rights reserved.
1. Introduction
Copper alloys, specially Cu30 wt.% Zn brass, have many applications in both industry and household utensils. Hence, recovery of copper and other constituents of copper alloys scraps has a considerable
economical benet. Present methods of copper recovery from these
sorts of scraps consist of smelting, re-rening and electrorening
(Davenport et al., 2002). This is a lengthy, highly energy consuming
and environmentally pollutant process.
Electrolytic recovery of metal values from alloy scraps is potentially very attractive in sense of economical and environmental considerations. Several processes have been developed using anodic
dissolution for the recovery of metals from certain alloy scraps such
as Ni-Co alloys and supperalloys (Jackson, 1986). There are a few reports concerning direct recovery of copper from its alloys through
electrolytic processes. Electrolytic recovery of copper from an alloy
scrap containing 82 wt.% copper, 7.5% tin and 10.5% other elements
has been tested in sulfate media under conditions similar to those
of the conventional copper electrorening process (Lupi and Pilone,
1998). Electrochemical recovery of copper from alloy scrap in chloride media has also been examined (Langer, 1975). Although the
104
Table 1
The conceived classication system for surface quality of copper deposits.
Deposit morphology index
Visual characteristics
1
2
3
4
5
y b0 bi xi bii xi bij xi xj
where y is the response, xi is the input variable and b values are the
polynomial coefcients. For the tting of a second order polynomial,
more than two levels of each variable are essential. The CCD is made
of two axial (star) points for each factor in the two-level factorial
(full or fractional) in addition to the central point with several replications. The axial points must be placed at the distances of and
from the central points. The fractional factorial design is expressed
with the symbol of 2 k p, where k is the number of variables and p
identies the type of the fractional factorial (1 for half, 2 for quarter
and so forth). The best value of for the axial points of a CCD design
to be constructed on the basis of 2 k p fractional factorial design
would be equal to 2 (k p)/4. Full explanation about the CCD could be
found in the relevant textbooks (Lazic, 2004; Montgomery, 2001). In
the present work, a 2 5 1 fractional factorial with 10 axial points and
105
Fig. 2. Actual pictures of copper deposits on cathode substrates representing ve categories of apparent morphological features (a, b, c, d and e corresponds to a DMI of 1, 2, 3, 4 and
5, respectively). The inserts exhibit the same deposits after detachment from the substrate (not to scale).
5 centre points was used for the design. Therefore, ve levels coded by
2, 1, 0, 1 and 2 was designated for each input factor.
The likely inuential factors in the process under study are supposed to be: Cu 2+, Zn 2+ and free H2SO4 concentrations in the electrolyte, cathodic current density and electrolyte temperature, denoted
for simplicity by letters A, B, C, D and E, respectively. Based on the
knowledge obtained from the literature, suitable levels were chosen
for each parameter. The actual values corresponding to the ve levels
of each operating parameter are given in Table 2.
The quality of the deposit is seemingly difcult to incorporate into a
model or relation as emphasized by Alfantazi and Valic (2003). However, by making use of the DMI described in Table 1 as the output variable,
surface quality features of the deposits could be translated into a quantitative response, feasible for statistical data analysis and modeling. The
software Design-Expert 7.1 was employed for this purpose. A DMI of 1
that corresponds to a compact and smooth copper deposit was considered the criteria for determination of the optimum process condition.
the key response of the experimentation is given in Table 3. Preliminary statistical analysis of the results suggested that the data could
be best described by a quadratic model. A summary of the Analysis
Table 3
The design matrix and the observed DMI response for the employed CCD.
Fractional
Factorial
Points
Axial Points
Table 2
Experimental parameters and levels used in the CCD.
Operating factor
2+
Cu concentration (g/L)
Zn2+ concentration (g/L)
Free H2SO4 concentration (N)
Cathodic current density (A/m2)
Temperature (C)
Symbol
A
B
C
D
E
Level
2
10
0
1
50
30
20
10
2
125
40
30
20
3
200
50
40
30
4
275
60
50
40
5
350
70
Center Points
Standard
order
Run
order
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
25
6
27
22
14
8
20
1
15
4
17
21
5
7
11
29
3
24
23
31
18
28
26
10
9
30
16
13
19
2
12
DMI
response
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
2
2
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
0
0
2
2
0
0
0
0
0
0
0
0
0
0
0
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
0
0
0
0
2
2
0
0
0
0
0
0
0
0
0
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
0
0
0
0
0
0
2
2
0
0
0
0
0
0
0
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
0
0
0
0
0
0
0
0
2
2
0
0
0
0
0
1
1
3
1
3
1
1
1
4
1
4
1
3
1
4
1
5
1
1
1
2
1
1
2
1
1
2
2
3
2
3
106
Table 4
ANOVA table for the quadratic model.
Source
Sum of
squares
Model
39.32
A
22.04
B
0.042
C
0.38
D
3.38
E
1.04
AB
0.063
AC
0.063
AD
3.06
AE
1.56
BC
0.56
BD
0.063
BE
0.063
CD
0.063
CE
0.063
DE
0.56
A2
1.79
B2
1.74
2
C
0.43
2
0.43
D
E2
1.74
Residual error
3.39
Lack of t
2.19
Pure error
1.20
Total
42.71
R-squared = 0.9207
DF
Mean
square
F-value
p-value
Remarks
20
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
10
6
4
30
1.97
22.04
0.042
0.38
3.38
1.04
0.063
0.063
3.06
1.56
0.56
0.063
0.063
0.063
0.063
0.56
1.79
1.74
0.43
0.43
1.74
0.34
0.36
0.30
5.81
65.08
0.12
1.11
9.97
3.08
0.18
0.18
9.04
4.61
1.66
0.18
0.18
0.18
0.18
1.66
5.27
5.13
1.27
1.27
5.13
0.003
b 0.0001
0.733
0.317
0.010
0.110
0.677
0.677
0.013
0.057
0.227
0.677
0.677
0.677
0.677
0.227
0.044
0.047
0.287
0.287
0.047
Signicant
Signicant
1.21
0.445
Signicant
Signicant
Signicant
Signicant
Signicant
Fig. 4. Perturbation plot showing the effects of the main factors on the DMI for copper
cathodes.
Fig. 5. Interaction plot of Cu2+ concentration (A) and current density (D).
only one variable factor while other factors are kept constant at the
midpoint (level 0). Sensitivity of the response value to the variation
of the variable factor becomes evident from the slope or curvature intensity of the plot. A relatively at line is an indication that the response is almost insensitive to the variable factor. Steep slop of
curve (A) corresponding to Cu 2+ concentration shows that this factor
has the largest effect on the deposit morphology. It is also evident
from this curve that sensitivity of deposit layer smoothness to Cu 2+
concentration in the electrolyte becomes low at higher Cu 2+ concentrations. This is because of the presence of A 2 term in Eq. (2). At low
concentrations of Cu 2+, the rate of diffusion is presumably slow and
therefore, the cathodic process becomes diffusion-controlled. Under
107
such conditions powder formation is favored, since the rate of nucleation becomes much greater than the rate of crystal growth (Habashi,
1998). Fig. 5 shows the interaction effect of Cu 2+ concentration and
current density symbolized by AD in Eq. (2). It indicates that high
levels of cathodic current density (D) at low Cu 2+ concentrations
(A) cause the low quality deposits.
3.2. Optimization for DMI
Response surface methodology indicates areas in the design space
where the process is likely to give desirable responses. A simple mean
to nd the desired operating condition would be construction and
Fig. 6. Contour plots showing the effects of Cu2+ concentration (A) and cathodic current density (D) on the DMI at low, mid and high levels of Zn2+ concentration (B) and electrolyte temperature (E), and xed level of free H2SO4 concentration (C).
108
7030 brass scrap, and to model and optimize the surface quality
using a CCD methodology. The main results achieved in the study
can be summarized as follow:
1) An inventive Deposit Morphological Index was employed to categorize the surface quality of copper cathode products with respect to
their apparent morphological features in an immediate and
straightforward manner. The index was employed as the response
variable for modeling and optimization.
2) Concentration of Cu 2+ in the electrolyte and cathodic current density was identied to be the most effective factors inuencing the
surface quality of copper cathodes.
3) Effects of the electrolyte temperature and Zn 2+ concentration
were found to be relatively small, while that of free H2SO4 concentration was essentially insignicant for the experimental objective
of this study.
4) Contour plots obtained from the quadratic model were employed
for optimization. It was found that high concentrations of Cu2+
(4050 g/L) together with high current densities (250350 A/m 2)
could generally produce a compact and smooth deposit irrespective
of the level of other factors. However, if the electrolyte temperature
is relatively high (about 60 C), low current densities and mid Cu2+
concentrations also could favor desirable deposits.
5) The presence of zinc ions in the electrolyte, even at very high concentrations of about 40 g/L, did not appreciably affect the surface
quality of copper deposits on the macroscopic level.
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