Hydrometallurgy 54 1999.

4148
www.elsevier.nlrlocaterhydromet

Statistical analysis of laboratory results of Zn

wastes leaching
L.J. Lozano Blanco ) , V.F. Meseguer Zapata, D. De Juan Garca

INQUICA Research Group, Department of Chemical Engineering, Uniersity of Murcia, Paseo Alfonso XIII,
50, 30203-Cartagena, Spain
Received 7 May 1999; received in revised form 21 August 1999; accepted 10 September 1999

Abstract
In Spain, several kinds of zinc-containing waste materials are available for zinc recovery. Zn
residue leaching studies were carried out using a central composition design of experiments to
show the application of statistical analysis to the results obtained. Ammonium carbonate 3M.
ammonia solutions were used for leaching. Zn recovery yields are ) 95% for this kind of waste
material. A regression equation for the dissolution of zinc was developed as a function of
temperature, pH and solids concentration. All the parameters were varied at two levels for
designing experiments and two base levels and six outer levels experiments were carried out to
estimate error and consider second order relationships among the variables. q 1999 Elsevier
Science B.V. All rights reserved.
Keywords: Zinc wastes; Ammoniacal leaching; Factorial design

1. Introduction
The dissolution of metal oxides assumes significance in view of its role in several
hydrometallurgical processes, such as removal of zinc from polymetallic residues and
wastes. The accumulation of large quantities of metallic scrap, as well as metallurgical
wastes, has led to a significant interest in processing these waste materials. Ammonia
has been widely used as an effective lixiviant in a number of hydrometallurgical
processes for many years. The leaching of metals in ammoniacal solutions is applied

Corresponding author. E-mail: ljlozano@plc.um.es

0304-386Xr99r$ - see front matter q 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 4 - 3 8 6 X 9 9 . 0 0 0 5 7 - 2

42

L.J. Lozano Blanco et al.r Hydrometallurgy 54 (1999) 4148

primarily to extraction of non-ferrous metals such as copper from oxide ores or ores
containing native copper. The application of this leaching technology is gradually
expanding from more traditional treatments of copper, nickel and cobalt to the extractive
metallurgy of zinc, cadmium, silver and gold.
The reason for such an expansion in the use of ammonia in hydrometallurgy is that
ammonia is an attractive lixiviant due to its low-toxicity, low cost and ease of
regeneration by evaporation. Furthermore, since solutions containing ammonia are
usually alkaline, the major wasteful components, such as iron and calcium in ores, are
insoluble in ammoniacal solutions. In addition, these metals exhibit poor complexation
ability with ammonia. This allows selective extraction of the desired metals, leaving the
undesirable components intact with the residue.
The EhpH diagram of the ZnNH 3 H 2 O system w1x shows that there are two stable
regions for zinc hydroxide. Zinc tetra-ammine, ZnNH 3 .q2
is stable only in the pH
4
range of 8-11. The stability region of the solid phase decreases or even disappears as the
activity of the soluble species or ammonia concentration increases. This is one of the
reasons why ammonia is often used to precipitate zinc from acidic solutions despite a
certain stability of zincammine in ammoniacal solutions. From the oxidation point of
view, zinc metal is more amenable to dissolution in the presence of ammonia than in the
absence of it. Furthermore, because of the favorable stability of zinc ammine at pH of
811, ammonia leaching of zinc from various materials is thermodynamically feasible.
Although ammonia leaching has been applied to zinc extraction for a long time w2x,
the leaching behavior of metallic zinc in ammoniacal solution has not been investigated
until recently. Maraszewska and Zembura w3x studied the kinetics of dissolution of zinc
in air or oxygen-saturated aqueous ammonia solutions by using the rotating disc
technique. It was found that the dissolution of zinc exhibits two kinds of characteristics.
First, the dissolution rate is constant or the dissolved zinc is a linear function of the
leaching time at high ammonia concentrations, say greater than 0.25 M. Second, the
dissolution rate of zinc decreases with time at low ammonia concentrations. The
dissolution behavior of zinc is somewhat similar to that of copper and cobalt in
ammonia solutions.
De Juan et al. w4,5x studied the leaching behavior of Waelz oxides when using
ammonium carbonate-ammonia AAC. and ammonium sulphate-ammonia AAS. solutions at ambient temperature and atmospheric pressure. Results showed that 94% of the
zinc contained in such oxides was recovered when 2.5 M ammonium carbonate solutions
at a pH of 10.110.5 fixed with ammonia. was used.

2. Experimental
The Zn residue sample was supplied by Espanola
del Zinc and was an undefined
mixture of zinc scrap and zinc dross resulting from the zinc cathode industry. Its
composition is shown in Table 1. The experiments were carried out in a 1 L glass vessel
submerged in a thermostatic bath Fig. 1.. The vessel had four necks: one for the stirrer,
one for the thermometer, one for the inlet of the sample and the last served the purpose
of withdrawal of samples at regular intervals of time.

L.J. Lozano Blanco et al.r Hydrometallurgy 54 (1999) 4148

43

Table 1
Elemental composition of Zn residue
Weight percentage
Humidity
Insoluble
Zn
Cu
Cd
Pb
Fe
Al
Co
Ni
K
Na
Ca
Cly
SO42y

1.40
11.62
51.01
2.70
0.05
4.28
1.60
6.64
N.D.
0.83
0.08
0.13
0.67
0.56
0.17

In this study, the sample was added to the vessel containing an AAC solution 3M in
ammonium carbonate and pH fixed with ammonia analytical reagents. and maintained

Fig. 1. Scheme of the glass vessel used for the experiments.

L.J. Lozano Blanco et al.r Hydrometallurgy 54 (1999) 4148

44

at a particular temperature. Due to the particle size of the sample less than 0.3 mm., it
was not necessary to use a previous grinding operation and grain size analysis was not
considered. The mixture was stirred throughout the experiment with the help of a
helicoidal stirrer. At pre-determined intervals, samples of the slurry were withdrawn 15
ml approx.., then filtered and total Zn and Cu in the clear filtrate were determined by
polarography. When three consecutive samples had the same Zn concentration, the
experiment was finished. Total ammonia in leach solutions was determined by titration
with sulphuric acid 0.5 M. using methyl orange as indicator.

3. Results and discussion

Leaching experiments were carried out according to the factorial design of experiments w6,7x. A central composition design was used, with several levels for the variables
studied. The three parameters varied were: temperature T, 8C., pH and solids concentration C, grl.. The reduced form of the variables follows:
X1 s

T y Tm

X2 s

DT

pH y pH m
D pH

X3 s

C y Cm
DC

1.

where
Tm s

Tqq Ty

pH m s
Cm s

DT s

2
pHqq pHy

2
Cqq Cy
2

Tqy Ty
2

D pH s

DC s

pHqy pHy
2

2.

Cqy Cy
2

Tq, Ty, pHq, pHy, Cqq y Cy are the maximum and minimum values of the three
variables in the range studied that means 458C258C, 10.59.5 and 250150 grl. and
were fixed in previous experiments. The matrix for the three variables using reduced
variables and corresponding Zn recovery yield Y . is shown in Table 2. According to
the design of experiments principle, central composition design of experiments has the
advantage of expanding two levels factorial design, with little increase in the number of
experiments. Additional experiments are two for the base level 0,0,0., and two extreme
points for each of 3 factors. These eight additional experiments are used to estimate
error and standard deviation. The distance a . between the base level and these extreme
points follows:

as N f .

0.25

s 23.

0.25

s 1.68

3.

The regression model equation can be written as follows

Y s a 0 q a1 X 1 q a2 X 2 q a3 X 3 q a12 X 1 X 2 q a13 X 1 X 3 q a23 X 2 X 3
q a123 X 1 X 2 X 3 q a11 X 12 q a 22 X 22 q a33 X 32

4.

L.J. Lozano Blanco et al.r Hydrometallurgy 54 (1999) 4148

45

Table 2
Parameters studied in their reduced and normal form
Experiment

T 8C.

X1

pH

X2

C grl.

X3

Y %.

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16

45
25
45
25
45
25
45
25
35
35
51.8
18.2
35
35
35
35

q1
y1
q1
y1
q1
y1
q1
y1
0
0
q1.68
y1.68
0
0
0
0

10.5
10.5
9.5
9.5
10.5
10.5
9.5
9.5
10
10
10
10
10.84
9.16
10
10

q1
q1
y1
y1
q1
q1
y1
y1
0
0
0
0
q1.68
y1.68
0
0

250
250
250
250
150
150
150
150
200
200
200
200
200
200
284
116

q1
q1
q1
q1
y1
y1
y1
y1
0
0
0
0
0
0
q1.68
y1.68

100.9
85.8
74.6
71.9
100.3
87.8
95.4
82.5
92.4
94.1
100.8
79.6
100.0
85.9
84.9
102.7

The values of calculated coefficients, when incorporated in Eq. 4., take the form of
Eq. 5.:
Y s 89.29 q 6.51 X 1 q 4.06 X 2 y 5.85 X 3 q 1.48 X 1 X 2 q 2.65 X 1 X 3
q 1.18 X 2 X 3 q 0.00 X 1 X 2 X 3 q 0.00 X 12 y 1.59 X 22 y 0.237 X 32

5.

where, Y s percentage of Zn recovered from the residue, X 1 s temperature, X 2 s pH

and X 3 s solids concentration. X 1 , X 2 , and X 3 are dimensionless coded factors.
Coefficient values were obtained by using the MarquardtLevenberg algorithm for
nonlinear regression w8x. The results of the statistical analysis of this model are shown in
Table 3.
The t-statistic tests the null hypothesis that the coefficient of the independent variable
is zero, that is, the independent variable does not contribute to predicting the dependent
variable. t is the ratio of the regression coefficient to its standard error. We can conclude
from large t values that the independent variable can be used to predict the
dependent variable i.e., that the coefficient is not zero..
The P value calculated for t is the probability of being wrong in concluding that the
coefficient is not zero. Traditionally, it is concluded that the independent variable can be
used to predict the dependent variable when P - 0.05.
3.1. Analysis of ariance
The F-test statistic gauges the contribution of the independent variables in predicting
the dependent variable. If F is a large number, one can conclude that the independent
variables contribute to the prediction of the dependent variable i.e., at least one of the
coefficients is different from zero, and the unexplained variability is smaller than

L.J. Lozano Blanco et al.r Hydrometallurgy 54 (1999) 4148

46

Table 3
Results of nonlinear regression
Rs 0.9125; standard error of estimates6.9651; power of performed test with alphas 0.05: 0.9998; normality
test: passed P s 0.5826.; constant variance test: passed P s 0.1013..

a0
a1
a2
a3
a12
a13
a 23
a123
a11
a 22
a 33

Coefficient

Standard error

89.2906
6.5133
4.0576
y5.8549
1.4803
2.6496
1.1840
0.0000
0.0000
y1.5932
y0.2370

3.5449
2.1680
2.3173
2.1795
2.9078
2.8955
2.7824
346 525 464.2858
346 525 464.2858
2.3849
2.1107

25.1883
3.0043
1.7510
y2.6863
0.5091
0.9151
0.4255
0.0000
0.0000
y0.6680
y0.1123

- 0.0001
0.0300
0.1403
0.0435
0.6324
0.4021
0.6882
1.0000
1.0000
0.5337
0.9149

Analysis of ariance
DF

SS

MS

Regression
Residual
Total

1206.4686
242.5614
1449.0300

120.6469
48.5123
96.6020

2.4869

0.1632

10
5
15

what is expected from random sampling variability of the dependent variable about its
mean.. If F is around 1, one can conclude that there is no association between the
variables i.e., the data are consistent with the null hypothesis that all the samples are
just randomly distributed..
The P value is the probability of being wrong in concluding that there is an
association between the dependent and independent variables i.e., the probability of
falsely rejecting the null hypothesis, or committing a Type I error, based on F .. The
smaller the P value, the greater the probability that there is an association. Traditionally, it is concluded that the independent variable can be used to predict the dependent
variable when P - 0.05.
3.2. Other statistics
The multiple correlation coefficient, R, is a measure of how well the regression
model describes the data. R values near 1 indicate that the equation is a good
description of the relation between the independent and dependent variables.
The power, or sensitivity, of a regression is the probability that the model correctly
describes the relationship of the variables, if there is a relationship. Regression power is
affected by the number of observations, the chance of erroneously reporting a difference
a alpha., and the slope of the regression.
Alpha a . is the acceptable probability of incorrectly concluding that the model is
correct. An a error is also called a Type I error a Type I error is when one rejects the
hypothesis of no association when this hypothesis is true.. The suggested value is
a s 0.05 which indicates that a one in twenty chance of error is acceptable. Smaller
values of a result in stricter requirements before concluding the model is correct, but a

L.J. Lozano Blanco et al.r Hydrometallurgy 54 (1999) 4148

47

greater possibility of concluding the model is bad when it is really correct a Type II
error.. Larger values of a make it easier to conclude that the model is correct, but also
increase the risk of accepting a bad model a Type I error..
The normality test results indicate whether the data passed or failed the test of the
assumption that the source population is normally distributed around the regression, and
the P value calculated by the test. All regressions require a source population to be
normally distributed about the regression line. Failure of the normality test can indicate
the presence of outlying influential points or an incorrect regression model. The
Normality test uses the KolmogorovSmirnov K-S. test.
The constant variance test result shows whether or not the data passed or failed the
test of the assumption that the variance of the dependent variable in the source
population is constant regardless of the value of the independent variable, and the P
value calculated by the test. The Constant Variance test uses the Levene Median test.
4. Conclusions
Factorial design of experiments has been applied in the study of a zinc residue
leaching with ammonium carbonateammonia solutions. From the above statements it
can be inferred that there is a first order relationship among Zn recovery yields and the
three variables studied. Second order relationships and combined effects of the variables
are negligible. Thus, the regression model equation can be re-written as follows.
Y s 88.13 q 6.28 X 1 q 4.28 X 2 y 5.56 X 3
6.
The results of the nonlinear regression are shown in Table 4. From the results
obtained in the nonlinear regression it is considered that Eq. 6. is adequate. Rewriting
Eq. 6. using experimental variables yields:
Y s 8.705 q 0.651 T q 8.12 pH y 0.117 C
7.
There is no dependence between ZnrNH 3 ratios in leach solutions and Zn recovery
yield achieved in each experiment. The values of these ratios vary between 1.5 and 4, so

Table 4
Results of nonlinear regression
Rs 0.8562; standard error of estimates 5.6765; power of performed test with alphas 0.05: 0.9960; normality
test: passed P s 0.2493.; constant variance test: passed P s 0.7629..
Coefficient
a0
a1
a2
a3

88.1321
6.2796
4.2826
y5.5622

Analysis of ariance
DF
Regression
Residual
Total

3
12
15

Standard error
1.4756
1.5715
1.5158
1.5562

SS
1062.3568
386.6732
1449.0300

59.7268
3.9959
2.8253
y3.5742

- 0.0001
0.0018
0.0153
0.0038

MS
354.1189
32.2228
96.6020

F
10.9897

P
0.0009

L.J. Lozano Blanco et al.r Hydrometallurgy 54 (1999) 4148

48

Table 5
Thermodynamic data for ZnNH 3 complexes w1x
DGf0 Jrmol.

Species
. 2q

ZnNH 3
ZnNH 3 . 22q
ZnNH 3 . 32q
ZnNH 3 .42q

y186 600
y226 299
y266 415
y304 648

it can be inferred that species ZnNH 3 . 2q, ZnNH 3 . 22q, ZnNH 3 . 32q and ZnNH 3 .42q
could be present. This assumption is consistent with thermodynamic data shown in
Table 5.
Taking into account Eq. 7., optimum leaching parameters to achieve Zn recovery
must be as follows.
Temperature as high as possible but less than boiling point of the ammonium
carbonateammonia solution used.
pH as high as possible. Ammonium carbonateammonia solutions are buffer
solutions, so it is very difficult to reach pH 11 or higher.
Solids concentration used will determine the capacity of the process i.e., the
volume of residue that can be treated..

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