Research Summary Aluminum
Extracting Aluminum from
Dross Tailings
A.M. Amer
Aluminum dross tailings, an indus-
trial waste, from the Egyptian Alu-
minium Company (Egyptalum) was used
to produce two types of alums: alumi-
num-sulfate alum [Al2 (SO4) 3.12H2O]
a n d a m m oniu m- alu minu m alu m
[(NH4 ) 2 SO 4AL 2 (SO 4 ) 3.24H 2O]. This
was carried out in two processes. The
first process is leaching the impurities
using diluted H 2 SO 4 with different
solid/liquid ratios at different tempera-
tures to dissolve the impurities present
in the starting material in the form of
solute sulfates. The second process is
the extraction of aluminum (as alumi-
num sulfate) from the purified aluminum
dross tailings thus produced. The effects
of temperature, time of reaction, and
acid concentration on leaching and
extraction processes were studied. The
product alums were analyzed using x-ray
diffraction and thermal analysis
techniques.
INTRODUCTION
Finding methods for producing useful
materials from industrial wastes is a
very important (potential) task for
1 7
Outlet
3 Inlet
4 6
8 5–stands, 6–glass beaker,
72
scientists all over the world, since billions
of tonnes of these industrial solid wastes
have been discarded, causing serious
pollution of the environment. The
aluminum industry is no exception in
this respect. For example, the aluminum
new scrap available at Egyptian Alu-
minium Company (Egyptalum) amounts
annually to about 15,000 tonnes. The
amount of aluminum dross tailings, the
parent material for the present study,
represents about 15% of this quantity.
Several studies have been devoted to the
production of aluminum-sulfate and
aluminum-ammonium-sulfate alums
from the byproduct aluminum oxide.1–4
Durward et al.4 treated aluminum dross
with water at elevated temperatures,
where aluminum nitride and aluminum
carbide contaminants decomposed to
aluminum-oxide trihydrate, ammonia,
and methane. The disadvantage of this
method is that ammonia gas escaped and
could not be utilized and, also, the
metallic impurities were not removed.
Other methods were applied1–3 in which
aluminum dross tailings were reacted
directly with diluted H2SO4 without
5
Figure 1. A schematic
diagram of an experimen-
tal leaching reactor:
1–Electric stirrer, 2–tem-
perature-controlled hot
plate, 3 –thermometer,
2 4–Teflon stirrer paddle,
7–condenser, 8–tempera-
ture probe, 9–temperature
controller.
pre-treatment of the impurities, espe-
cially heavy metals, iron, and ammonium
sulfate.
The main objective of the present
study is the utilization of aluminum dross
tailings to produce a highly pure
aluminum sulfate, which is known as
paper-makers’ alum or filter alum.5,6 It is
usually used in purposes such as water
treatment,6,7 dying, fire-proofing fabrics,
and cellulosic insulation.8,9
In this study, the reduction of impuri-
ties is based on washing the aluminum
dross tailings with diluted H 2SO 4
solutions. The major impurities (e.g.,
AIN, AL4C3, CuO, Fe2O3, MnO, etc.) are
transformed into soluble metal sulfates.
EXPERIMENTAL
Starting Material
Homogeneous aluminum dross (par-
ticle diameter is less than 1 mm) was
produced from the drossing machine. It
was mechanically mixed for five hours
to ensure homogeneity.
Elemental Analysis of Dross
The aluminum content in the dross
tailings was calculated by EDTA titration
and by atomic absorption spectropho-
tometry10,11 (model Jerrel Ash 801). Other
metallic impurities (e.g., Mg, Mn, Si,
Fe, Zn, Cu, V, Na, As, and Pb) were
determined using the atomic-absorption
method. Nitrogen was determined by
the Kejidhal method and spectrophoto-
metrically by complexation with Nessi-
er’s reagent. Carbon and chlorine were
determined using combustion analysis.
X-ray diffraction analysis of the
striating material, the products of the
leaching process, and the final alum
products was carried out using a JECL
JXS-CO PA diffractometer with Cu
K radiation.
JOM • November 2002
 Thermogravimetry (TG), derivative
thermogravimetry (DTG), and dif-
ferential thermal analysis (DTA) were
carried out using a Du Pont-9900
instrument.
Leaching Experiments
Leaching experiments were carried
out in a specially designed reactor, a
schematic diagram of which is shown in
Figure 1. For each experiment, 100 g of
dross sample were used. The appropriate
volume of sulfuric acid, equivalent
to 160 g of concentrated H2SO2, was
used to keep the dross/acid ratio as
100/160. This amount of acid was used
in different diluted forms (Ca 5, 7.5, 10,
and 12.5% by weight).
An acid solution of known concentra-
reactor and time was measured. At the
end of the leaching time, the contents
of the reactor were poured into a filtra-
tion system. The filtrate and washing
solutions were collected quantitatively
into a volumetric flask, completed,
shaken well, and then subjected to
quantitative analysis of all leached
elements. The aluminum dissolved
during the leaching process is recov-
ered in the form of a double sulfate
[(NH 4 ) 2 SO 4 .AL 2 (SO 4 ) 3 .24 H 2 O] as
crystals.
APPARATUS AND LEACHING
TECHNIQUE
The same reactor, Figure 1, was used
for these extraction experiments. The
solid residue obtained after leaching
stirred to dissolve the anhydrous
aluminum sulfate. The slurry was washed
several times with boiled water. The
filtrate and washing solution were
collected in a measuring flask, which
was marked, and consequently a full
analysis was made.
RESULTS AND DISCUSSION
Elements Analysis of the
Aluminum Dross Sample
The aluminum content was calculated
by EDTA titration to be 50.43% by
weight and 49.54% using the atomic-
absorption method. Nitrogen was
calculated by the Kejldhal method as
24

Weight of Aluminum Dissolved (per g)

tion was transferred into the reactor impurities was used as the starting ● ● 4
● 1—Solid/Liquid = 0.166
and was heated, with constant stirring, material for extraction of aluminum 20 ●
2—Solid/Liquid = 0.125
to the selected temperature. The 100 g (as aluminum sulfate). Extraction was ● 3—Solid/Liquid = 0.111
16
dross sample was added quickly to the carried out using solutions of H2SO4 ● ● 4—Solid/Liquid = 0.090
(30%, 40%, and concentrated 96% by 12 ● ●
●● 3
weight). One hundred grams of the ● ●
●
8 ●
sample were used in each experiment ●
●●
with the stoichiometric amount of H2SO4 ●
4 ●● ● ● 2
● ●
at 100°C
calculated from the equation: ● ● ● 1
48 ● ● AL2O3 + 3 H2SO4 = AL2(SO4)3 + 3
●
% Al Dissolved

● 40 80 120 160 200 240 300 340

at 70°C
H2O Time (min.)
● ●
● ● ●
32 Diluted H2SO4 of the required concentra- Figure 4. The aluminum dissolved during
● ●
● at 60°C● tion was transferred into the reactor and leaching the impurities as a function
● ● of time for various solid/liquid ratios at
16 ● ● at 50°C heated until the required temperature
● ●
100°C using 10% H2SO4.
●
(near the boiling point of the solution)
was attained. One hundred grams of the 40
2 3 4 1 5 6 dross were added to the acid solution ●2
● ● ●1
% Al Extracted

Leaching Time (h) 32 ● ●

in the reactor and time was measured. ● ●
Figure 2. The aluminum dissolved during ●
At the end of the reaction, the mixture 24 ● ●
leaching the impurities from 100 g of
the sample as a function of time at was cooled quickly by adding 100 ml ●
16
different leaching temperatures using of cold water to stop the reaction and 1—H2SO4 30%
10% H2SO4. 8 2—H2SO4 40%
to facilitate the filtration process.
An analysis of all elements present
6 8 10 12 14 16 2 4
was performed on the quantitatively Time of Extraction (h)
collected filtrate and washing solution. Figure 5. The aluminum extracted from
100 g of the sample at 105°C as a
● 4
Extraction with function of time using 30% and 40%
48 ● ● ● 3
● ● Concentrated H2SO4 H2SO4 solutions.
● 2
% Al Dissolved

● ●
● ● ● ●
● 1 One hundred grams of the purified
32 ● ●
● ● 56 100
● 1—Leaching with 5% H SO dross were placed in a porcelain dish, ■●
Reaction Efficiency

● 2 4 ● ● ● ●
and the appropriate amount of concen- ■
% Al Extracted

16 2—Leaching with 7.5% H2SO4 40 80

3—Leaching with 10% H2SO4
4—Leaching with 12.5% H2SO4
1 2 3 4 5 6
Leaching Time (h)
Figure 3. The aluminum dissolved during
leaching the impurities from 100 g of the
sample as a function of time for different
acid concentrations.
trated H2SO4 was added carefully to the ■
■
sample. The acid was mixed well with 24 60
■
the sample using a glass rod until a
homogeneous paste was obtained. The 8 40
dish was kept in a furnace (maintained at 1.0 1.2 1.4 1.6 1.8 2.0 2.2
the selected temperature for 1 h). The Acid/Dross Ratio
contents of the dish were quantitatively Figure 6. The effect of acid/dross ratio on
the aluminum extracted and the reaction
transferred to a beaker, boiled for 15 efficiency.
min. with 1 L of distilled water, and

2002 November • JOM 73


Table I. Analysis of Metal Impurities in the Dross Sample
Element Mg Mn Si Fe
Wt.% 1.840 0.230 0.40 0.57
6.48% by weight and as 6.75% using the
spectrophotometric measurements.
Combustion analysis gave the extent of
chlorine as 4.4% and carbon as 1.8% by
weight.
All other impurity metals were
measured by atomic absorption analysis.
The results are given in Table I.
Leaching Experiments
Effect of Time and
Temperature on Leaching
Figure 2 shows four leaching curves
performed at four different temperatures.
For each curve, the amount of aluminum
leached increases with time until it
reaches a constant value, which is
maintained to the end of the experiment.
The total amount of aluminum leached
depends on the leaching temperature.
Figure 2 shows that the amount of
aluminum leached after 5 h at 100°C
(curve 4) is 2.5 times greater than leached
at 50°C (curve 1) after the same time.
Effect of Acid Concentration
Figure 3 displays four leaching
experiments carried out at four different
concentrations of H2SO4 (5%, 7.5%,
10%, and 12.5%). It shows that the
amount of aluminum leached increases
with increasing acid concentrations. At
12.5% H2SO4 (curve 4), there is a 5%
increase in the amount of leached
aluminum than that leached with 5%
H2SO4 (curve 1).
Effect of Solid/Liquid Ratio
Because of the complicated composi-
tion of the dross sample, it was difficult
to exactly calculate the stoichiometric
quantity of H2SO4 with respect to the
dross. Therefore, four different solid/
liquid ratios (0.09, 0.111, 0.125, and
0.166) were used to study the rate of
leaching of aluminum. Figure 4 shows
the results of these studies.
Curve 1 (the highest solid/liquid ratio,
0.166) shows an initial rapid increase in
the amount of aluminum leached up to a
maximum value. It falls dramatically
afterward until it reaches a minimum.
74
Zn Cu V Na
0.32 0.01 0.02 2.9
The same behavior is seen for curves 2
and 3 (solid/liquid ratios of 0.125 and
0.111, respectively) except that after the
maximum value of leached aluminum is
attained, these curves fall, but not as
sharply as curve 1. This means that the
amount of aluminum leached (after
reaching the maximum value) decreases
as the solid/liquid ratio decreases (i.e.,
as the concentration of acid gets greater).
Curve 4 represents the mixture of lowest
solid/liquid ratio (i.e., 0.09). With the
highest concentration of acid, curve 4
differs from the previous three curves
(1–3) in that the percent of aluminum
leached increases with time until it
reaches a constant value with no further
drop. This behavior is attributed to the
fact that increasing the amount of H2SO4
resulted in a dissolution of the basic
aluminum sulfate, Al6(OH)10(SO4)4, thus
precipitated in experiments 1–3 which
contained a low concentration of acid
(basic aluminum sulfate is formed12 as a
result of the release of ammonia
produced from the reaction between
aluminum nitride, AIN, and H2O in the
absence of H2SO4 after consumption of
H2SO4 in a solution containing a low
I/I0 (Relative Intensity)
a
I/I0 (Relative Intensity)
b
concentration of acid). This behavior
disappeared, however, for curve 4, due
As Pb to the presence of acid in a quantity
0.002 0.003
greater than the stoichiometric value.
Extraction Experiments
Effect of Time and Acid Concentration
Figure 5 displays two extraction
curves using 30% and 40% acid concen-
trations. It was found that extraction
increases rapidly at first, and then slows.
Also, extraction increases with increas-
ing acid concentration.
Extraction of Aluminum
Using Concentrated H2SO4
The use of concentrated H2SO4 (96%)
in the extraction process showed that the
amount of aluminum extracted increases
with time and temperature up to a
maximum value, which remained
unchanged. This maximum was always
attained after 40–60 min., depending on
the reaction temperature.
Effect of Acid/Dross Ratio and
Efficiency of Extraction
Figure 6 shows that the maximum
amount of aluminum extracted reached
a maximum at an acid/dross ratio of 1.4.
Afterwards, no further increase resulted
from increasing the acid/dross ratio. The
efficiency of the reaction was measured
at 200°C at different acid/dross ratios.
Figure 6 shows, again, the same behavior
2θ
Figure 7. X-ray diffracto-
grams of (a) aluminum
sulfate and (b) ammonium-
aluminum sulfate prod-
ucts.
2θ
JOM • November 2002
(i.e., the efficiency increases, reaching
its maximum at an acid/dross ratio of
1.4, then the efficiency falls sharply
afterwards).
Kinetic Aspects
Leaching and extraction data were
analyzed by means of a simple program
using the following simple equation:
dc/dt = k (1/t)n where k = rate constant
(time) and n= order of reaction. Values
of k and n at different acid concentrations
for leaching experiments are given in
Table II.
Extraction experiments were also
analyzed by the same equation. Values
of k were calculated to be 2.15 h and
2.26 h for 30% and 40% acid concentra-
tions, respectively, and the corresponding
n values were calculated as 0.738 and
0.754.
Product Analysis
The two product alums were subjected
to several analyses. An elemental
analysis of both alums was in close
agreement with the theoretical expecta-
tion for the formulae Al2(SO4)3.12H2O
and [(NH4)SO4.Al2(SO4)3.24H2O].
The extent of impurities was found to
be in the acceptable range13 for alumi-
num-sulfate alum required for water
treatment.
Results of x-ray diffraction of the two
product alums (Figure 7) were in
accordance with the standard ASTM
data. The XRD of aluminum sulfate
matches well the d-spacing of ASTM
card no. 21-11. On the other hand, the
results of ammonium-aluminum alum
also matches ASTM card no. 7-22 of
0 DTA
20 335.5°C
40
60
Weight Loss (%)
80
0 126°C
20
40 217.9°C
60
80 123.9°C
100.4°C
0 200 400
Temperature (°C)
Figure 8. TG and DTA curves of (a)
aluminum sulfate and (b) ammonium-
aluminum sulfate products.
2002 November • JOM
Table II. Values of n and k Leaching
Experiments
Acid Conc. (%) k n
5 3.80 0.70
7.5 3.67 0.75
10 3.67 0.78
12.5 3.08 0.90
[(NH4)2SO4.Al2(SO4)3.24H2O].
Thermal analyses (TG and DTA) of
the two product alums are shown in
Figure 8. The TG curve of aluminum
sulfate shows three weight-loss steps,
accompanied by 34.6%, 10.9%, and
35.3% weight loss, respectively. This
brings the total weight loss up to 80.8%,
which is in close agreement with the
theoretical calculations (i.e., 81.17)
expected from Al2 (SO4)3. The 12H2O
DTA curve shows these three endother-
mic events maximized at 126°C,
335.5°C, and 814.1°C.
Similarly, the TG of ammonium-
aluminum alum shows five weight-loss
steps of 17.3%, 24.7%, 4.9%, 14%, and
26.45%, respectively. The total weight
loss (87.35%), again, is close to theoreti-
cal expectation (88.7%) for the molecular
formula [(NH4)2SO4.Al2(SO4)3.24H2O].
These five weight loss steps appeared in
the DTA curve as five endotherms at
109°C, 141°C, 235°C, 502.1°C, and
805.6°C, respectively.
CONCLUSION
From these experiments, leaching
conditions were specified to permit the
maximum removal of impurities with
minimum dissolution of aluminum
oxide. These optimum conditions,
chosen to be used in the bench scale
(a) work, were specified as follows: Tem-
814.1°C perature: 100°C; H2SO4 concentration:
TG
10%; time of the reaction: 5 h; and
solid/liquid ratio: 0.111. For extraction,
DTA
it was found that when acid concentra-
538.5°C tions of 30% or 40% were used, the rate
837.6°C
(b) of extraction was very slow (only 32%
of aluminum was extracted after 16 h at
108°C). The use of concentrated H2SO4
TG
(96%), on the other hand, resulted in the
600 800 1,000
completion of the extraction process at
the same temperature in 30–40 min.
Thus, concentrated H2SO4 was preferred
for the bench scale experiments.
The maximum value of aluminum
extracted was found to take place at the
neutralization point between acid and
dross. At this point, the production of
AIN is still free after the consumption of
acid, so it reacts with water as follows:
AIN + 4 H2O = Al(OH)3 + NH4OH.
The ammonium hydroxide then reacts
with aluminum sulfate to give basic
aluminum sulfate as follows: 10 NH4OH
+ 3 Al2(SO4)3 = Al6(OH)10(SO4)4.5H2O +
5(NH4)2SO4. For this reason, an appropri-
ate solid/liquid ratio should be used.
When a solid/liquid ratio of 0.111 was
used, it was found that about 88.5% of
both aluminum and nitrogen were
recovered as ammonium-aluminum
alum. The presence of Al6(OH)10(SO4)4
5H2O was detected by x-ray diffraction.
References
1. L.W. Garrett, “Process for the Production of Sulfates”
(U.S. patent 4,337,228, 29 June 1982).
2. J.A. Huckabay, “Method for Treatment of Aluminum
Dross Oxides” (U.S. patent 4,434,142, 24 February
1984).
3. D.A. Huckabay and A.D. Skiathas, “Aluminum Dross
Processing” (U.S. patent 4,252,776, 28 February
1984).
4. A. Durward and D.S. Arthur, “Aluminum Sulfate
Manufacture from Aluminum Dross Tailings” (U.S.
patent 4,320,098, 16 March 1982).
5. American Encyclopedia, vol. 1 (Grolier Enterprise,
1988), p. 640.
6. W.L. Faith, D.B. Keyes, and B.L. Weand, Process
Chemistry for Water and Waste Water Treatment
(Upper Saddle River, NJ: Prentice-Hall, Inc., 1982).
7. L.D. Benefield, J.F. Judkins, and B.L. Weand,
Process Chemistry for Water and Waste Water
Treatment (Upper Saddle River, NJ: Prentice-Hall,
Inc., 1982).
8. J.N. Stephenson, Pulp and Paper Manufacture, Vol.
2 (New York: McGraw-Hill, Inc., 1951).
9. G.T. Austin, Shreve’s Chemical Process Industries
(New York: Hill-Hill, Inc., 1985).
10. Aluminium Ores—Determination of Alulminum
Content—EDTA Titrimetric Method (Geneva, Switzer-
land: International Organization for Standardization,
1985).
11. American Society for Testing and Materials, Vol.
03.06 (New York: Meltzen, Inc., 1989).
12. D.E. Shanks, “High Temperature Hydrolysis of
Aluminum Sulfate Solution” (U.S. patent 4,394,368,
19 July 1983).
13. Egyptian Standard—Aluminium Sulphate for
Purification of Potable Water, ES: 1700 (Cairo, Egypt:
Egyptian Organization for Standardization and Quality
Control, 1989).
A.M. Amer is a professor with the Environmental
Science Department Faculty of Science at
Alexandria University.
For more information, contact A.M. Amer, Alexandria
University Faculty of Science, Environmental
Science Department, Mohrrem bek, Alexandria
00203, Egypt; ashraf.amer@37.com.
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