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Recovery of high surface area alumina from

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Journal of Chemical Technology and Biotechnology

J Chem Technol Biotechnol 75:394402 (2000)

Recovery of high surface area alumina from

aluminium dross tailings
Ezzat A EI-Katatny,1 Samih A Halawy,2 Mohamed A Mohamed3* and
Mohamed I Zaki4
1

Aluminium Company of Egypt, Nag-Hammady, Egypt

Chemistry Department, College of Education, King Faisal University, PO Box 1759 Al-Hofouf 31982, Eastern Province, Saudi Arabia
3
Chemistry Department, Faculty of Science at Qena, South Valley University, Qena 83523, Egypt
4
Chemistry Department, Faculty of Science, Kuwait University, PO Box 5969 Safat, 13060 Kuwait
2

Abstract: Aluminium dross tailings (ADT), a chemical waste from a factory producing aluminium in
Egypt, was used for the recovery of the aluminium content in the form of alumina (Al2O3). Extraction
of the aluminium was carried out via atmospheric- and high-pressure leaching with caustic soda.
Then, it was separated from the sodium aluminate solutions thus obtained, using six different
precipitation methods. The precipitates were ltered, washed, dried and calcined at 600 C to produce
the test aluminas. The precipitates and the calcination products were analysed for their chemical and
crystalline phase compositions. The calcination products (aluminas) were subjected to sorpometry for
surface area determination, and to particle sizing. The results indicated that highly pure (SiO2 < 0.53%
and Na2O < 0.14%), well-dened crystalline g-aluminas of high surface areas (>200 m2 g1) and
) could be efciently recovered from ADT. Optimal recovery
uniform small crystallite sizes (6070 A
conditions were examined and determined.
# 2000 Society of Chemical Industry

Keywords: alumina; industrial wastes; recovery; precipitation; XRD; surface area

INTRODUCTION

Recovery of useful materials from corresponding

industrial chemical wastes has been the subject matter
of a large amount of research work.14 The thrust has
been two-fold: (i) the economic feasibility, and (ii) the
environmental necessity.57 The aluminium industry
is no exception in this respect. Therefore, several
research attempts have been published, dealing with
the recycling of aluminium industrial chemical wastes,
particularly aluminium dross tailings (ADT), to
produce a wide range of practical aluminium compounds. For example, aluminium sulfate and aluminium ammonium sulfate alums,8 aluminium oxides
and hydroxides,9 abrasives,10 quick-set cement11 and
aluminium metal12 have been successfully recovered.
The amount of ADT generated by the Egyptalum
Company (a major producer of aluminium in Egypt) is
c 12 800 tonnes per year. It is an aluminium-rich (45
wt% Al) chemical waste and, hitherto, neither properly
dispensed, nor adequately utilized.
The present study was designed to investigate
methods of recovering high-surface area aluminas,
for catalytic and other purposes, from a local ADT
waste, and to establish the effects of recovery variables
on the physicochemical properties of aluminas thus
produced.

EXPERIMENTAL
Materials

Aluminium dross tailings (ADT)

ADT, the target waste material of the present
investigation, is produced during the production of
aluminium metal sheets, or during recycling of
aluminium scrap, by the Egyptalum Co (NagHammady/Egypt). It is a loose grey powder with a
bulk density of 0.88 kg dm3 and a particle size in the
range 0.200.40 mm. About 90 samples of ADT were
collected over a period of 3 months. These samples
were mixed thoroughly, and test samples were selected
from the resulting mixture using the standard method
detailed previously.8
Reagents, gases and other chemicals
Hydrogen peroxide (H2O2) was an ultra pure product
of Merck (Germany), with a concentration of 30% by
weight; sodium hydroxide (NaOH) was a 99% pure
product of Merck (Germany); lime (CaO) was
prepared by calcination of calcium carbonate (pure
product of Merck) at 1200 C for 6 h and kept dry over
CaCl2; ammonium carbonate ((NH4)2CO3) was an
AnalaR-grade product of Riedel-de-Haen AG
(Germany), with a nominal concentration of 32%
(expressed as NH3); ammonium hydrogen carbonate

* Correspondence to: Mohamed A Mohamed, Chemistry Department, Faculty of Science at Qena, South Valley University, Qena 83523,
Egypt
(Received 1 September 1999; revised version received 12 November 1999; accepted 2 December 1999)

# 2000 Society of Chemical Industry. J Chem Technol Biotechnol 02682575/2000/$17.50

394

Recovery of alumina from aluminium dross tailings

((NH4)HCO3) was a 99.8% pure product of Riedelde-Haen AG and aluminium ammonium sulfate
((NH4)Al(SO4)2) was prepared via acid treatment of
ADT, according to the method described earlier.8
CO2 gas was obtained as a 99.2% pure product of
Egyptian Sugar & Integrated Industries Company (AlHawamdyia/Giza) and used without further purication, and the deionized water used had a resistivity of
about 16 MOcm.

Table 2. Leaching variables of the aluminium content of ADT under high

pressure

Variable

Magnitudes

CSA (g-Na2O dm3) 100, 130, 150, 170, 200 Tp = 180 C

tm = 100 min
SLR = 0.3 g cm3
Tp ( C)

120, 160, 180

tm = 20 min
= 40 min
= 60 min
= 80 min
= 100 min
CSA = 150 g dm3
SLR = 0.3 g cm3

SLR (g cm3)

0.2, 0.3, 0.4, 0.5

Tp = 180 C
tm = 100 min
CSA = 150 g dm3

Alumina recovery processes and methods

Three processes were applied to recover alumina from

ADT: (i) leaching of the aluminium content of ADT in
the form of soluble sodium aluminate (SA), (ii) transformation of the aluminium content of SA into a
sparingly soluble salt (precipitation), and (iii) ltration, washing, drying and calcination of the precipitates.
The leaching process was carried out, using sodium
hydroxide and adopting the Bayer process,13 under
atmospheric- and high-pressure (in an autoclave)
conditions as follows:
(i) Atmospheric leaching: An appropriate quantity
(c 100 g) of ADT was placed in a specially designed
1 dm3 open stainless-steel vessel, equipped with a
speed-controllable mechanical stirrer (model
RW20, IKA, Germany) and a thermostatic temperature controller (model 730 Cole-Parmer,
USA), and it was stirred with an aqueous solution
of NaOH of the required concentration and
volume. During stirring, lime (CaO) was added
(0.5% of the amount of ADT), and sufcient
water was subsequently added to maintain the total
volume (dm3) constant. Leaching experiments
were carried out under the different conditions
listed in Table 1 for the following process variables:
temperature (Tp), time (tm), sodium aluminate

Table 1. Leaching variables of the aluminium content of ADT under

atmospheric pressure

Variable

Magnitudes

Constants

CSA (g-Na2O dm3) 100, 150, 200, 250, 300 Tp = 100 C

tm = 150 min
SLR = 0.3 g cm3
Tp ( C)

50, 70, 100

tm = 15 min
= 30 min
= 40 min
= 60 min
= 100 min
= 150 min
= 200 min
CSA = 200 g dm3
SLR = 0.3 g dm3

SLR (g cm3)

0.2, 0.3, 0.4, 0.5

Tp = 100 C
tm = 150 min
CSA = 150 g dm3

J Chem Technol Biotechnol 75:394402 (2000)

Constants

concentration (CSA), caustic ratio (Cs) and solid/

liquid ratio (SLR).

(ii) High-pressure leaching: These experiments were

carried out in specially designed autoclaves under
the different conditions listed in Table 2. The
autoclaves were stainless steel, of a cylindrical ballmill type, with a volume capacity of 250 cm3 and
an internal diameter of 52 mm. Each autoclave
was charged to 45% of its volume with stainless
steel balls of various diameters. Six autoclaves
were heated simultaneously with the temperature
being regulated automatically, using a thermocouple circuit accurate to within 1 C. Heating
was facilitated by an electric furnace equipped
with rollers for the autoclaves and, also, stirrers for
the internal bulb.
In all these experiments, the autoclaves (containing
the ADT, NaOH solution, lime (CaO) and the
stainless steel balls) were tightly closed, placed in the
furnace, and heated to the desired temperature. The
mixture was stirred for 15 min to prevent formation of
hard masses between the bulb and the balls; time for
each experiment (tm) was measured at the beginning of
stirring, after reaching the set temperature inside the
autoclave. The autoclaves were allowed to cool, and,
then, discharged and the mixture washed thoroughly.
The resulting slurry was ltered under vacuum, and
washed thoroughly with distilled water until a constant
ltrate volume was obtained. The collected ltrate was
subjected to chemical analysis.
It should be stated here that lime is added to the
reaction mixture, in both atmospheric- and highpressure leaching, for quasticization and desilication
purposes.13,14 Soda recovery (ie quasticization) takes
place through the reaction between Na2CO3 (formed
by the reaction between soda and CO2 gas) and
Ca(OH)2 (formed by the reaction between lime and
395

EA EI-Katatny et al

water) as follows:
Na2 CO3 Ca(OH)2 ! 2NaOH CaCO3
In addition, the presence of lime in the reaction
mixture causes desilication of SA solution via liberation of soda combined with silica (in the form of
sodium aluminium hydrosilicate or sodalite,
1.33Na2O.Al2O3.2SiO2), leaving silica combined as
an insoluble dicalcium silicate, Ca2SiO4.
In the precipitation process, stock solutions of SA
(the above leaching ltrates) were desilicated using a
standard process,14 and stored at 18 C until further
use, so as to avoid the separation of aluminium
hydroxide.
The following six different precipitation methods
were applied to transform the aluminium leached into
sparingly soluble salts:
(i) Method 1, precipitation via H2O2: In this method, a
1250 cm3 portion of 30 wt% H2O2 solution was
added to a 500 cm3 portion of SA solution
(CS = 100 g dm3), while being continuously stirred
at 800 rpm. The reaction was carried out in a 4 dm3
glass beaker at ambient temperature. The resulting
precipitate was ltered, washed and dried. Further
information about this method can be found
elsewhere.15
(ii) Method 2, precipitation via carbonation: A 300 cm3
portion of SA solution (80 g dm3) was placed into
the precipitator (a Buchner ask of 1 dm3 capacity). The initial temperature and pH of the
solution were 45 C and 12.5, respectively. Then,
CO2 gas was passed at 5 dm3 min1 until pH 10.5
was reached, and the nal temperature was set to
be 60 C. The resulting precipitate was ltered,
washed thoroughly with distilled water, and, then,
suspended in hot water at 85 C with constant
stirring at 100 rpm. HCl (1:1) was added to the
suspension until pH 3 was reached. The precipitate was allowed to settle at 85 C for 1 h, then
ltered, washed and dried.
(iii) Method 3, precipitation via ammonium carbonate:
Ammonium carbonate solution (150 g dm3) was
added to a 1 dm3 portion of SA solution (120 g
dm3) placed in a 4 dm3 glass beaker, and stirred
at 700 rpm. The addition of ammonium carbonate was continued until pH 10.5 was reached.
Subsequently, the precipitate was ltered,
washed, and dried.
(iv) Method 4, precipitation via ammonium bicarbonate:
Ammonium bicarbonate solution (150 g dm3)
was added to the same volume (and concentration) of SA solution as in Method 3. Similar
procedures of precipitation, washing and drying
were followed.
(v) Method 5, precipitation via ammonium aluminium
sulfate: A 150 cm3 portion of SA solution (120 g
dm3) was added to a 2.5 dm3 portion of ammonium aluminium sulfate solution (100 g dm3)
placed in a 4 dm3 glass beaker and stirred at 800
396

rpm. The resulting precipitate was ltered, washed

until sulfate-free, and dried.
(vi) Method 6, precipitation via addition of active seeds: A
1 dm3 portion of SA solution (120 g dm3) was
mixed with freshly prepared aluminium hydroxide gel (prepared by neutralization of SA solution
with HCl) in a 2 dm3 glass beaker. The content of
Al2O3 in the added gel was 60 g, which was
equivalent to about 50% of the Al2O3 content of
the aluminate solution. The mixture was vigorously stirred for a few minutes to ensure homogeneity, then a stream of air was passed
throughout via a diaphragm pump, model
ME2C Vacuubrand (Germany). The ow rate
was controlled with a ow-meter model 3217-45
of Cole-Parmer (USA) and the ow maintained
for 24 h at 30 C. Subsequently, the precipitate
was ltered, washed and dried.
All of the precipitates (denoted PSA were thoroughly washed with deionized water until the ltrate was
neutral to litmus paper. The precipitates were dried at
120 C for 12 h, and the dried materials (denoted
PSA(120)) were crushed into ne powders using agate
mortar. They were then analysed to establish their
chemical composition, crystalline bulk structure and
amount of yield, prior to calcination.
Calcination of the dried materials was conducted in
a static atmosphere of air at various temperatures
(Tc = 4001100 C) for 3 h, using a temperature controlled mufe furnace. The actual Tc was within 1 C
of the set temperature. The calcination products were
withdrawn from the furnace at 600 C, and cooled
down to ambient temperature over CaCl2. Eventually,
they were crushed into ne powders (using an agate
mortar) and readmitted into the desiccator until
further use. The calcination products are classied
according to calcination temperature applied, eg,
PSA(600) is the calcination product at 600 C.
Apparatus methods and techniques

Elemental analysis
Elemental analysis of the test materials was carried out
using the inductively coupled plasma (ICP) technique.
A model OES 3560 ARL (Switzerland) was used, and
standard procedures were followed.16 Solid test
materials were dissolved, prior to ICP analysis, in a
mixture of concentrated H2SO4 and H3PO4 in a
platinum crucible, using an acido rapid instrument,
model ACI Gerhardet (Germany). The temperature
was raised gradually until complete digestion of the
mixture. The digested material was dissolved in
deionized water, transferred into a volumetric ask
and lled to the mark.
X-ray powder diffractometry (XRD)
A model D 5000 Siemens diffractometer (Germany)
was used for crystalline phase analysis of the test
materials. The diffractograms were recorded stepwise
(0.02 Cs1) at ambient temperature. The instrument
J Chem Technol Biotechnol 75:394402 (2000)

Recovery of alumina from aluminium dross tailings

Figure 1. X-ray powder diffractogram for the test aluminium dross tailings (ADT): A = AlN, JCPDS 8-0262; B = Al2O3, 42-1468; C = NaAl11O17, 32-1033; D = SiO2,
33-1161; E = Al4C3, 35-0799; F = Al, 4-0787 and G = Na3AlF6, 18-1214.

was equipped with a copper anode generating Ni , 40 kV, 30 mA

ltered CuKa radiation (l = 1.5406A
back monochromator) in the 2y range between 10 and
80. An on-line data acquisition and handling system
facilitated an automatic JCPDS library search and
match (Diffrac AT software, Siemens) for phase
identication purposes.

tions). In contrast, a-Al2O3 and AlF3 were found to

require high temperatures and prolonged periods of
time to react with NaOH.

Surface area determination

Nitrogen adsorption measurements were determined
on test materials at liquid nitrogen temperature, using
a model ASAP 2010 Micromeritics sorpometer
(USA). The test samples were outgassed at 130 C
for 3 h prior to measurements. The specic surface
area (m2 g1) was calculated from the resulting
isotherms by BET analysis.17

RESULTS AND DISCUSSION

Chemical and crystalline phase composition of ADT

The chemical composition of ADT (expressed in

weight percentage) was determined: Al (44.8%); N
(6%); C (2%); Mg (1.5%); Si (1.1%); Fe (1.2%); Na
(0.7%); F (0.3%); Ti (0.03%); V (0.02%) and Mn
(0.2%). XRD results obtained for ADT (Fig 1)
suggest the presence of the following crystalline phase
compositions: metallic Al, aluminium nitride (AlN),
aluminium carbide (Al4C3), aluminium uoride
(AlF3), as well as different modications of aluminium
oxide (Al2O3). Corresponding model compounds
showed different behaviour in reaction with NaOH
solutions. Some of these compounds were found to
react readily with NaOH solutions at moderate
temperatures, viz. Al, AlN, and Al4C3, and the
transitional phases of Al2O3 (g, y, d and b-modicaJ Chem Technol Biotechnol 75:394402 (2000)

Figure 2. Effect of time (tm) and temperature (Tp) on recovery of aluminium

via atmospheric leaching at CSA = 200g dm3 and SLR = 0.3.

397

EA EI-Katatny et al

Figure 3. Effect of soda concentration (CSA) on recovery of aluminium via

atmospheric leaching at Tp = 100C, tm = 150 min and SLR = 0.3.

Analytical assessment of SA as a function of

leaching variables

SA obtained via atmospheric leaching

Figure 2 shows that the atmospheric leaching of
aluminium from ADT increases with the temperature
(Tp). A value of 40% recovery was obtained at 100 C,
as compared with 20 and 27% at 60 and 80 C,
respectively. Figure 2 also shows the initial high rate of
leaching to slow down markedly after the elapse of
100 min of leaching, regardless of the temperature
applied.
The atmospheric leaching process was also found to
be inuenced by the concentration of the soda solution
(CSA). Figure 3 indicates that the amount of aluminium recovered has increased from 33% at CSA =
100 g dm3 to 50% at CSA = 300 g dm3. The effect of
variation of the solid/liquid ratio (SLR) on the
recovery of aluminium was studied at Tp = 100 C,

Figure 4. Effect of the solid/liquid ratio (SLR) on the recovery of aluminium

via atmospheric leaching at 100C, tm = 150min and CSA = 150 g dm3.

CSA = 150 g dm3 and tm = 150 min. Figure 4 shows

that the % recovery insignicantly decreased on
increasing the SLR value up to 0.5.
SA obtained via high-pressure leaching
Table 3 summarizes the effects of Tp, tm, CSA and SLR
on the amount of aluminium recovered via highpressure leaching. The experiments were carried out at
the temperatures of 120, 160 and 180 C, which
correspond to the vapour pressures of 4, 7 and 10 bar,
respectively. Table 3 shows that the % recovery
increased rapidly during the rst 2060 min, after
which time it slowed down noticeably. The % recovery
is also shown to increase with temperature, reaching
the value of 73% after 100 min leaching at 180 C, and
to increase with the soda concentration (CSA) at
180 C (and tm = 100 min), reaching a maximal value
of 75% at CSA of 200 g dm3. It is clear from Table 3

Tp ( C)

Table 3. Amount of aluminium leached (Al2O3%)

under high-pressure as a function of temperature
(Tp), time (tm), soda concentration (CSA) and
solid/liquid ratio (SLR) at the constant values
indicated

398

Time (min)

120

160

180

20
40
60
80
100

11
35
42
45
46

15
42
55
59
61

20
52
65
71
73

CSA = 200 g dm3 and

SLR = 0.3 g cm3

150 200 250

67 73 74

300
75

Tp = 180 C, SLR = 0.3

and tm = 100 min

CSA (g-Na2O dm3) 125

62
SLR (g cm3)

0.2
77

0.3
73

0.4
57

Constants

0.5 Tp = 180 C, CSA = 200 dm3

44
and tm = 100 min

J Chem Technol Biotechnol 75:394402 (2000)

Recovery of alumina from aluminium dross tailings

that the % recovery is inversely proportional to SLR. A

maximal recovery value of 77% is shown to occur at
SLR = 0.2 as compared with a value of 44% at
SLR = 0.5.
It is to be noted that the maximal recovery of
aluminium from ADT via high-pressure leaching
(73%) is much higher than that (50%) reached via
atmospheric leaching, under given optimal conditions
(CSA = 300, tm = 150 min, SLR = 0.3 g cm3 and
Tp = 100 C), but still less than that (99.3%) expected.
This result may be attributed to the fact that ADT
contains a signicant amount of a-Al2O3, which is not
readily leachable under the conditions examined.
Crystalline phase composition of dried precipitates
(PSA(120))

Figure 5 displays XRD results for the PSA(120)

precipitates obtained via the various precipitation
methods attempted (Methods 16). The diffractogram (a) of PSA(120) recovered via Method 1 (H2O2
effected) exhibits peaks assignable to crystalline
boehmite, g-AlO(OH). The obvious broadness of
most of the diffraction peaks monitored may be due
to the presence of gelatinous boehmite. The diffractogram (b) of the precipitate recovered via Method 2
(carbonation) is dominated by peaks of crystalline
boehmite; presence of a minor proportion of gelatinous boehmite can not be ruled out. The crystallinity

of this precipitate appears to be relatively less than that

of the precipitate of Method 1.
The diffractogram (c) of PSA(120) produced via
Method 3 (ammonium carbonate effected) shows a
major pattern assignable to crystalline boehmite, and a
minor one (*-labelled peaks) due to bayerite, (aAl(OH)3). PSA(120), recovered using ammonium
bicarbonate (Method 4), gave an XRD pattern (d)
similar to that recorded for the product of Method 1
(pattern a); the sole detectable phase using this
method is crystalline boehmite, g-AlO(OH). The
presence of a minor proportion of gelatinous boehmite
is still likely.
The obviously broad, weak peaks displayed in the
diffractogram (e) of PSA(120) produced via Method 5
(using ammonium aluminium sulfate solution) may
imply the presence of gelatinous boehmite (pseudoboehmite) as the dominant bulk phase. On the other
hand, the very sharp peaks displayed in the diffractogram (f) of PSA(120) obtained via Method 6 (Bayer
process) are characteristic of strongly crystalline
gibbsite, g-Al(OH)3. It is evident, therefore, that the
formation, subsequent crystallization and particle
growth of gibbsite take place favourably under the
precipitation conditions applied.
In summary, the above results reveal that the
PSA(120) precipitates obtained via Methods 14
are essentially crystalline boehmite, (g-AlO(OH)).

Figure 5. X-ray powder diffractograms (af) of the

dried precipitates, PSA(120), obtained via
precipitation Methods 16, respectively.

J Chem Technol Biotechnol 75:394402 (2000)

399

EA EI-Katatny et al

Figure 6. X-ray powder diffractograms of the

calcination products of PSA(120) obtained via
precipitation Method 1, at the temperatures
indicated for 3 h. (Crystalline phases identified are
indicated.).

Pseudo-boehmite is the identied phase for the product

of Method 5, whereas that of Method 6 is identied as
being a strongly crystalline gibbsite, (g-Al(OH)3).

Thus, the phase transition sequence of pseudoboehmite can be summarized as follows:

400 500 C

900 C

Crystalline phase composition of precipitates as a

function of calcination temperature

Figure 6 exhibits X-ray powder diffractograms obtained for calcination products (at 6001200 C) of the
parent boehmite (precipitate of Methods 14). The
results therein displayed indicate that the major phase
compositions formed at 600900 C are of g-, d- and
y-Al2O3. The calcination product at 900 C is shown
to suffer a partial transformation into a-Al2O3. This
transformation is almost complete at 1200 C. Thus,
the phase transition of boehmite as a function of
calcination temperature is shown to follow the following sequence:


600 C

800 C

900 C

Boehmite ! Al2 O3 !  Al2 O3 !

1200 C

 Al2 O3 !  Al2 O3
A similar sequence has been previously reported in the
literature.18
XRD results obtained for the phase transition of
gelatinous boehmite (product of Method 5) during
calcination at 4001100 C are presented in Table 4
which shows that pseudo-boehmite was converted into
r-Al2O3 at 500 C, and into g- Al2O3 at 700 C.
y-Al2O3 appeared as a major phase at 900 C. It was
incompletely transformed into a-Al2O3 at 1100 C.
400

600 700 C

Pseudo boehmite !  Al2 O3 !

1100 C

Al2 O3 !  Al2 O3 !  Al2 O3

The phase transition course of gibbsite (product of
method 6) is also revealed in Table 4. Gibbsite is
shown to convert into boehmite at c 400 C, whereas at
600 C g-Al2O3 was the predominant product phase.
Subsequently, d-Al2O3 appeared at 800 C, and
y-Al2O3 at c 1000 C. At 1200 C, however, a considerable modication into a-Al2O3 phase took place.
The phase transition sequence of gibbsite can, therefore, be summarized as follows:
400 C

600 C

800 C

Gibbsite ! boehmite ! Al2 O3 !

1000 C

1200 C

 Al2 O3 !  Al2 O3 !  Al2 O3

It is obvious from the above results that PSA(600),
the calcination product at 600 C, is composed almost
entirely of g-Al2O3, independent of the parent
PSA(120) material used.
Chemical composition of calcined alumina
precipitates (PSA(600))

A full chemical analysis of the PSA(600) products was

carried out, and the results, given in Table 5, indicate
that the test materials are 99% pure Al2O3 and
that SiO2 is the major contaminant. The amount of
J Chem Technol Biotechnol 75:394402 (2000)

Recovery of alumina from aluminium dross tailings

Table 4. Crystalline phase composition of gelatinous boehmite and gibbsite
as a function of calcination temperature

Gelatinous boehmite
(Method 5)

Gibbsite (Method 6)
Calcination
Crystalline
temperature Crystalline
phase
Proportion
phase
Proportion
( C)
400
500
600
700
800

-Al2O3

g-Al2O3

Sole

Sole

900

y-Al2O3
a-Al2O3

Major
Minor

y-Al2O3
a-Al2O3

Minor
Major

1000
1100
1200

g-AlO(OH)

g-Al2O3

-Al2O3
g-Al2O3

Sole

Sole

Major
Minor

y-Al2O3
-Al2O3

Major
Minor

a-Al2O3
y-Al2O3

Dominant
Trace

SiO2 is known19 to be a function of the SiO2

concentration in the parent SA solution. The presence
of SiO2 in alumina improves its acidity and thermal
stability.20,21 The SiO2 content of all the test materials
is shown (Table 5) to occur in the range 0.250.53%,
which is acceptable, both for non-metallurgical and
catalytic aluminas.
The second major contaminant in the test materials
is Na2O, which originates from the sodium inherited in
the processed liquor. Sodium is known22 to have
negative impacts on the catalytic performances of
alumina in acid-catalysed reactions, because it poisons
centres of Lewis and Brnsted acidity. To reduce the
extent of soda in the PSA samples, the 600 C
calcination products were placed in Teon beakers
and boiled with suitable amounts of deionized water
for a few minutes. The samples were separated by
ltration and dried in platinum dishes. The results
given in Table 5 were obtained. The amount of soda in
these PSA(600) samples before the reduction procedure were determined to be: 0.53, 0.51, 0.54, 0.56,
0.65 and 0.93% for products of Methods 16,
respectively. Efforts to reduce further the amount of
Na2O are still being conducted, and results will be
published in due course.

Table 6. Specific surface area (m2 g1) and average particle size for the
recovered PSA(600) aluminas via the various precipitation methods
attempted

Precipitation
method
Method
Method
Method
Method
Method

Specic
surface area,
SBET (1m2 g1)

1
2
3
4
5

252
200
173
121
155

Method 6

156

`Air-Liquide'
commercial
g-Al2O3a

157

Average particle size ( 3A)

Before
calcination

After
calcination

64
62
91
64
Hard to
determine
733

64
72
61
67
Hard to
determine
82

Not
determined

Not
determined

For comparison purposes.

Specific surface area and particle size of the

recovered PSA(600) aluminas

The specic surface area (m2g1) for the various

PSA(600) aluminas recovered was determined by
BET-analysis of N2 adsorption data measured at
liquid nitrogen temperature. Table 6 compares the
SBET values observed with that determined for a
commercial g-Al2O3 produced and distributed by
`Air Liquide' (France) for catalytic and desiccant
applications. It is evident from Table 6 that the surface
area is higher for the aluminas produced via Methods
13 (252173 m2g1) than for those obtained via
Methods 46 (156121 m2g1). Table 6 also indicates
that the alumina produced via Method 1 (H2O2
assisted) assumes the highest specic surface area
(c 252 m2g1), and that most of the test materials have
surface areas comparable to or higher than that
(157 m2g1) of the commercial product.
The average particle (crystallite) size was calculated
for PSA(120) and PSA(600) products by means of the
XRD line broadening technique.23 The results show
(Table 6), that the average particle size values of
boehmite-based PSA(120) products (Methods 14)
are within the normal range of boehmite used to
produce catalytic aluminas.24 It is also evident that the
thermal treatment applied (600 C) to produce the test
aluminas does not cause particle sintering of any

Composition (wt%) a

Table 5. Chemical analysis results of the

600C calcination products (PSA(600)) of the
precipitates (PSA(120)) obtained via the
various methods (16) of precipitation applied

Precipitation method

Fe2O3

SiO2

TiO2

V2O5

Method 1
Method 2
Method 3
Method 4
Method 5
Method 6

0.010
<0.001
<0.001
0.008
<0.001
0.011

0.480
0.530
0.450
0.250
0.433
0.370

0.010
<0.001
<0.001
<0.001
<0.001
<0.001

<0.001
<0.001
<0.001
0.001
<0.001
0.020

J Chem Technol Biotechnol 75:394402 (2000)

CaO Na2O

ZnO

MnO

0.020
0.003
0.003
0.008
0.013
ve

0.040
0.040
0.040
0.060
0.050
0.020

0.001
<0.001
<0.001
<0.001
<0.001
<0.001

0.080
0.082
0.083
0.085
0.090
0.140

In all test materials, the Al2O3 content amounted to 99 wt%.

401

EA EI-Katatny et al

signicance. On the contrary, it appears to disperse the

) to
large particles of PSA(120) of Method 6 (733 A
).
produce g-Al2O3 of much ner particles (82 A
CONCLUSION

(1) The high-pressure leaching technique of aluminium from ADT has given a higher maximal
recovery value (c 73%) as compared with the
atmospheric leaching technique, which gave a
maximal recovery value of 50%, even when strong
leaching conditions were applied.
(2) The presence of an appreciable amount of
unleachable corundum (a-Al2O3) in the source
ADT suppresses the complete recovery of aluminium present in the dross material (theoretical
%Al in ADT = 99.3%).
(3) The various precipitation methods used in the
present investigation were found to affect, to some
extent, the crystalline modication of the precipitate obtained. For example, crystalline
boehmite, g-AlO(OH), was the product of
Methods 14, while gelatinous boehmite (pseudoboehmite) was that of Method 5. On the other
hand, strongly crystalline gibbsite, g-Al(OH)3, was
the product of Method 6.
(4) The calcination products (at 600 C) of all
precipitates consisted of 99% pure high-surface
area Al2O3 assuming the g-modication and
exposing high-area surfaces comparable with
some commercial alumina products. The product
of Method 1 resulted in g-Al2O3 of the highest
surface area of 252 m2 g1.
(5) ADT chemical waste can be protably utilized in
recovering catalytic-grade aluminas by implementing an economically feasible and technically
attainable procedure.

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J Chem Technol Biotechnol 75:394402 (2000)