Journal of the University ofB.

Chemical
Lucheva,Technology
Ts. Tsonev, and
R. Petkov
Metallurgy, 40, 4, 2005, 335-338

NON-WASTE ALUMINUM DROSS RECYCLING

B. Lucheva, Ts. Tsonev, R. Petkov

University of Chemical Technology and Metallurgy Received 03 November 2005

8 Kl. Ohridski, 1756 Sofia, Bulgaria Accepted 24 November 2005
E-mail: plasma@uctm.edu

ABSTRACT

The possibility for non-waste utilization of aluminum dross and converting it into commercial useful products was
investigated in this work. The object of this study is the secondary aluminum dross, which results from a primary “white”
aluminum dross fluxless processing in a rotary DC electric arc furnace.
The chemical composition of metallic and non-metallic phases of the secondary aluminum dross is determined.
The metal aluminum from dross was recovered by a method similar to Bayer’s process. The neutralization of the obtained
sodium aluminate solution by carbon dioxide resulted into the formation of aluminum hydroxide.
The method proposes a non-waste technology for secondary aluminum dross treatment – obtaining aluminum
hydroxide and a non-metallic product, containing about 80 % aluminum oxide. The aluminum hydroxide was used for
increasing the molar ratio of aluminum to chlorine in the aluminum oxychloride solution, which is applied as a coagulant
for water purification. The non-metallic product can be used in refractory production.
Keywords: aluminum dross, alkaline leaching, sodium aluminate, aluminum hydroxide.

INTRODUCTION aluminum dross salt-free processing in a rotary DC elec-

In the last decade many various pyrometallurgi-
cal [1-3] and hydrometallurgical technologies have been
developed in order to recover metal aluminum and valu-
able compounds from the aluminum dross. Secondary
aluminum dross with lower metal content is obtained in
primary aluminum dross pyrometallurgical processing.
According to the hydrometallurgical technologies the
metal aluminum from primary or secondary aluminum
dross has been leached by base [4] or acid [5] and the
final product in most cases is an aluminum hydroxide.
The aim of this work is to investigate the possi-
bility for non-waste recycling of aluminum dross in or-
der to produce useful commercial products.
EXPERIMENTAL
Analysis of secondary aluminum dross
The object of this study is the secondary alumi-
num dross (fraction - 1 mm), obtained from primary
tric arc furnace.
For determination of the metal phase content of
the secondary dross, a sample of 50 g was melted in a
graphite crucible at a temperature of 800o C in an in-
duction furnace under flux having the composition of
70 % NaCl, 28 % KCl and 2 % CaF2. The amount of
flux was added to the sample in mass ratio 1:1.
Two phases – metal and non-metal were ob-
tained. The non-metal phase was dissolved in water and
after that was filtered from the non-dissolved metal
phase. The metal phase was dried, weighed and its con-
tent in the sample was determined
According to this method the average metal con-
tent in the secondary aluminum dross (fraction -1 mm)
is 35 %. The chemical composition of the metal phase
in the secondary aluminum dross analyzed by scanning
electron microscopy (JEOL JSM 35) is presented in
Table 1. The element composition of the secondary alu-
minum dross was analyzed by AES ICP and is repre-
sented in Table 2.

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 Journal of the University of Chemical Technology and Metallurgy, 40, 4, 2005

Table 1. Metal chemical composition of the secondary content and can be utilized effectively for production
aluminum dross, mass. %. of different aluminum compounds.
Alkaline leaching of metal aluminum from the
Mg Al Si Mn Fe Cu Zn
secondary aluminum dross
0,00 90,28 5,93 0,34 1,10 1,82 0,53
For recovery of aluminum from the secondary
dross a method, similar to Bayer’s method for alumina
The main components of the investigated dross production was employed.
according to X-ray analysis (Fig. 1-1) are: metal alumi- A sample of 150 g secondary aluminum dross
num, magnesium aluminate spinel, graphite, aluminum was dissolved in 1 liter 10 % NaOH in molar ratio (al-
nitride, aluminum carbide, γ - alumina, á – quarz. kaline module) Na2O:Al2O3 = 2. The reaction between
The secondary aluminum dross is a valuable and aluminum and caustic soda is realized after:
less expensive raw material because of its high metal
2Al+2NaOH+6H 2 O → 2NaAl(OH) 4 +3H 2 ↑ (1)

Reaction (1) was strongly exothermic and in or-

der to control its rate the starting material was in por-
tions. The leaching of aluminum runs in parallel with
the aluminum nitride and carbide hydrolysis:

AlN+3H 2 O → Al(OH)3 +NH 3 ↑ (2)

Al4 C3 +12H 2 O → 4Al(OH)3 +3NH 3 ↑ (3)

Reactions (1-3) generated explosive gases which

during the experiments were sent off in the atmosphere,
but they could be burned or utilized. The duration of
the process was 2 hours.
The experiments were carried out at the follow-
ing conditions:
- Without heating and stirring;
- Without heating, with stirring;
- With heating (during the second hour of the
process) and stirring.
After filtering of the non-leaching product, the
Fig. 1. X-ray analysis of: 1 – secondary aluminum dross; sodium aluminate solution was analyzed for determin-
2 – NMP, obtained from alkaline leaching; 3 – NMP, calcined at
ing of aluminum, caustic soda and sodium carbonate
1000 oC
¢ - aluminum; H - graphite; £ - magnesium alu- content by titration with sodium gluconate and hydro-
minum spinel; ³-γ- alumina; - aluminum car- chloric acid.
bide; - aluminium nitride;š - nordstrandite; ¸ - The results of the alkaline leaching of metal alu-
á – quarz; I - á - alumina. minum from the dross at different conditions are pre-
sented in Table 3.

Table 2. Element composition of the secondary aluminum dross (fraction -0,1 mm), mass. %.

Al Mg Si Mn Fe Cu Zn Ti Ca Na K P S ÇÏÍ
42,10 3,83 2,68 0,11 1,22 0,63 0,18 0,31 0,79 0,11 0,26 0,01 0,26 3,86

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 B. Lucheva, Ts. Tsonev, R. Petkov

Table 3. Alkaline leaching of metal aluminum from the aluminate solution can be realized without using of stir-
secondary aluminum dross. ring and heating.
Carbonation of sodium aluminate solution
Final
Conditions ¹
Al2O3, Na2O(alk..), Recovery
alkaline The neutralization of the sodium aluminate so-
g/l g/l rate, %
module
1 79.61 68.56 80.27 1.42
lution was realized by blowing carbon dioxide through
Without heating 2 80.51 68.04 81.18 1.39 the solution and as a result aluminum hydroxide was
and stirring 3 79.10 68.85 79.76 1.43 obtained:
Average: 79.74 68.48 80.40 1.41
2NaOH+CO2 → Na 2 CO3 +H 2 O (4)
4 82.44 66.92 83.13 1.34
Without heating 5 83.60 66.25 84.30 1.30 The alkaline module of the solution decreases,
with stirring 6 82.87 66.68 83.56 1.32 the solution becomes unstable and at these conditions
Average: 82.97 66.62 83.66 1.32 the sodium aluminate decomposes according to the fol-
7 85.72 65.03 86.44 1.25 lowing equation:
With heating and 8 85.00 65.45 85.71 1.27
stirring 9 85.22 65.32 85.93 1.26
NaAlO2 +2H 2 O → Al(OH)3 +NaOH (5)
Average: 85.31 65.27 86.03 1.26 The obtained free caustic soda reacted with new
portions of carbon dioxide and the sodium aluminate
decomposition continued. The process is realized at
Practically stable aluminate solutions were ob- room temperature and continuous stirring in order to
tained from the alkaline leaching. The sample of the adjust solution concentration and to avoid falling of a
aluminate solution No9 was analyzed by AES ICP for finely dispersed and difficult to wash precipitate. The
determining of impurity amounts (Table 4). carbon dioxide blowing through 1 liter of sodium alu-
The obtained results shaow that an economically minate solution (No 3) was realized by bubble ring at
advantageous process with a satisfactory aluminum re- rate of 5 l.min-1 for a period of 5 min. The process was
covery rate (about 80 %) and production of a stable carried out under the stoichiometric ratio in order to

Table 4. AES ICP analysis of sodium aluminate solution, mg/l.

Al Na Pb Zn Cu Ni Co Cd K Mg Ca
45115 50880 <45 <10 <10 <10 <10 <10 415 <150 <150

Table 5. Element analysis of NMP.

avoid the generation of Na2O.Al2O3.2CO2.nH2O pre-
Elemental basis, mass. % Oxide basis, mass. %
cipitate. At those conditions the aluminum hydroxide
Before After Before After
calcination calcination calcination calcination production rate was 85 %. The obtained precipitate
Al 34,10 42,64 Al2O3 64,45 80,58 was identified by X-ray analysis as two polymorphs of
Mg 2,32 2,90 MgO 3,85 4,81 aluminum hydroxide – bayerite (â Al2O3.3H2O) and
Si 2,06 2,58 SiO2 4,41 5,51 bemite (á Al2O3. H2O).
Mn 0,11 0,14 MnO 0,14 0,18 Analysis of the undissolved product, obtained
Fe 0,92 1,15 Fe2O3 2,63 3,29 from alkaline leaching
Cu 0,6 0,75 CuO 0,75 0,94
The undissolved non-metal product (NMP), ob-
tained from the alkaline leaching was analyzed by X-
Zn 0,3 0,38 ZnO 0,37 0,47
ray diffraction (Fig. 1-2). The main components are
Ti 0,14 0,18 TiO2 0,23 0,29
magnesium aluminate spinel, g - alumina, graphite, á –
Ca 0,63 0,79 CaO 0,88 1,10
quartz, some metal aluminum and aluminum hydrox-
Na 0,50 0,63 Na2O 0,67 0.84
ide in a polymorph of nordstrandite. The latter is most
K 1 1,25 K2O 1,20 1,51
likely formed by aluminum nitride or aluminum car-
P 0,03 0,04 P2O5 0,07 0,00 bide hydrolysis. The X-ray analysis did not detect AlN
Loss on ignition 20,02 %

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 Journal of the University of Chemical Technology and Metallurgy, 40, 4, 2005

and Al4C3, so as a result of the leaching their harmful CuCl H Secondary aluminum dross H NaOH

effect is neutralized.
Dissolving in CuCl Dissolving in NaOH
The NMP was analyzed by AES ICP.The results
are presented in Table 5. CO

CuCl
Regenerated
Most of the leached residue is oxides, but be- precipitate NaAl(OH)" NMP

solution of
cause of the existence of a small quantity of metal alu-

Calcination
Al(OH)!
minum, the NMP is subjected to oxidation in order to HCl

convert the remaining metal into oxides. The NMP was
calcinated after being washed with water and dried. The
calcination was carried out at 1000o C for 1 hour and
qualitatively analyzed by XRD (Fig. 1-3), which indi-
cated that the main phases were a-alumina, a- quartz
and magnesium aluminate spinel. According to Table 5
the NMP consists of average 80 % Al2O3, 5 % MgO
and 6 % SiO2 and can be used successfully for produc-
tion of alumina refractory materials.
The aluminum hydroxide obtained from the alu-
minum dross alkaline leaching has been used for cor-
rection of the molar ratios Al:Cl and Al:OH in the pro-
duction of the Al2(OH)5Cl coagulant [6] (Fig. 2).
CONCLUSIONS
It is established that the average metal content in
the investigated secondary aluminum dross (fraction -
1 mm) is 35 %.
The possibility for alkaline leaching of metal alu-
minum from dross was investigated and economically
acceptable parameters of the process ensuring 80 % re-
covery rate were determined.
Practically stable aluminate solutions with alka-
line module 1,4 are formed as the result of the dross
alkaline leaching, and aluminum hydroxide is produced
by carbonation of the solutions.
According to the proposed non-waste technol-
ogy the aluminum dross is converted into useful com-
mercial products: aluminum hydroxide (which has been
used for correction of the molar ratio Al:Cl in alumi-
num oxychloride solutions) and a non-metal product
with more than 80 % alumina content (which can be
used for refractory materials production).
Aluminum NaOH
Dissolving compounds
Al (OH)#Cl
NMP For water
treatment
For refractory
materials
Calcination
Fig. 2. Non-waste technological scheme for the secondary
aluminum dross recycling.
REFERENCES
1. S. Lavoie, G. Dube, A salt-free treatment of aluminum
dross using plasma heating, JOM, February, 1991, 54-55.
2. S. Lavoie, J.Lachance, Five years of industrial expe-
rience with the plasma dross treatment process,
Proc. 3rd International symposium, Recycling of
metals and engineered materials, The minerals,
metals and materials society, November 12-15,
1995, pp.791-801.
3. M. Drouet, J.Meunier, Claude B.Laflamme, My
D.Handfield, A.Biscaro, C.Lemire, A rotary arc fur-
nace for aluminum dross processing, Proc. 3rd In-
ternational symposium, Recycling of metals and
engineered materials, The minerals, metals and ma-
terials society, November 12-15, 1995, pp. 803-812.
4. Lee Hoo-in, Park Hyung-Kyu, Yoon Eui-Pak, Pro-
cess for recycling waste aluminum dross, Patent
US6296817, 2001-10-02.
5. B.J. Jody, E.J. Daniels, P.V. Bonsignore, D.E. Karvelas,
Recycling of aluminum salt cake, Journal of Resource
Management and Technology, 20, No1, 1992, pp.38-49.
6. B. Lucheva, R. Petkov and Tz. Tzonev, Method for
aluminum dross utilization, Proc. 3rd BMC, Ohrid,
R. Macedonia, Sept.24-27, 2003, pp.259-264.

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