Desalination and Water Treatment 170 (2019) 265–276

December
www.deswater.com
doi: 10.5004/dwt.2019.24732

Synthesis of high-grade alumina from aluminium dross and its utilization

for the sorption of radioactive cobalt

Mohamed Mahmoud E. Breky*, Emad Hassan Borai, Amany T. Kassem

Hot Laboratories and waste Management Center, Atomic Energy Authority, Cairo 13759, Egypt,
emails: [email protected] (M.M.E. Breky), [email protected] (E.H. Borai), [email protected](A.T. Kassem)

Received 28 February 2019; Accepted 26 July 2019

abstract
Aluminium dross (AD) forms on the surface of molten metal as the latter reacts with the furnace
atmosphere and is usually considered a waste of aluminium production. AD contains a complex
mixture of mostly aluminium oxide (AO), nitride, carbide and sulfide, some alloying elements and
salts. Nevertheless, AD is considered as hazardous waste and a rich source of alumina. In the present
study, waste dross rich in alumina was treated with either acid or base dissolution to recover alu-
mina. Aluminium sulphate (AS) and AO were produced using sulfuric acid and sodium hydroxide
leaching, respectively. AS sample was calcined at 500°C, 700°C and 900°C, individually. At 900°C,
AS was thermally degraded and transformed into AO. Also AO, (AO/H2SO4) and (AO/HCl), was
prepared using AD dissolution by NaOH and neutralized by dropwise addition of either 2 N H2SO4
(AO/H2SO4) or 2 N HCl (AO/HCl). The resulting samples were characterized by X-ray diffraction,
X-ray fluorescence and scanning electron microscopy. The resulting samples produced from acid and
base leaching were applied to remove a harmful radionuclide (Co2+) from liquid waste. The maximum
Co2+ adsorption capacity was 193, 180, 197, 296 and 235 mg g–1 for the as-prepared AS, where AS
calcinated at 700°C, AO calcinated at 900°C, AO/HCl and AO/H2SO4, respectively.
Keywords: Aluminium dross; Alumina; Cobalt radionuclide; Removal capacity; Radioactive waste
treatment

1. Introduction a long continuous network in which aluminium is entrapped.

The molten flux breaks this framework and facilitates the
The disposal and recycling of the dross produced by the
coalescence of aluminium drops that sink in the aluminium
aluminium industry are the global problems. Serious water
bath [2]. In most cases, a salt bath is used to maximize the
pollution problems result from the leaching of toxic metal
recovery of aluminium. In this process, the oxide gener-
ions into ground water because the majority of dross is dis-
ation is less, but the resultant dross is toxic because of its
posed of in landfill sites [1]. Furthermore, many noxious
salt content, making the disposal of dross and recovery of
gases, such as NH3, CH4, PH3, H2 and H2S, are emitted when
aluminium from dross more complex.
aluminium dross (AD) comes in contact with water [1]. AD
Drosses are classified into white and black dross accord-
is formed by the natural oxidation of molten aluminium.
ing to their metal content. White dross has higher metal
When the metal is in contact with air, aluminium oxide (AO)
aluminium content and is produced from primary and
forms on the outer surface of the melt. The residual metal in
secondary aluminium smelters; black dross has a lower
the dross is removed by re-melting the AD by adding a salt
metal content and is generated during aluminium recycling
flux to minimize oxidation. The oxide in dross is present as
(secondary industry sector). White dross may contain from

* Corresponding author.

1944-3994/1944-3986 © 2019 Desalination Publications. All rights reserved.

266 M.M.E. Breky et al. / Desalination and Water Treatment 170 (2019) 265–276

15% to 70 % recoverable metallic aluminium and is a fine transformations of alumina due to the effect on the kinet-
powder due to skimming molten aluminium. Black dross ics of transformation [19–22]. According to Gitzen [23],
typically contains a mixture of AOs and slag with a recov- γ-Al2O3 transforms to δ-Al2O3 when calcined above 800°C.
erable aluminium content ranging from 12% to 18% and a The δ-Al2O3 transforms to θ-Al2O3 when calcined above
much higher salt content (typically higher than 40%) than 1,000°C. Finally, θ-Al2O3 transforms to α-Al2O3 when cal-
white dross. The non-metallic residues generated from dross cined above 1,100°C. However, the presence of impurities
smelting operations are often termed ‘salt cake’ and contain alters the barrier of phase transformations. For example,
3%–5% residual metallic aluminium [1]. calcinations of γ-Al2O3 with 3% platinum impurity can cause
Although aluminium production is highly energy inten- the α-Al2O3 to form below 1,100°C [23–25].
sive, dross recycling is very attractive from both energy Boehmite, aluminium oxyhydroxide (AlO(OH)), is a ver-
and economic standpoints [3]. Recycling AD to obtain val- satile material employed in sol–gel ceramics, surface coat-
ue-added products has received significant interest. The ings, rheology control applications, and pharmaceuticals
authors have demonstrated the conversion of AD to vari- [14]. It is also an important precursor for preparing alumina.
ous high-value materials, including anion exchangers for γ-Al2O3 is commonly produced from boehmite by calcina-
the removal of toxic ionic substances [4–10] and adsorbents tion at 500°C in air [26]. Amer [14] produced two types of
for gasses [11,12]. Murayama et al. [8] synthesized Mg–Al, alums (aluminium sulfate) by dividing the alumina leach-
Ca–Al and Zn–Al as layered double hydroxides using the AD ing process into two steps. In the first step, leaching was
leachates as a raw material and examined their performance carried out with dilute H2SO4 to remove impurities, and in
as an anion exchanger. The Egyptalum Company (a major the second step, alumina was extracted from the purified
producer of aluminium in Egypt) generates approximately dross tailings using concentrated H2SO4 [14]. El-Katatny et
12,800 tonnes of aluminium dross tailings (ADT) per year. al. [26] described a process where aluminium can be recov-
ADT are aluminium-rich (45 wt.% Al) chemical waste and ered from dross by precipitating aluminium hydroxide
are currently neither properly dispensed nor adequately using a NaOH solution. The aluminium hydroxide powder
utilized [13]. In Egypt, large quantities of aluminium slag is then activated at 600°C to obtain γ-Al2O3.
(dross) and moderate quantities of aluminium sludge are Radioactive wastewater is documented as a very risk
disposed of as waste by the aluminium industry, causing hazardous material and the main sources of this waste are
many ecological and health problems [14]. the radioactive isotopes. Radioactive isotopes are continuous
Sulfuric acid plays an important role in the aluminium sources for radiations like beta and gamma [27]. In addi-
process and has an interest in an alkaline acid, which allows tion to the previous, 60Co radioactive isotopes are known as
it to quickly dissolve and increase the concentration of sul- hazardous radioactive isotopes which produce gamma rays
fate ions. Sulfuric acid will reduce the precipitation rate of with the high possibility of penetration into the human body
aluminium sulfate and ensure the utilization of AD in a con- to cause internal irradiation in the human cells and may lead
centrated sulfuric acid solution. A sulfur ion concentration to the death [28].
can be created in a solution, and the concentration depends The main aims of the present study is (i) to prepare
on the availability of both acid and water to preserve dis- purified alumina from AD by different dissolution meth-
solved aluminium sulfate during the solubility process [15]. ods, (ii) to optimize the condition required for the effec-
Previously, sodium hydroxide is used for dissolving tive removal of radioactive cobalt from waste solution by
aluminium from bauxite, for opening monazite sand, and means of batch adsorption experiments and (iii) to convert
for leaching wolframite and scheelite ores [16,17]. Leaching AD waste to high value materials and minimize its environ­
by bases has the following advantages; (a) negligible corro- mental impact.
sion problems, (b) suitability for ores containing carbonate
gangue and (c) more selectivity, since iron oxides will not
be leached out. 2. Materials and methods
Previously, sodium hydroxide is used for dissolving alu- 2.1. Materials and reagents
minium from bauxite, for opening monazite sand, and for
leaching wolframite and scheelite ores [16,17] AD is a waste material and was obtained from the
Alumina is one of the most important structural materi- Egyptalum Company, Nag Hammady, Egypt. The H2SO4,
als with several transition phases that have enormous tech­ HCl and NaOH used in the AD leaching experiments were
nological and industrial significance [18]. Alumina is the analytical grade reagents (Merck Company, Germany).
most commonly used catalyst and catalyst support in hetero-
geneous catalysis due to its low cost, good thermal stability, 2.2. Acidic leaching of AD
high specific surface area, surface acidity and interaction
with deposited transition metals. Alumina has eight different First, 313.7 g of AD was added to 400 ml concentrated
polymorphs – seven metastable phases (γ, k, p, η, θ and x) sulfuric acid at 90°C, and 100 ml of 1 N sulfuric acid was
as well as the thermally stable α-phase. The metastable (also added to complete digestion. As the dissolution reaction is
known as transition) phases of alumina are intrinsically exothermic, the temperature of the leaching medium spon-
nanocrystalline and can be easily synthesized by a variety taneously increased up to 80°C–85°C. A hot plate was uti-
of methods. lized to maintain the temperature at 90°C ± 2°C. A paste was
Al2O3 can be transformed into a different phase by heat formed and then dissolved in 7 L of hot distilled water at 70°C.
treatment. Factors such as particle size, heating rate, impu- The pH of the solution was 1.5. The leach solution obtained
rities, and atmosphere may influence the sequence of phase (soluble aluminium sulfate), after filtration, was subjected to
 M.M.E. Breky et al. / Desalination and Water Treatment 170 (2019) 265–276 267

direct precipitation using 50% aqueous ammonia that was cobalt chloride to obtain cobalt concentrations in the range
added dropwise. The resulting pH was 7. The produced gel of 100–500 ppm. Batch experiments were conducted with
was left to stand for 2 h (aging time) in the mother liquor at different shaking times of 15, 30, 60, 120, 180 and 1440 min
80°C. Following the ageing step, the gel was washed until at 25°C. The adsorption isotherms were obtained under the
no additional sulfate ions were detected in the washings. optimum conditions for the adsorption of Co. The effect of
Finally, the gel was dried at 60°C for 24 h, ground and cal- the initial pH of the Co solution on the sorption process
cined for 3 h in a muffle furnace in air at 500°C, 700°C and was investigated at pH values of 2, 4, 6 and 8.
900°C. After reaching equilibrium, the solid/liquid phases were
During the sulfuric acid leaching of the dross, all the alu- separated by centrifugation (4,000 rpm). For the adsorption
minium present in the dross was converted to water-soluble of contaminants, the adsorption capacity qe (mg of adsor-
aluminium sulfate, as shown in the following reaction. bate/g of adsorbent) of the adsorbent was calculated as
follows:
2.3. Leaching of AD by NaOH
V × ( Ci − C e )
20 g of aluminium slag was dissolved in 50 ml 2 N qe = (2)
m
NaOH (exothermic reaction accompanied by effervescence).
The solution sat overnight under vigorous stirring at 80°C. where Ci is the initial concentration of the metal in solution
The pH of the solution was 10.8. The resulting solution (in mg L−1), Ce is the metal concentration at equilibrium, V is
(soluble sodium aluminate, Na[Al(OH)4](aq)) was divided the volume of solution in litres, and m is the weight of the
into two aliquots. The first one was neutralized by dropwise adsorbent in grams.
addition of 2 N H2SO4 until a white precipitate formed at pH The uptake percent (U %) of Co2+ was calculated by the
8. The precipitate was washed by distilled water. The second following equation:
part of the solution was neutralized by dropwise addition of
2 N HCl until a white precipitate formed at pH 7. The pre-
cipitate was washed by distilled water. The two precipitates
U% =
(A 0
− A)
× 100 (3)
were dried at 85°C and calcined in air at 700°C. A0

2.4. Characterization where A0 and A are the activities expressed in counts per
minute of the radioisotope in a 2 mL solution before and
Chemical analyses of the AD and prepared materials after contact with the prepared aluminium samples.
were performed using a Philips sequential X-ray fluores-
cence (XRF) spectrometer (2400). X-ray diffraction (XRD)
patterns were recorded at room temperature using a powder 3. Results and discussion
diffractometer (Bruker Axis D8 Advance, Germany) with a The synthesis processes of Al2O3 from AD through acid
Cu-Kα radiation source, λ  =  1.5406  Å and 2θ in the range and base leaching are summarized in Fig. 1. During sulphuric
of 10°–80°. The average crystallite size of the nanoparticles acid leaching of the dross, all the aluminium presented in
was determined according to the Scherrer equation [29]. dross converted to water-soluble aluminium sulphate (AS)
as shown in the following equations:
0.9λ
D= (1)
( cos θ )
β Al 2 O 3 + 3H 2 SO 4 = Al 2 ( SO 4 )3 + 3H 2 O (4)

where λ is the X-ray wavelength, θ is the Bragg angle of

the peak of interest and β is the line broadening measured 2 Al + 3H 2 SO 4 = Al 2 ( SO 4 )3 + 3H 2 (5)
from the peak width at half height. The porous structure of
alumina was characterized by adsorption–desorption of N2
2 Al + 6H 2 SO 4 = Al 2 ( SO 4 )3 + 3SO 2 + 6H 2 O (6)
Brunauer–Emmett–Teller (BET method) at the temperature of
liquid nitrogen (77 K) (JEOL-JSM 6510 LA, Japan). Scanning
electron microscopy (SEM) was used to examine the pore On the other hand, the alkali leaching process is based
structure of the prepared aluminium samples. on dissolution of Al and Al2O3 in strong sodium hydroxide
solution at atmospheric condition. Aluminium can be recov-
2.5. Adsorption study ered as aluminium hydroxide by precipitation. Alumina
can be then produced by calcination at high temperature as
The radioisotope (60Co) used in this study was supplied shown in the following equations [30,31].
by Hot Laboratories and Waste Management Centre (HLWMC)-
Egyptian Atomic Energy Authority (EAEA). A 60Co solu-
Al 2O 3 + 2 NaOH → 2 NaAlO 2 + H 2 O (7)
tion with high specific activity was used as a tracer. The
radio­active 60Co tracer was measured by a NaI scintillation
detector connected to a multi-channel analyser (Genne 2000, 2 Al + 2 NaOH + 2H 2 O → 2 NaAlO 2 + 3H 2 ↑ (8)
USA). Stock solutions of 1,000 mg L–1 Co(II) in distilled
water were prepared from the salt precursor CoCl2·(H2O)6.
The 60Co tracer was mixed with known amounts of inactive NaAlO 2 + HCl + H 2 O = Al ( OH )3 ↓ + NaCl (9)
268 M.M.E. Breky et al. / Desalination and Water Treatment 170 (2019) 265–276

Aluminium
dross

Characterization

Base Leaching Acid Leaching

NaOH H2SO4

HCl/ H2SO4/ Aluminium sulfate

NaAlO2
Hydrolysis Hydrolysis solution

Al(OH)3 Ammonia
Calcination Calcination Aluminium sulfate

500 °C 900 °C
Al2O3/H2SO4 700 °C
Al2O3/HCl
Aluminium
Aluminium α-Al2O3
Sulfate
Sulfate

Fig. 1. Flow chart for the synthesis of Al2O3 from aluminium dross through acid and base leaching.

Table 1
NaAlO 2 + H 2 SO 4 + H 2 O = Al ( OH )3 ↓ + Na 2 SO 4 (10)
XRF analyses of aluminium slag and the treated AO samples

Analyte Concentration
2 Al ( OH 3 ) + heat → Al 2 O 3 + 3H 2 O (11)
Dross Aluminium α-AO AO/HCl AO/H2SO4
sulfate
3.1. Characterization
Al 92.355 47.729 98.794 97.599 96.394
The chemical composition of the AD is given in Table 1.
The XRF analysis of the AD, AS, α-alumina, alumina/HCl and Si 1.301 0.714 0.473 2.011 2.097
alumina/H2SO4 (expressed in concentration percentages). S 1.069 50.136 0.411 0.39 1.509
The results indicated that highly pure alumiuim oxide Cl 0.212 0.24 0.123
samples can be obtained. The concentrations of Al analyet Ca 0.578 0.177
increased from 92.355% in AD to 98.794, 97.599 and 96.394 Ti 0.13 0.108
for α-AO, AO/HCl and AO/H2SO4. Some trace elemental Zr 0.018 0.894
oxides of Ca, Ti and Zr were detected in AD and disappeared
in aluminum oxides samples.
The XRD pattern of the AD is shown in Fig. 2. The AD by calcination of the resulted sample from acid leaching
contained corundum or α-alumina (Al2O3, 49.2%), calcium at 900°C.
AO (38.1%) and AO (12.7%).
Solubility of the black dross in sulfuric acid can be deter-
3.2. Effect of the calcination temperature on aluminium
mined from the initial weight of dross and dry residue. During
sample morphology
sulfuric acid digestion, 70% of Al dross was dissolved at
80°. Fig. 3 shows the XRD pattern of the as-prepared Al To study the effect of the calcination temperature on the
sample after acid digestion and precipitation at pH 7 by aluminium sulfate morphology, the prepared sample from
30% ammonium hydroxide at room temperature. The sam- H2SO4 digestion was calcined at 500°C, 700°C and 900°C.
ple contains three compounds, Tohdite (5Al2O3·H2O, 48.3%), Fig. 5 shows the effect of calcination temperature on the as
aluminium chloride hydrate (AlCl3 (H2O)6, 13.1%), and prepared aluminium hydrogen sulphate. The XRD results
aluminium hydrogen sulphate hydrate (Al(HSO4)3·6H2O, indicated that aluminium hydrogen sulfate was stable up to
38.6%). Calcium AO was not detected in the prepared alu- 700°C. At 900°C, the as-prepared aluminium hydrogen sulfate
minium sample. The detected chloride is mainly attributed was converted to α-Al2O3. Alumina powders were produced
to the high chloride concentration in the original dross from the conversion of the Al2(SO4)3 at high temperatures.
(NaCl). In this respect, the prepared sample was not washed Al2(SO4)3·18H2O is a complex molecule. Calcinations on the
enough. Al2(SO4)3·18H2O break down the bond in the complex mol-
XRD analysis (Fig. 4) confirms the transformation of ecule and provide sufficient interaction for the elements
Tohdite, aluminium hydrogen sulphate hydrate and alumin- to form a new compound that is simpler and more stable.
ium chloride hydrate into alumina (α-Al2O3 or corundum) At sufficiently high calcination temperatures, Al2(SO4)3·18H2O
 M.M.E. Breky et al. / Desalination and Water Treatment 170 (2019) 265–276 269

Fig. 2. XRD patterns of the original dross

Fig. 3. XRD pattern of the as-prepared Al sample after acid digestion.

is fully converted into alumina by eliminating water vapor, Al 2 (SO 4 )3 ( s ) → Al 2 O 3 ( s ) + 3SO 3 ( g ) (13)
followed by the elimination of sulfur trioxide gas; these reac-
tions are shown in Eqs. (12) and (13) [32–34]. Some volatile
impurities in the gaseous state are also driven off. The calci- These results indicate that 900°C is sufficient to form AO
nations provide heat energy to the alumina, which is needed crystals and activate AO by eliminating most of the water.
for it to undergo further phase transformations to form Also,these results confirm the presence of impurities alters
α-alumina, the most stable crystalline structure of alumina. the barrier of phase transformations. In the previous stud-
ies, calcinations of γ-Al2O3 with 3% platinum impurity can
Al 2 (SO 4 )3 × 18H 2 O ( s ) → Al 2 (SO 4 )3 ( s ) + 18H 2 O (g ) (12) cause the α-Al2O3 to form below 1,100°C [23–25]. The XRD
270 M.M.E. Breky et al. / Desalination and Water Treatment 170 (2019) 265–276

Fig. 4. XRD pattern of alumina synthesized from AD leachate of H2SO4 calcined at 900°C.

results from Table 2, related to Fig. 5, confirm the presence Table 2

of α-Al2O3 XRD diffraction data of resulted α-Al2O3 calcined at 900°C

Position Area Cry size L(nm) Peak identity

3.3. AD leaching using NaOH
25.68311 74.53126 91.8 α-Al2O3
Fig. 6 illustrates the XRD patterns of alumina (Al2O3/
35.2535 121.2017 90.1 α-Al2O3
H2SO4, Al2O3/HCl) from the NaOH leachate and neutralized
by acid (2 N H2SO4 and 2 N HCl). The as-prepared alumin- 37.87103 57.45199 73.2 α-Al2O3
ium hydroxide (boehmite) was heat treated at 700°C to obtain 43.45542 132.9412 94.3 α-Al2O3
γ-Al2O3, which is a high-value activated alumina form that 52.63905 64.02469 88.3 α-Al2O3
can be used as an adsorbent. Table 1 shows the XRF analysis 57.58051 130.3576 83.6 α-Al2O3
for the alumina samples after base leaching and neutralized 59.81626 5.739617 53.4 α-Al2O3
by H2SO4 and HCl. The result confirm the increasing the con- 61.34287 17.59781 45.9 α-Al2O3
centration of alumina and decreasing the content of impuri-
66.59101 62.9386 63.3 α-Al2O3
ties and salts.
68.27992 78.41881 87 α-Al2O3
76.99669 32.73482 52.3 α-Al2O3
3.4. Surface area results
The BET specific surface area, pore diameter and pore
volume of the different aluminium samples were obtained. alumina/H2SO4. The morphologies of the samples appear to
The BET analysis results for the synthesized aluminium be lumpy, consisting of dense aggregates of lumpy amor-
samples are summarized in Table 4. A comparison of the sur- phous macro-crystallites. The micro-crystallites appeared
face areas of the samples as a function of the calcination tem- to be very small, that is, in the nano-size range; the actual
perature showed that the surface area of AD was 1.274 m2 g–1 crystal size could not be determined from the SEM images.
and increased to 9.341 m2 g–1 after acid digestion. The α-Al2O3 Additionally, all samples show significant differences in
calcined at 900°C had a surface area of 36.466 m2 g–1. Based terms of shape and size uniformity.
on these results, H2SO4 leaching of AD increases the surface
area, pore volume and pore diameter of the resulting mate-
rial, as shown in Table 4. These improvements in the surface 4. Sorption study
area and pore volume reflect the efficient expected uses of 4.1. Effect of shaking time
alumina (α-Al2O3) as sorbent for hazardous metals removal.
The effect of shaking time on radioactive Co2+ distribution
is tested to clarify its insights into reaction kinetics. The sorp-
3.5. SEM results
tion kinetics of radioactive Co2+ was studied at different
Fig. 7 shows the images of the as-synthesized alumin- time intervals ranging from 10 min to 24 h at constant V/M
ium sulfate, alumina calcined at 900°C, alumina/HCl and (0.1 L g–1) ratio. As shown in Figs. 8 and 9, the equilibrium
 M.M.E. Breky et al. / Desalination and Water Treatment 170 (2019) 265–276 271

(e) Al2O3 calcined 900 °C

(d) Al sulphate calcined 700 °C

(c) Al sulphate calcined 500 °C

(b) Dry Al sulphate

(a) Al dross

10 20 30 40 50 60 70 80
2-Theta-scale

Fig. 5. XRD patterns of (a) AD, (b) prepared aluminium sulphate, (c) aluminium sulfate calcined at 500°C, (d) aluminium sulfate
calcined at 700°C and (e) aluminium oxide calcined at 900°C.

Fig. 6. XRD patterns of alumina synthesized from Al dross leached by NaOH (a) neutralized by H2SO4 calcined at 700°C and
(b) neutralized by HCl calcined at 700°C.

Table 3
Summary of the results for the aluminium samples at different stages (acid leaching) based on the XRD results

Sample name Compound name

Aluminium dross Calcium aluminium oxide
Corundum or α-alumina, Al2O3
Aluminium oxide
Dried Al sample after acid digestion and sulfate hydrolysis Tohdite, aluminium oxide hydroxides, 5Al2O3·H2O
Aluminium chloride hydrate, AlCl3(H2O)6
Aluminium hydrogen sulfate hydrate- Al(HSO4)3·6H2O
Al sample after acid digestion calcined at 500°C Al2(SO4)3
Al sample after acid digestion calcined at 700°C Al2(SO4)3
Al sample after acid digestion calcined at 900°C Alumina, α-Al2O3
272 M.M.E. Breky et al. / Desalination and Water Treatment 170 (2019) 265–276

Fig. 7. SEM images of (a) synthesized aluminium sulphate, (b) alumina calcined at 900°C, (c) alumina/HCl and (d) alumina/H2SO4.
 M.M.E. Breky et al. / Desalination and Water Treatment 170 (2019) 265–276 273

Table 4
Results of the BET analyses of aluminium samples for nitrogen adsorption–desorption (SBET) and crystallite size (XRD)

Sample Specific surface Average pore Total pore Mean crystallite

area (m2 g−1) radius volume (cc/g) size (nm)
Aluminium dross 1.274 192.162 0.01224 54
Al originally prepared 9.341 100.00512 0.04695 22
α-Al2O3 calcined at 900°C 36.466 60.31627 0.1152 75

time for radioactive Co2+ on the originally prepared AS, alu- initial concentration respectively of Co(II) at pH 4, (Fig. 9).
mina calcined at 700°C, alumina calcined at 900°C, alumina/ The fast sorption process at initial stage could be attributed
HCl and alumina/H2SO4 is reached at 2 h. As shown in Fig. 8, to fact that large number active sites are available for sorp-
it could be observed that, at pH 4, the sorption uptake of tion on to aluminium sample.
Co(II) increases from ~17% to ~51%, ~7% to ~33% and ~92%
to ~98% for Al-sulphate, Al-sulphate calcined at 700°C and 4.2. Effect of pH on the sorption process
alumina calcined at 900°C, respectively.
For the alumina resulted from base leaching the sorption To assess the effect of pH on adsorption, experiments
of Co(II) on alumina/HCl and alumina/H2SO4 increases were performed at different pH values ranging from 2 to 8
from ~93% to ~98% and ~92% to ~97% respectively, of the with active Co2+ ions and a contact time of 120 min. This pH

100

80

60
uptake %

40

20
Al as prepared
Al sulphate 700 °C
Al2O3 900 °C
0 200 400 600 800 1000 1200 1400 1600
Time, min

Fig. 8. Effect of contact time on the adsorption of radioactive Co2+ on the as-synthesized alumina, alumina calcined at 700°C and
alumina calcined at 900°C; adsorbent dosage: 10 g L–1.

100
Alumina/H2SO4
99 Alumina/HCl

98

97
Uptake %

96

95

94

93

92

0 200 400 600 800 1000 1200 1400 1600

Time, min

Fig. 9. Effect of contact time on the adsorption of radioactive Co2+ on alumina/HCl and alumina/H2SO4 from base digestion; adsorbent
dosage: 10 g L–1.
274 M.M.E. Breky et al. / Desalination and Water Treatment 170 (2019) 265–276

range was selected to avoid metal hydrolysis. Figs. 10 and 11 H2SO4 as a function of their concentration ranged from 100
showed the effect of pH on the adsorption of radioactive to 500 mg L–1 at the corresponding optimum pH (pH 4).
Co2+ on the as-synthesized aluminium sulfate, aluminium The equilibrium capacity of Co2+ ions increased as increas-
sulfate calcined at 700°C and alumina calcined at 900°C, ing amounts of metal ions were added. The maximum Co2+
alumina/HCl and alumina/H2SO4 (from base leaching). As adsorption capacity was 193, 180, 197, 296 and 235 mg g–1
expected, higher acidity conditions led to lower adsorption for the as-synthesized alumina, alumina calcined at 700°C,
of metal ions, which may be due to protonation of func- alumina calcined at 900°C, alumina/HCl and alumina/
tional groups. As the pH of the solution increased, adsorp- H2SO4, respectively. This means that the alkaline digestion
tion increased due to deprotonation of functional groups on of AD followed by acidic neutralization (HCl or H2SO4) pro-
all alumina samples. When the pH decreased, competitive vided efficient adsorbents with higher retention capacities
adsorption occurred between H+ ions and the radioactive than that of acidic digestion. Therefore, both alumina/HCl
Co2+ ions in solution. Therefore, the uptake increased as and alumina/H2SO4 could be applied for efficient removal
the pH increased, and the maximum uptake was observed of radio-cobalt ions from radioactive liquid waste.
at pH 4 for radioactive Co2+.
5. Conclusion
4.3. Maximum retention capacity of Co2+
Alumina as useful sorbent material can be recovered
As shown in Fig. 12, the retention capacity of Co2+ ions by from environmental hazard AD by acidic or alkaline diges-
the as-synthesized aluminium sulfate, AS calcined at 700°C, tion process. The process developed for the treatment of AD.
alumina calcined at 900°C, alumina/HCl and alumina/ The treatment dissolution processes by H2SO4 or NaOH

100

80

Aluminum sulphte as-prepared

Aluminum sulphte cakcined at 700
Uptake %

60 Aluminum oxide cakcined at 900

40

20
2 3 4 5 6 7 8
pH

Fig. 10. Effect of pH on the adsorption of radioactive Co2+ on the as-synthesized aluminium sulfate, aluminium sulphate calcined at
700°C and alumina calcined at 900°C; adsorbent dosage: 10 g L–1.

100

90

80

70
Alumina/ H2SO4
Alumina/ HCl
Uptake %

60

50

40

30

20
2 3 4 5 6 7 8
pH

Fig. 11. Effect of pH on the adsorption of radioactive Co2+ on alumina/HCl and alumina/H2SO4 from base digestion; adsorbent
dosage: 10 g L–1.
 M.M.E. Breky et al. / Desalination and Water Treatment 170 (2019) 265–276 275

300

250

200
qe (mg/g)

150

as-synthesized
100 700
900
50 H2SO4
HCl
100 200 300 400 500
Intial Concentration (ppm)

Fig. 12. Sorption isotherm of Co2+ ions on different aluminium samples at pH 4, V/M = 0.1 L g–1.

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