Canadian Metallurgical Quarterly

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THE PRODUCTION OF ACTIVATED ALUMINA FROM

ALUMINUM HYDROXIDE BASED WASTE

M.N. SARIDEDE, Z. ÇİZMECİOĞLU & S. DEĞERLİ

To cite this article: M.N. SARIDEDE, Z. ÇİZMECİOĞLU & S. DEĞERLİ (2005) THE PRODUCTION
OF ACTIVATED ALUMINA FROM ALUMINUM HYDROXIDE BASED WASTE, Canadian Metallurgical
Quarterly, 44:1, 131-136, DOI: 10.1179/cmq.2005.44.1.131

To link to this article: http://dx.doi.org/10.1179/cmq.2005.44.1.131

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Canadian Metallurgical Quarterly, Vol 44, No 1 pp 131-136, 2005

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Published by Canadian Institute of Mining, Metallurgy and Petroleum
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THE PRODUCTION OF ACTIVATED ALUMINA FROM

ALUMINUM HYDROXIDE BASED WASTE
· · ·
M.N. SARIDEDE1, Z. ÇIZMECIOĞLU1 and S. DEĞERLI2
1
Yildiz Technical University, Department of Metallurgical and Materials Engineering
Davutpasa Campus, 34210 Esenler, Istanbul, Turkey
2
Seydişehir Eti Aluminum Works, Seydişehir, Konya, Turkey

(Received in revised form July, 2004)

Downloaded by [Orta Dogu Teknik Universitesi] at 20:17 09 April 2016

Abstract — Activated alumina is a member of a special alumina group and considered to be more valuable
and important than commercial quality alumina. Activated alumina is produced by different methods and
generally used as a desiccant, an adsorbent and a catalyst.
In the present study, the production of activated alumina from aluminum hydroxide based waste was
investigated. This waste was obtained from the Seydişehir Eti Aluminum Works and contained aluminium
hydroxide in high ratio. Three different production methods were employed in the experiments: acid
activation, heat activation and a combination of both these processes. The variables investigated were
particle size range, acid medium (HCl, HNO3, H2SO4), activation temperature and time.
The experimental results showed that aluminum hydroxide based waste could be converted to activated
alumina effectively by using a combination of acid and heat activation processes. Total specific surface area
of the whole sample determines the rate of the reaction for each activation method and thus the particle size
must be lower than a critical value which is determined as 0.4 mm in this study. Optimum production
conditions are determined as HCl-HNO3 solution mixture for acid activation, 390 °C and 1 hour for the heat
activation process.

Résumé — On considère que l’alumine activée, membre d’un groupe particulier d’alumine, a plus de valeur
et est plus importante que l’alumine de qualité commerciale. On produit l’alumine activée par différentes
méthodes et on l’utilise généralement comme dessiccatif, comme agent adsorbant et comme catalyseur.
Dans la présente étude, on a étudié la production d’alumine activée à partir de rejet à base d’hydroxyde
d’aluminium. Ce rejet, obtenu de l’usine d’aluminium de Seydişehir Eti, contenait un rapport élevé
d’hydroxyde d’aluminium. On a employé trois différentes méthodes de production dans les expériences:
activation à l’acide, activation à la chaleur et une combinaison de ces deux traitements. Les variables
étudiées incluaient la gamme de taille de particule, le milieu acide (HCl, HNO3, H2SO4), la température
d’activation et la durée.
Les résultats expérimentaux ont montré que l’on pouvait convertir efficacement le rejet à base
d’hydroxyde d’aluminium en alumine activée en utilisant une combinaison de traitements d’activation à
l’acide et à la chaleur. La surface spécifique totale de l’échantillon entier détermine le taux de réaction pour
chaque méthode d’activation. Ainsi, la taille de particule doit être plus petite qu’une certaine valeur critique,
déterminée dans cette étude comme étant 0.4 mm. On a déterminé que les conditions optimales de
production consistaient en une solution mélangée d’HCl-HNO3 pour l’activation à l’acide et en une
température de 390 °C et 1 heure pour le traitement d’activation à la chaleur.

INTRODUCTION
Activated alumina is a common name for aluminum
hydroxide heat treated at a temperature under 1000 °C. It
is in the group of special alumina. The most important
and vast use of the activated alumina is as a desiccant, an
adsorbent and a catalyst. It is a more effective moisture
desiccant than calcium cloride and silica gel and reduces
moisture in gases to ppm level. Also, activated alumina is
used to absorb the flourine on fluosilicate acid which is
used to remove micro-organisms in drinking water. Also
it is used to adsorb phosphate, arsenic, anionic dyes, col-
loidal silica, mercury, selenium and other metals in waste
water [1-12].

CANADIAN METALLURGICAL QUARTERLY, VOL 44, NO 1

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132 M.N. SARIDEDE, Z. ÇIZMECIOĞLU and S. DEĞERLI
Activated alumina is produced by different methods
depending on the application. Generally, the following
steps are carried out to produce activated alumina:
1. Production of aluminum hydroxide (a-trihydrate, gibb-
site, alumogel and amorphic etc.)
2. Preshaping (depending on area used)
3. Heat treatment
4. Final shaping (if necessary) [13].
Activated alumina has chemically bonded water in dif-
ferent ratios (0<n<0.6) depending on the temperature of the
heat treatment. This product is supplied as a powder, a
granule or porous hard spheres [14]. It has a low chemical
capacity and a high capacity for moisture absorption. The
factors that affect these properties are the crystal structure
of the product (a, t alumina), pore shape and specific sur-
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face area.
Yoldas [15] disclosed a transparent activated nonpartic-
ulate alumina and a method of preparation. In the pyrolyz-
ing step, most of the weight loss occurred at a temperature
range of 375 to 475 °C. The resultant solid product was
transparent and activated. The nonparticulate product had
about 63% pore capacity.
In the patent of Vorobiev et al. [16], the method of
preparing granulated activated alumina is based on the
decomposition of alumina trihydrate by bringing it in con-
tact with the bed of a solid heat carrier over a temperature
range of 350 to 600 °C. After mixing with water and
hydrating, the decomposition product is treated with an
acid. Dried and calcined activated alumina has the specific
surface area of 200 to 400 m2/g, the total pore capacity of
0.45 to 0.90 cc/g and various pore structures.
Goodboy [17] activated the sized alumina particles by
exposure to relatively high temperatures of higher than
300 °C. After agglomeration, ageing and activation at rela-
tively high temperatures starting from 350 to 900 °C, the
activated alumina catalyst was produced which had a spe-
cific surface area greater than 100 m2/g (BET- Brunauer-
Emmett-Teller).
Table I – Particle size analysis of the aluminum hydroxide based waste after crushing
Sıze range (mm) +5 -5+3 -3+1 -1+0.4
% 30.1 16.9 14.1 19.2
Table II – Chemical composition of the aluminum hydroxide based waste
Element Al(OH)3 Fe2O3 SiO2 TiO2
% 97.51 1.13 0.44 0.005
CANADIAN METALLURGICAL QUARTERLY, VOL 44, NO 1
·
A method for producing activated alumina catalyst was
given by Rendall et al. [18]. This method is capable of pro-
ducing activated alumina with specific surface areas
exceeding 120 m2/g (BET) and possessing highly active
acid sites and convenient to be used as a catalyst.
In this study, the production of activated alumina from
aluminum hydroxide based waste generated in Seydişehir
Eti Aluminum Work (Turkey) was investigated.
EXPERIMENTAL PROCEDURE
Raw Materials
Aluminum hydroxide based waste was received from the
hydrate precipitator (crystallizer) in the Seydişehir Eti
Aluminum Works which produces alumina of metallurgical
grade by the Bayer process. The hydrate precipitator has
the dimensions of 15 m in diameter and 30 m in height. A
layer 0.5 to 1 m in thickness is accumulated in the inner
surface of hydrate precipitator over a period of time. This
waste layer cannot be recycled and is transferred to a red
mud dam as a waste.
Pre-research had been done by Yüzer et al. [1] on the
activated alumina production from an aluminum hydroxide
crust, but it was not developed.
In this study, firstly, the characterization of the waste
was conducted by chemical analysis, X-ray diffraction and
differential thermal analysis and thermogravimetric analy-
sis (DTA-TG analysis). Secondly, samples of the waste
were crushed and screened. Acid activation with different
acids and heat activation at different temperatures and for
various time periods were done for different particle sizes.
Lastly, the characterization study was carried out on acti-
vated alumina samples.
In the crushing operation, the representative sample of
40 kg of aluminum hydroxide based waste was crushed to
less than 5 mm by a jaw crusher. Later, the sample was
crushed to thinner sizes and screened from sieves of 5, 3, 1,
-0.4+0.2 -0.2+0.1 -0.1+0.05 -0.05
7.5 4.6 4.1 3.5
Na2O Moisture (110 °C) LOI (1100 °C)
0.31 10.50 34.67
 THE PRODUCTION OF ACTIVATED ALUMINA FROM ALUMINIUM HYDROXIDE BASED WASTE 133

0.4, 0.2, 0.1 and 0.05 mm. Size range analysis of waste
sample was given in Table I. The waste had the chemical
composition as shown in Table II. The chemical analysis
showed that the waste contained mainly Al2O3. An X-ray
diffraction pattern of the as-received waste is shown in
Figure 1. The pattern was taken in Siemens 92D5000. It
shows that gibbsite (Al(OH)3) is the most predominant
phase. Other compounds could not be determined exactly
because of the high peak level (%300) of gibbsite. The
compounds in Table II were then used to aid the identifica-
tion of XRD peaks. It was more probable that the other
peaks were Fe2O3, SiO2 and Na2O.

A Rigaku thermal analyser Ver. 2.22 E2 was used for the

DTA-TG analysis of the waste sample. The result is shown Fig. 2. DTA-TG analysis of the waste sample.
in Figure 2. Two endothermic reaction peaks are revealed.
The weight loss obtained in the big peak at 341.8 °C is
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about 26%. At the small peak, the weight loss obtained is
about 5%.
Activation
In the activation experiments, two methods were used: acid
activation and heat activation. In the acid activation process,
samples with different particle sizes (-1+0.4, -0.2+0.1 and
-0.1+0.05 mm) were activated by using different acids
(HNO3, HCl and H2SO4) and mixtures of them. The con-
centration of acids was 1 M. Purities of HNO3, HCl and
H2SO4 were 65%, 37% and 95%, respectively. Densities of
HNO3, HCl and H2SO4 were 1.41, 1.19 and 1.84 g/L,
respectively. Mixing ratio of acids was given in volumetric
scale. The flow sheet of acid activation process is given in
Figure 3.
Heat activation experiments were done either with acid
activation or without acid activation at different tempera-
tures. The samples were activated at temperatures of 300,
390, 500, 560 and 600 °C. At the selected temperatures, the
extension times were 1, 2, 3 and 4 hours.
Measurements of specific surface area of activated alu-
mina obtained from activation processes were carried out

Fig. 1. XRD pattern of the aluminum hydroxide based waste. Fig. 3. Process steps of the acid activation.

CANADIAN METALLURGICAL QUARTERLY, VOL 44, NO 1

 · · ·
134 M.N. SARIDEDE, Z. ÇIZMECIOĞLU and S. DEĞERLI

by Quantachrome specific surface area measurement ter result was obtained at 500 °C for 2 hours than at 600 °C
equipment that works according to the BET theory. for 1 hour. At higher temperatures, smaller particles tend to
Scanning electron microscopy (SEM) analysis was per- coalesce at contact points and coarser particles were
formed using JEOL JSM 5410 LV. formed and thus less specific surface area is obtained.

Like the previous experiments, specific surface area

RESULTS AND DISCUSSION
Acid Activation
The results for the acid activation experiments of aluminum
hydroxide waste are shown in Table III. It can be seen that
decreasing the particle size resulted in significant improve-
ments in the specific surface area of samples. Also, the spe-
cific surface area increased with the temperature of the acid
medium. Also, using HCl and HNO3 mixtures contributed to
the increase of activated surfaces. On the contrary, no surface
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increased with decreasing size. It is expected that a smaller
size of the sample would give a larger specific surface area
when it is activated by acid or heat activation.
Combination of Acid and Heat Treatment Processes
The combination process included heat activation after acid
activation. The experimental data for the effect of particle
size, acid type and heat activation temperatures on the spe-
cific surface area of samples are shown in Figures 4 and 5.

development was obtained when H2SO4 was used with HCl.
Heat Activation
The results obtained from heat activation experiments
showed that time has no significance in the heat activation
process at a relatively low temperature (390 °C). Specific
surface area of the particle size ranging between -0.4 + 0.2
mm was determined as 149 m2/g for 1 hour and 160 m2/g
for 2 hours. Specific surface area for -0.1 + 0.05 mm parti-
cle size range was measured as 225 m2/g and 215 m2/g for
1 and 2 hours, respectively. These results showed that the
time of 1 hour is enough for activation. Table IV gives the
effect of the relatively high temperature on the specific sur-
face area. Time has more importance than temperature for
activation at a higher temperature. It can be seen that a bet-
According to Figures 4 and 5, the activated specific surface
area increased with a decreasing particle size in both the
HCl-HNO3 solution and H2SO4. The characteristics of the
curves showed that the specific surface area increased up to
the temperature of 390 °C. After this temperature, it
decreased slowly. The characteristic of decrease was the
same for all sizes. The highest specific surface area was 211
m2/g for the site average of -0.4 t +0.2 mm at 390 °C for 1
hour when a HNO3-HCl solution was used. Under the same
conditions, the specific surface area obtained in HCl-HNO3
solution was higher than H2SO4 at each temperature stage
and for each particle size.
SEM analyses of the activated samples were shown in
Figures 6 and 7. Figure 6 clearly shows the cracks, broken
surfaces and deterioration of particles when the heat acti-

Table III – Specific surface area of samples after acid activation.

No. Size range (mm) Acid activation Surface area (m2/g)

1 +5 HNO3, Room temp. 10

2 HCl, 90 °C 40
3 -1+0.4 HNO3/HCl=1/5*, 90 °C 75
4 HCl/H2SO4=1/6*, 90 °C No surface development
5 HCl, 90 °C 45
6 -0.2+0.1 HNO3/HCl=1/5*, 90 °C 85
7 HCl/H2SO4=1/6*, 90 °C No surface development
*Volumetric ratio
Table IV – Summary of heat activation results at elevated temperatures.

No Size range (mm) Heat activation Surface area (m2/g)

1 -6+5 600 °C, 1h No surface development

2 600 °C, 1h 167
-1+0.4
3 500 °C, 2h 188
5 -0.2+0.1 600 °C, 1h 178
6 500 °C, 2h 205

CANADIAN METALLURGICAL QUARTERLY, VOL 44, NO 1

 THE PRODUCTION OF ACTIVATED ALUMINA FROM ALUMINIUM HYDROXIDE BASED WASTE
Fig. 4. Effect of heat activation temperature for 1 hour and particle size
on the specific surface area after acid activation in HNO3-HCl solution.
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vation was performed at 390 °C for 1 hour for a sample of
-0.1 + 0.05 mm. Figure 7 also shows the effect of the com-
bination process of acid and heat activation. After the sam-
ples were activated in a HCl-HNO3 solution, heat activation
was carried out at 500 °C for a period of 2 hours. The effect
of acids is clearly seen in that deeper cracks and deteriora-
tion were formed. When the heat activation was applied
after acid activation, more porosity and deeper cracks
appeared.
X-ray analysis of samples which were obtained from
acid and heat activation process were performed, but the
phases were not identified precisely.
Comparison of Activation Processes
Figure 8 provides a direct comparison of acid and heat acti-
vation methods in this study. The specific surface area is
Fig. 6. Example of particle morphology in the heat activated sample in
the size range of –0.1 +0.05 mm. Heat activation conditions are 390 °C for
1 hour.
135
Fig. 5. Effect of heat activation temperature for 1 hour and particle size
on the specific surface area after acid activation in H2SO4.
plotted as a function of processes which were carried out
with different parameters for a size of -0.4 +0.2 mm. Figure
8 indicates that the specific surface area reaches a maxi-
mum level of 211 m2/g in a combination of an acid and heat
activation process. The conditions of the process with max-
imum specific surface area were as follows: HCl-HNO3
solution for acid activation, 390 °C and 1 hour for heat acti-
vation.
The highest specific surface area was obtained at 390 °C
for both the heat activation process and the heat activation
after acid activation processes. This result is due to exceed-
ing the phase transformation temperature which was given
as 341.8 °C in the DTA-TG analysis in Figure 1. The phase
transformation was realized at this temperature as Al(OH)3-
gAl2O3. Thus, the specific surface area increased. The max-
imum specific surface area of 211 m2/g obtained from this
study is sufficient for most industrial applications.
Fig. 7. The particle morphology of heat and acid activated sample of
-0.2 +0.1 mm. Heat activation was carried out at 500 °C for 2 hours fol-
lowing acid activation in HCl-HNO3 solution.
CANADIAN METALLURGICAL QUARTERLY, VOL 44, NO 1
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136 M.N. SARIDEDE, Z. ÇIZMECIOĞLU and S. DEĞERLI
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Fig. 8. Comparison of the results derived from various activation
processes (AAc: Acid Activation, HAc: Heat Activation).
CONCLUSIONS
From the above results, the following conclusions can be
drawn:
1. In the acid activation process, HCl with HNO3 was
found to be a more effective reagent than a HCl and HCl-
H2SO4 mixture.
2. Acid activation can not give enough specific surface
area by itself for industrial application.
3. The smaller original size resulted in a larger specific
surface area. A 0.4 mm particle size is the maximum to
obtain a sufficient specific surface area.
4. In the heat activation process phase transformation tem-
perature of about 342 °C had to be exceeded, but higher
temperatures over 500 °C must not be employed.
5. Optimal activation process conditions are as follows:
acid activation in HCl-HNO3 solution, then heat activation
at 390 °C for 1 hour.
CANADIAN METALLURGICAL QUARTERLY, VOL 44, NO 1
·
ACKNOWLEDGEMENTS
The authors would like to thank the Seydişehir Eti
Aluminum Works for providing samples and information
pertaining to the operation. The authors also wish to thank
the Head of the Department of Metallurgical and Materials
Engineering, Yildiz Technical University, for providing the
experimental facilities.
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