Journal of Crystal Growth 373 (2013) 8891

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Journal of Crystal Growth

journal homepage: www.elsevier.com/locate/jcrysgro

Purification of Al(OH)3 synthesized by Bayer process for preparation

of high purity alumina as sapphire raw material
No-Kuk Park a, Hee-Young Choi a, Do-Hyeong Kim a, Tae Jin Lee a,n, Misook Kang b,
Won Gun Lee c, Heun Duk Kim c, Joon Woo Park c
a

School of Chemical Engineering, Yeungnam University, 214-1 Daedong, Gyeongsan, Gyeongbuk 712-749, Korea
Department of Chemistry, Yeungnam University, 214-1 Daedong, Gyeongsan, Gyeongbuk 712-749, Korea
c
TPS Inc., 193 Galsan-dong, Dalseo-gu, Daegu 704-900, Korea
b

a r t i c l e i n f o

a b s t r a c t

Available online 10 December 2012

To produce high purity alumina as the raw material for sapphire growth, gibbsite, which is the
precursor for the synthesis of alumina, was synthesized by the Bayer process, and treated with an acid
solution to remove the sodium component. In this study, the digestion process was carried out under
the following conditions: an Al/Na ratio of 0.9 with a 5 N NaOH solution and a temperature of 140 1C.
Bauxite containing 75 wt% alumina was converted to a sodium aluminate solution, and 60 wt% of the
dissolved aluminate was crystallized to gibbsite. The sodium content in the gibbsite, which was
measured by inductively coupled plasma/optical emission spectroscopy, was reduced by approximately
5700 ppm and below 2900 ppm after the water washing and acid treatments, respectively. The sodium
content decreased with increasing acid concentration in the solution, temperature and acid
treatment time.
& 2012 Elsevier B.V. All rights reserved.

Keywords:
A1. Purification
A2. Industrial crystallization
B2. Semiconducting aluminum compounds
B3. Light emitting diodes

1. Introduction
Alumina (Al2O3) is used widely in many industrial fields, such
as in thermal processes, electrical processes, semi-conductors,
ceramic processes, catalytic process, etc., on account of its high
thermal stability, high electric resistance, high porous structure
and catalytic activity. Alumina can be prepared by a range of
synthesis methods. The Bayer process is used commercially for
the large scale production of alumina. Recently, alumina as a
substrate material for LEDs (light emitting diodes), which is high
efficiency illumination, has been used to grow sapphire ingots.
High purity sapphire is used as a substrate material in LEDs. High
purity alumina must be used as the raw material for the growth of
sapphires to reduce the lattice defects in single crystal sapphires.
Because the aluminum component in bauxite is digested in a 5 N
sodium hydroxide solution, the purity of alumina produced by the
Bayer process is approximately 99.8% with the remainder Na2O.
Therefore, the sodium contained in alumina must be removed to
allow the growth of sapphire. The commercial Bayer process
consists of an aluminum digestion process, separation process
for red mud, crystallization process for gibbsite, water washing
process for purification, and a calcination process to produce
alumina [19]. The water washing process is needed to remove

Corresponding author. Fax: 82 53 810 4631.

E-mail address: tjlee@ynu.ac.kr (T.J. Lee).

0022-0248/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jcrysgro.2012.12.004

the residual sodium contained in gibbsite obtained from the

crystallization process. Nevertheless, a few thousand parts per
million of sodium remains in gibbsite after water washing [10].
Therefore, in the present study, an acid treatment process was
applied to high purity Bayer gibbsite, and the effects of the acid
concentration, temperature of the acid solution and the acid
treatment time were investigated.

2. Experiments
2.1. Materials and agents
The bauxite (alumina content !5459 wt%) used as the raw
material in the Bayer process for the synthesis of alumina was
obtained from a mine at Weipa in Queensland, Australia. The
bauxite ores were crushed to a particle size of o10 mm using an
attrition mill. Table 1 lists the composition of bauxite supplied
from the support company. A 5 N sodium hydroxide solution was
used for the digestion of alumina from bauxite. Aluminum
hydroxide powder (Al(OH)3, Aldrich) was used as the seed
material for the crystallization of gibbsite(Al(OH)3) from the
sodium aluminate solution. A 17.3 N acetic acid (CH3COOH,
Aldrich) solution was used as the acid solution for the acid
treatment process due to its low price and because it is a
relatively weak acid, and thus does not dissolve gibbsite.

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N.-K. Park et al. / Journal of Crystal Growth 373 (2013) 8891

Table 1
Composition of the bauxite mined in Queensland
of Australia.
Compounds

Composition (wt%)

Al2O3
SiO2
Fe2O3
TiO2
L.O.I

53
7
13
3
24

The solution was diluted to 5.8, 7.0, 8.7, and 10 N to examine the
effect of the acid concentration.
2.2. Synthesis of gibbsite by Bayer process
An autoclave with a 500 ml volume was used to digest the
aluminum component from the bauxite powder. Bauxite powder
and the sodium hydroxide solution were mixed to give Al2O3/
Na2O ratio of 0.9. The solidliquid reaction between the bauxite
powder and sodium hydroxide solution was carried out at 140 1C
for 1.5 h in the autoclave reactor. The pressure in the autoclave
was maintained at 3.4 atm, which corresponds to the vapor
pressure at 140 1C. The red mud of solid phase remaining after
the digestion process was removed by filtering through filter
paper, and the separated liquid sample was used for the crystallization of gibbsite. Aluminum hydroxide powder (48.86 g) was
added as a seed material to the filtrate. This mixture solution was
stirred vigorously for 1.5 h at 80 1C and the seed material was
removed by filtration through a filter paper. The seed material
added for gibbsite crystallization removed approximately 70 wt%
of the Al component contained in the sodium aluminate solution.
After filtering the seed material, the sodium aluminate solution
was left to stand for 48 h at 50 1C. The gibbsite powder grown
during the crystallization process was washed 5 times and dried
using a rotary vacuum evaporator. As gibbsite crystallization is a
very slow process, the seed material was filtered after contact for
1.5 h to separate the pure gibbsite produced by crystallization.
2.3. Purification of Al(OH)3 by acid treatment
The gibbsite synthesized by the Bayer process in this study
was treated with acid solution to reduce the small Na contaminant. Acetic acid diluted to 5.8, 7.0, 8.7, and 10 N was used as the
acid solution. The mass of gibbsite and the volume of the acetic
acid solution used for the acid treatment process were 20 g and
480 ml, respectively. The temperature of the acetic acid solution
for the acid treatment process was controlled to 2580 1C using a
heating mantle. The change in the sodium content contained in
the gibbsite was investigated as a function of the acid treatment
time at 80 1C and the sodium content was analyzed by inductively
coupled plasma/optical emission spectroscopy (ICP-OES, Perkin
Elmer, Optima 2100 DV). The change in pH in the acetic acid
solution was also measured during the acid treatment process.

The solid sample separated by filtration is called red mud and the
aluminum content digested from bauxite was calculated by
subtraction of the content of aluminum contained in the red
mud from that contained in the original bauxite. Table 2 lists the
element compositions of bauxite and red mud analyzed by energy
dispersive X-ray spectroscopy (EDX, HITACHI, S-4200). 72 wt% of
the alumina contained in bauxite had been digested with the
sodium hydroxide solution.
The sodium aluminate solution obtained after the digestion
process was maintained at 80 1C on a heating mantle, and was
mixed with Al(OH)3 seeding powder for 1.5 h. The sodium
aluminate solution was then separated from the seed material
and left to stand in a heating oven at 50 1C for 48 h. The gibbsite
produced by the crystallization process was 460 wt% and
approximately 80 wt% of the aluminum contained in the sodium
aluminate solution had crystallized to gibbsite fine powder after
12 and 48 h, respectively. The color of the gibbsite produced by
the crystallization was a light brown. This was changed to white
after washing five times with distilled water due to removal of the
iron component. The XRD pattern of the white sample analyzed
by the X-ray diffractometer (XRD, PANalytical, MPD for Bulk
(powder)) revealed the typical pattern of gibbsite, as shown in
Fig. 1. The sodium content in gibbsite powder after water washing
was approximately 5700 ppm, which corresponds to 0.29% Na2O,
and is similar to the content of Na2O contained in commercial
Bayer alumina.
3.2. Acid treatment of gibbsite
An acid treatment process was carried out to remove the
sodium component contained in gibbsite produced by the Bayer
process because sodium as an impurity produces crystal defects
during sapphire growth. The removal efficiency was investigated
according to the concentration of the acetic acid solution, temperature and acid treatment time, respectively.
To examine the effect of the acid concentration, the acid
treatments were carried out using 5.8, 7, 8.7 and 10 N acetic acid
at room temperature for 12 h. Table 3 lists the sodium content in
the gibbsite samples after the acid treatment, as measured by ICPOES. On the other hand, the acid concentration had some effect, as
shown in Table 3. This shows that the removal of sodium by the
acid treatment is dependent to some extent on the concentration
of the acid solution in the high concentration range.
To investigate the effect of temperature for the purification of
gibbsite, the temperature was controlled to 40, 50, 60, 70 and 80 1C
during the acid treatment process. The concentration of the acetic
acid solution was fixed at 7 N because a change in pH can affect the
behavior of the solidliquid reaction system. Therefore, the change
in pH in the solution was observed for the initial 3.5 h (Fig. 2).
Table 2
Composition of bauxite and red mud after the digestion process according to EDX
analysis.
Elements Bauxite
Weight
%

Atomic
%

Wt%

Weight
%

Atomic
%

Al

19.35

12.88

11.71

8.41

Na
Si
Ti
Fe

2.37
1.13
7.09

1.52
0.42
2.28

68.32
(Al2O3)

4.37 (SiO2)
3.52 (TiO2)
18.86
(Fe2O3)

8.60
4.82
2.02
13.75

7.25
3.32
0.82
4.77

3. Results and discussion

3.1. Digestion of aluminum component
In this study, the aluminum contained in bauxite was dissolved in the 5 N sodium hydroxide solution to form sodium
aluminate, and the gibbsite powder was obtained from the
sodium aluminate solution during the crystallization step.
The slurry phase was cooled to 80 1C after the digestion process
and filtered to separate the solid and liquid samples by filtration.

Red mud

Weight of bauxite
digestion 33.18 g.

before

digestion 66.6 g;

weight

Wt%

31.9 (Al2O3)
16.70
18.07
5.00
28.33

of

red

(Na2O)
(SiO2)
(TiO2)
(Fe2O3)

mud

after

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N.-K. Park et al. / Journal of Crystal Growth 373 (2013) 8891

Table 4
Na and Na2O contents in gibbsite with temperature at an acetic acid solution
concentration of 7 N.
Temperature
(1C)

Content of Na
(ppm)

Content of Na2O
(wt%)

Removing efficiency
(%)

40
50
60
70
80

2440
2333
1844
1767
1423

0.122
0.117
0.092
0.088
0.071

57.2
59.1
67.7
69.0
75.0

Fig. 1. XRD pattern of gibbsite synthesized by the Bayer process.

Table 3
Na and Na2O contents in gibbsite with acid concentration in the acid treatment at
room temperature.
Concentration of acetic acid
solution (N)

Na
(ppm)

Na2O
(wt%)

Removing efficiency
(%)

5.8
7.0
8.7
10

2980
2716
2511
1867

0.149
0.136
0.126
0.093

47.7
52.4
55.9
67.2

Fig. 3. Change in the pH of the acid solution with acid treating time in a 7 N acetic
acid solution at 80 1C for 5, 12, 25 and 50 h.

the gibbsite washed with distilled water had been removed at

80 1C for 12 h.
To examine the effect of the reaction time, the acid treatment
of the gibbsite powder was carried out at 80 1C for 5, 12, 25 and
50 h, successively. The concentration of the acetic acid solution in
these experiments was 7 N. Fig. 3 also shows the change in pH of
the acetic acid solution. The change in pH in the 4 experiments
performed for different times showed a similar trend, and reached
dpH/dt 0 after 20 h. However, the Na content in gibbsite
measured by ICP-OES decreased with time on stream, as shown
in Table 5. It was concluded that the decrease of pH after 20 h
investigated in Fig. 3 occurred by the increasing hydrogen ions
contained in acetic acid solution due to the evaporation of
moisture heated during the acid treatment. Therefore, it was
confirmed that Na in gibbsite is quickly removed with the acid
treating process approximately 20 h after reaction start.
Fig. 2. Changing pH of the acid solution for the initial time with temperature in
the acid treatment with a 7 N acetic acid solution.

The pH of the acetic acid solution increased with time on stream

and the slope of the pHtime curves increased with increasing
temperature, indicating a temperature dependency in the process.
The change in the Na content was confirmed by ICP-OES, as
shown in Table 4. The removal efficiency of sodium was approximately 57% when gibbsite washed with distilled water was
treated with the acetic acid solution at 40 1C for 12 h, and the
Na2O content remaining after the acid treatment was 0.12 wt%.
When gibbsite was treated with the acetic acid solution at 80 1C,
the Na content analyzed by ICP-OES was 1423 ppm, which
corresponded to 0.071 wt% Na2O. Therefore, 75 wt% of the Na in

3.3. SEM and XPS analyses

The gibbsite washed with water and acetic acid solution was
observed by a scanning electron microscope (SEM, HITACHI, S-4200).
Large crystals, 420 mm in size, which were agglomerates of hexagonal gibbsite, were observed in the gibbsite washed with distilled
water, as shown in Fig. 4(a). These were not observed after the acid
treatment of gibbsite, as shown in Fig. 4(b). The gibbsite structure was
well dispersed with a crystal size of 24 mm due to the removal of
impurities such as Na2O by the acid treatment.
X-ray photoelectron spectroscopy (XPS,ULVAC-PHI, Quantera
SXM) was carried out on the same samples to determine the Na
content on the gibbsite surface (Fig. 5). Two peaks for Na 1s were
confirmed at a binding energies of 1701.6 eV and 1702.5 eV.

N.-K. Park et al. / Journal of Crystal Growth 373 (2013) 8891

91

Table 5
Na and Na2O contents in gibbsite with acid treating time at an acetic acid solution
concentration of 7 N at 80 1C.
Time (h) Content of Na (ppm) Content of Na2O (%) Removing efficiency (%)
5
12
25
50

2706
1423
637
254

0.135
0.071
0.032
0.013

52.5
75.0
88.8
95.5

Fig. 5. XPS binding energy of Na 1s contained in gibbsite (a) before and (b) after
the acid treatments in a 7 N acetic acid solution at 80 1C.

The low effect of the concentration of the acid solution was confirmed
from the experimental results. The removal rate of sodium showed a
temperature dependence. The removal content of sodium on gibbsite
also increased with time on stream for the acid treatment process. In
this study, the sodium content on gibbsite synthesized by the Bayer
process after the acid treatment for 50 h at 80 1C was 0.013 wt%,
which approaches the usable grade for the growth of sapphire. Na in
gibbsite was quickly removed with the acid treating process approximately 20 h after the reaction start. However, the acid treating rate is
rapidly reduced after 20 h for the acid treatment. Therefore, it was
concluded that Na contained in gibbsite synthesized by the Bayer
process is removed with multi-stage acid treatment to 20 h at high
temperature and high concentration acetic acid in order to obtain
high purity gibbsite.

Acknowledgments
This study was financially supported by the Ministry of
Education, Science Technology (MEST) and National Research
Foundation of Korea (NRF) through the Human Resource Training
Project for Regional Innovation.
Fig. 4. SEM images of gibbsite (a) before and (b) after the acid treatments in a 7 N
acetic acid solution at 80 1C.

The strong peak of 1701.6 eV revealed the presence of Na in the

lattice of the metal oxide, such as zeolite. The peak at 1702 eVwas
assigned to the Na 1s binding energy in the form of Na2O.
Na2O can produce sodium acetate (CH3COONa) and H2O by a
reaction with the acetic acid solution, and the sodium in the lattice
of the crystal can be replaced with H ions from acetic acid through
the exchange of cations between Na and H ions. The peak
intensity of Na 1s in gibbsite was reduced remarkably after the acid
treatment, as shown in Fig. 5. The sodium exists in the lattice of
gibbsite and as Na2O, and can be removed by ion exchange.
4. Conclusion
The sodium component contained in gibbsite (Al(OH)3) synthesized by the Bayer process was removed by an acid treatment process
to use high purity gibbsite as the raw material for the growth of
sapphires. An acetic acid solution was used for the acid treatment of
gibbsite and the removal of sodium was investigated according to
the change in acid concentration, temperature and treatment time.

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