INDONESIAN MINING JOURNAL Vol. 13, No.

1, February 2010 : 16 - 25

EXTRACTION OF ALUMINA FROM BAUXITE RESIDUE

FOR PREPARATION OF ALUMS AND
POLY ALUMINUM CHLORIDE

MUCHTAR AZIZ and AGUS WAHYUDI

R&D Centre for Mineral and Coal Technology
Jalan Jenderal Sudirman No. 623 Bandung 40211,
Ph. 022 6030483, fax. 022 6003373
e-mail: [email protected]

ABSTRACT

The chemical composition of West Kalimantan bauxite is 45 pct Al2O3 and 16 pct Fe2O3 that has been
extracted to produce alumina and bauxite residue (red mud). The residues contains Al2O3 20 pct and Fe2O3
about 37 pct, wich was furthermore processed by roasting or lime-soda sinterization at temperature of 800-
1100°C. The sintered product was leached with sodium carbonate solution to produce soluble sodium
aluminate (2NaAlO2). The solution obtained was then precipitated to produce hydrated alumina (Al(OH)3.
Hydrated alumina was then sulfateized by adding ammonium hydroxide, and followed by crystallization to
produce high purity of ammonium aluminum sulfate crystals (alums). In addition, hydrated alumina was
also chlorinated in stoichiometric amount at mol ratio of OH/Al = 0.5 – 1.5 to form polyaluminum chloride
(PAC). The residue obtained from leaching was concentrated by 1000 gauss of magnetic separator to
produce iron concentrate as a by product. As the results, sulfatation of hydrated alumina with addition of
ammonium hydroxide results high grade of ammonium aluminum sulfate (NH 4Al(SO4)2 .12H2O) crystals.
Chlorination of hydrated alumina in stoichiometric amount at mol ratio of OH/Al = 1.0 results polyaluminum
chloride (PAC) that quality is adjacent to the first type of PAC. Through the soda-lime sinter process, it can
also produce iron concentrate having grade of 66 % Fe2O3 with 40 % of recovery.

Keywords : bauxite residue, lime-soda sinter process, hydrated alumina, alums, PAC.

INTRODUCTION tering to the red mud with soda-lime at 800-1200OC

resulting sintered sodium aluminate solution
Indonesia has potential bauxite resources, espe- (2NaAlO2). Separation of sodium aluminate solu-
cially in West Kalimantan, Bintan island and sur- tion from residue followed by precipitation of so-
rounding of the area. West Kalimantan bauxite ore dium aluminate solution result hydrated alumina
contains main compounds of Al-2O3 44,79 %, (Al(OH)3). Hydrated alumina can be used as a raw
Fe2O3 15,76 %, SiO2 1,56 % and TiO2 1,11 %. material (aluminum resources) for alums and
The processing of bauxite (Bayer Process) has polyaluminum chloride (PAC). Then the residue of
been applied in producing alumina, however, the solution can be concentrated by magnetic sepa-
bauxite residue still contains significant Al2O3 20 rator to result iron concentrate as a by product.
% and Fe2O3 37 %.
The aim of this research is to produce hydrated
Many ways have been tried and keep being devel- alumina from West Kalimantan bauxite residue by
oped for reusing bauxite residue by many coun- soda-lime sintering process as raw materials for
tries which have alumina industries, one is Aus- making alums and poly aluminum chloride (PAC).
tralia. In Australia, it is not less than 30 million It also results iron concentrate from residue of
ton of bauxite residue accumulates every year leaching as a by product. Alums and PAC was
(40% from world production) [Sharif, 2005]. selected because these products are currently
required for water treatment. As known that the
Research on extraction of alumina (Al2O3) from community is often difficult to obtain clear water
West Kalimantan bauxite residue was done by in dry season. Besides alums, Indonesia still im-
soda-lime sintering process that consists of sin- ports PAC (in the form of hydrated alumina).

16 Received : 25 November 2009, first revision : 19 January 2010, second revision : 02 February 2010, accepted : February 2010
 Extraction of Alumina from Bauxite Residue for Preparation ... Muchtar Aziz and Agus Wahyudi

FUNDAMENTAL - Sinter Leaching

Leaching of the sinter with sodium carbonate
Alumina solution causes calsium aluminate to react
with sodium carbonate to form sodium alumi-
- Alumina from aluminosilicate minerals nate and solid residue of calsium carbonate
Padilla (1985) and Alp (2002) used lime-soda (CaCO3). [Habashi, 1997] :
sinter process method to get alumina from alu-
minosilicate materials. In this process, alumi- 3CaO.Al2O3 + 3Na2CO3 + H2O J 2NaAlO2 +
nosilicate was reacted with lime (CaO) or cal- 4NaOH + 3CaCO3 ................................................ (6)
cium carbonate (CaCO3) and sodium carbon-
ate (Na2 CO3 ) at high temperature (800- Aluminum Sulfate Forming
1200 O C) to form sodium aluminate
(Na2O.Al2O3 or 2NaAlO2) that is soluble in Sulfatation of aluminum hydrate results aluminum
alkaline solution (Na2CO3 or NaOH) and to form sulfate, and sulfatation with adding ammonium
dicalsium silicate (Ca2SiO4 ) which is not hydroxide results ammonium aluminum sulfate.
soluble in alkaline solution.
Al(OH)3 + H2SO4 + H2O J Al2(SO)3.18H2O + H2O
The sintering reaction of clay materials can ...................................................................... (7)
be stated as below [Padilla, 1985] :
Al(OH)3 + H2SO4 + H2O + NH4OH J
Al2Si2O7 + Na2CO3 + 4CaCO3 J 2NaAlO2 + NH4Al(SO4)2.12H2O + H2O ............................ (8)
2Ca2SiO4 + 5CO2 ................................................ (1)
Ammonium aluminum sulfate solution can be crys-
- Alumina from aluminous ores and bauxite resi- tallized in room temperature.
due
Aluminous ores (Al2O3) was reacted with
Na2CO3 at temperature about 1000OC to form PAC FORMING
sodium aluminate. SiO2 in aluminous ores
causes sodium carbonate to react with SiO2 The mechanism of forming Poly Aluminum Chlo-
during sintering process to form dissolved so- ride (PAC) can be explained by the reaction of
dium silicate (Na2SiO3). The equation for that AlCl3 (aluminum chlorides) with Al(OH)3 at mol
reaction [Habashi, 1997] : ratio of OH/Al = 0.5 – 1.5 (Magnus, 1990). Alumi-
num chlorides are resulted through chlorination of
Al2O3 + Na2CO3 J 2NaAlO2 + CO2 ........... (2) Al(OH)3. Furthermore, the reaction of AlCl3 with
Al(OH)3 proceeds like ‘polymerization’ to form ‘poly
SiO2 + Na2CO3 J Na2SiO3 + CO2 .............. (3) aluminum chlorides’.

If sintered feed is added with CaO, sodium EXPERIMENTAL

silicate will react with CaO and Al2O3 to form
soluble sodium aluminate compound and Red mud from bauxite processing residue was
unsoluble dicalsium silicate. The reaction is prepared and mixed with CaO and Na2CO3 both
[Padilla, 1985] : in stoichiometric amount of 10 % excessive, it was
formed as pellets and need to be dried. Sintering
Na2SiO3 + 2CaO + Al2O 3 J 2 NaAlO2 + of the dried pellet was done at variation of the tem-
Ca2SiO4 .................................................................... (4) perature of 800 - 1100 OC. Sintered product was
leached in 2 % wt. of sodium carbonate solution
Calcium can replace sodium to form calsium at room temperature with agitation to get sodium
aluminate (3CaO.Al2O3) with chemical reac- aluminate solution (Na2O.Al2O3). The solution was
tion [Habashi, 1997] : then separated from its residue by filtration, and
the residue was washed with aquades twice. Fil-
4Al2O3 + Na2CO3 + 3CaO J 2NaAlO2 + trate and residue were analyzed by atomic ad-
3CaO. Al2O3 + CO2 ............................................ (5) sorption spectrometry (AAS) for the chemical com-
position.

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 INDONESIAN MINING JOURNAL Vol. 13, No. 1, February 2010 : 16 - 25

The chemical composition of residue, filtrate and drated alumina (polymerization) at mol ratio of OH/
washed filtrate were used to calculate the recov- Al = 0.5 – 1.5 to form poly aluminum chloride. The
ery of alumina. Hydrated alumina was added sul- residues of filtration was concentrated by mag-
furic acid and ammonium hydroxyde to produce netic separator (1000 Gauss) results iron concen-
ammonium aluminum sulfate compound, and then trate as a by product, and it was analyzed by AAS
was crystalized (Husaini, 2008). In addition, hy- for its chemical composition and recovery. Figure
drated alumina was chlorinated with HCl to form 1 shows the simplified scheme of the research.
AlCl3, and then it was reacted by excess of hy-

Bauxite Residue
( red mud
(red mud))
(from Bayer Processs)
Sodium Carbonate Lime

PREPARATION

SINTERING
(soda-lime sinter)

LEACHING
Residue

MAGNETIC
FILTRATION Tailing
SEPARATOR

Sodium aluminate
Iron
solutaion
concentrate

Chemical Analysis PRESIPITATION

Al(OH)3
NH4(OH) HCl

SULFATATION
CHLORINATION
AND
‘POLYMERIZATION’
CRYSTALIZATION

Poly aluminum chloride

Amm. Al. S ulfate crystal
(PAC)
(NH4 Al(SO4 )2 .12H2 O)

Figure 1. Scheme of bauxite residue processing to produce hydrated alumina Al(OH)3), ammonium
aluminum sulfate (NH4Al(SO4)2 .12H2O) and poly aluminum chloride (PAC)

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 Extraction of Alumina from Bauxite Residue for Preparation ... Muchtar Aziz and Agus Wahyudi

RESULTS AND DISCUSSION Figure 3 shows the XRD graphic of West

Kalimantan bauxite residue, it contains dominantly
Bauxite Residue gibbsite (Al(OH)3. 3H2O), the others are hematite
(Fe2O3) and goethite (Fe+3O(OH)). Gibbsite is re-
Microscope optic examination shows a part of iron quired as source of alumina for alums and PAC
still interlock in gibsite particle (0.6 mm) and the after being extracted from bauxite residues.
other has already been liberated (Sutanto, 2008)
shown in Figure 2.

a b
Figure 2. Photomycrograph of bauxite; (a) a particle of gibsite (white) 0.6 mm interlock with iron particles
(black), (b) a particle of gibbsite has already been liberated (white)

The chemical composition of West Kalimantan Sodium Aluminate Solution

bauxite and its residue are shown in Tabel 1. Baux-
ite residue resulted from alumina extraction of Alumina was extracted from sinter by leaching with
bauxite ores by Bayer process still contains alu- 2 % wt. of sodium carbonate solution. The result
mina 20% and iron 37 %. is shown in Figure 4. Sintering process in various
temperature (800, 900, 1000, 1100OC) show that
the highest amount of extracted alumina is 75%
Tabel 1. Chemical composition by AAS of West occured at 800OC with solid percentage of 11.8%.
Kalimantan bauxite and its bauxite Between temparature of 900-1100OC, the extrac-
residue tion is downword to become 50% at 900OC and
45 % at 1100OC. The present results of leaching
Bauxite Bauxite residue are more accurate than that of the last (Aziz, et.al.,
Compound
(%) (%)
2009) because the process used sodium carbon-
SiO2 1,56 3,40 ate solution 1 % wt. The present leaching how-
Al2O3 44,79 20,17 ever, uses 2 % wt. of sodium carbonate solution
Fe2O3 15,76 37,48 in order to leach as much as calcium from cal-
MnO 0,06 0,16 cium aluminate compounds (3CaO.Al2O3) to form
MgO ttd 0,14
sodium aluminate solution (Alp, 2002).
CaO 0,02 0,06
Na2O ttd 3,03
K2O ttd ttd Extracted alumina as function of sintering time is
TiO2 1,11 3,43 shown in Figure 5. Sintering temperature at 800OC
P2O5 0,09 0,09 results the highest extracted alumina of 85.20 %,
H2O 36,04 31,21 occured in ½ hours. However, within time interval
Note: ttd means undetected
of 1-4 hours the extraction tends to reduce. The
alumina extraction is decreasing to become 47%

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 INDONESIAN MINING JOURNAL Vol. 13, No. 1, February 2010 : 16 - 25

a
c
b ca
b b ba
b ac a c aa a ba a

2θ
Figure 3. XRD graphic of West Kalimantan bauxite residue (note: a=gibbsite; b=hematite; c=goethite)

100
90
Alumina terekstraksi, %

80
70
60
50
40
30
20
10
0
700 800 900 1000 1100 1200

Figure 4. The effect of sintering temperature to the extracted alumina

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 Extraction of Alumina from Bauxite Residue for Preparation ... Muchtar Aziz and Agus Wahyudi

Figure 5. The effect of sintering time to the extracted alumina for sintering temperature of 800°C

Table 2. The concentration of main soluble elements in

sodium aluminate solution, detected by AAS

Al Na Si Fe Ca
No.
(103 ppm) (103 ppm) (ppm) (ppm) (ppm)
1. 50,41 32,39 0,37 1,95 1,74
2. 52,22 31,42 0,34 1,76 1,66
3. 51,71 36,11 0,32 1,54 1,77

in 1 hour and 25% in 4 hours of the sintering time. Precipitated Hydrated Alumina
The concentration of soluble main elements (Al+,
Na+, Si+, Fe+, Ca+) in sodium aluminate solution Hydrated alumina was precipitated by
is shown in Tabel 2. carbonatation process. The chemical composition
of hydrated alumina from precipitation of sodium
The data show that sinter soda-lime process of aluminate solution and its anhydrated alumina af-
bauxite residue produced sinter containing sodium ter calcinations is shown in Tabel 3. The grade of
aluminate (NaAlO2) compound that is soluble in alumina in hydrated alumina is 64.5 % Al2O3 and
sodium carbonate solution, producing sodium alu- the anhydrated alumina from calcination contains
minate (Na2O.Al2O3) solution, and leaving the solid 98.67 % Al2O3.
residue.

Tabel 3. Chemical composition of hydrated alumina or aluminum hydroxyde (Al(OH)3) and its anhydrated
alumina from presipitation of sodium aluminate solution, detected by AAS

Na2O CaO Al2O3 Fe2O3 TiO2 SiO2 H2O Al2O3 anhydrate

No.
(%) (%) (%) (%) (%) (%) (%) (%)
1. 0,43 0,048 64,52 0,007 0,002 0,014 34,96 98,67
2. 0,45 0,047 64,53 0,008 0,003 0,012 34,95 98,69
3. 0,41 0,049 64,52 0,009 0,001 0,011 34,96 98,67

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 INDONESIAN MINING JOURNAL Vol. 13, No. 1, February 2010 : 16 - 25

The chemical composition of imported alumina From above figures (Figure 6 & 7), we can see
(from Australia) is shown in Table 4. The grade of that all aluminum hydoxide has already changed
Al2O3 resulted from extraction of bauxite residue to ammonium aluminum sulfate hydrate (alums)
is 98.67 % (Table 3), and it is likely similiar to the by sulfatation process. No iron detected in this
quality of imported alumina (Table 4). alums, so that is physically shown of transparent
alums. Husaini (2008) prepared alums who applied
direct sulfatation of bauxite powder, however it pro-
Tabel 4. Chemical composition of imported duced brown colour of alums. The brown colour
alumina may be due to dissolved iron and other impurities
from bauxite. This method needs next process after
Na2O CaO Al2O3 Fe2O3 TiO2 SiO2 reducing the impurities from alums.
(%) (%) (%) (%) (%) (%)
0,42 0,043 98,7 0,010 0,002 0,016 Chlorination of Hydrated Alumina

Hydrated alumina was chlorinated with HCl in sto-

ichiometric amount to produce aluminum chloride
Figure 6 shows the XRD graphic of hydrated alu- (AlCl3), then it was reacted by excess of hydrated
mina which is resulted from precipitation of so- alumina at mol ratio of OH/Al = 0.5 – 1.5 to form
dium aluminate solution. It contains bayerite poly aluminum chloride (Al(OH)1.2 Cl1.8). Table 5
(Al(OH)3) and sodium aluminum carbonate hydrox- shows the products on chlorination of hydrated
ide (NaAlCO3(OH)2). This hydrated alumina can alumina at various mol ratio of OH/Al.
be used as raw material for alums and PAC.
Sulfatation of Hydrated Alumina There are 2 (two) types of PAC in applications
(Anonimous, 2010); the first type can be used for
Hydrated alumina obtained from extraction of baux- most applications, its contains Al2O3 18-20 % (9.5-
ite residue was reacted with sulfuric acid, then it 10.6 % Al) and Cl 21-22 %, the second type mostly
is added ammonium hydroxide and crystallized uses for drinking water treatment, its contains
to produce ammonium aluminum sulfate crystals Al2O3 8.8-9.2 % (4.6-4.9 % Al) and Cl 9.8-11 %.
(NH4Al(SO4)2 .12H2O) with high purity as shown The PAC resulted from this experiment (Code No.2)
in Figure 7. is considerably adjacent to the first type of PAC.

2θ
Figure 6. XRD graphic of hydrated alumina
(note: a=bayerite (aluminum hydroxide); b=sodium aluminum carbonate hydroxide)

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 Extraction of Alumina from Bauxite Residue for Preparation ... Muchtar Aziz and Agus Wahyudi

Figure 7. XRD graphyc of ammonium aluminum sulfate hydrate

Tabel 5. The reactans and products on chlorination of hydrated alumina with HCl at mol ratio of
OH/Al = 0.5, 1.0, and 1.5 in PAC forming, detected by AAS

Product,Al and Cl content in liquid PAC

Al(OH)3 HCl 12 % weight mol ratio (Al(OH)1,2Cl1,8)
CodeNo.
g (ml) OH : Al
% Al % Cl
1. 229 681 1.5 12.9 19.35
2. 235 732 1.0 10.1 19.33
3. 241 782 0.5 8.1 19.3

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 INDONESIAN MINING JOURNAL Vol. 13, No. 1, February 2010 : 16 - 25

Figure 8 shows comparison floc setting time be- CONCLUSION

tween experimental PAC (code-2) and imported
PAC from Taki Chemicals, Japan. The figure shows – Amount of 75-85 % alumina could be recov-
that both of them have the same trend by pH, but ered from bauxite residue by soda-lime sinter
experimental PAC resulted from this research has process at 800 OC, followed by leaching with
floc setting time little bit slower than that of im- sodium carbonate at room temperature.
ported one, it means that application of experi-
mental PAC need more time to form floc and settle – The highest extraction of alumina from baux-
down to the bottom. ite residue is 85.20%, it is formed in such
experimental condition (sintering temperature
Iron Concentrate as By Product 800OC, sintering time is ½ hours, leaching
with 2 % wt. of sodium carbonate solution at
Iron content in leached residue was separated by room temperature, solid percentage is 11.8%,
magnetic separator at intensity of 1000 gauss to and agitation time is 2 hours). The value of
produce iron cocentrate 58-62 % Fe2O3. Table 6 alumina results up to 98,67 % Al2O3, it shows
shows the chemical composition of main com- the same quality as imported alumina.
pounds in iron concentrate. The value and recov-
ery of Fe2O3 in iron concentrate for various sinter- – Sintering temperature and time are very influ-
ing time were shown in Figure 9. At time interval enced to the recovery of alumina from bauxite
of 1-4 hours, the iron content and recovery tend to residue. Higher sintering temperature would
decrease, the highest iron recovery (40 %) is decrease the alumina extraction, and sinter-
occured at ½ hours of sintering time. To get better ing time more than ½ hours reduces the ex-
result, the iron concentrate need to be up graded traction result.
by higher magnetic intensities.

(a) (b)

Figure 8. Floc setting time of resulted PAC code-2 (a); and imported PAC (b)

Table 6. Chemical composition (major compound)

in iron concentrate, detected by AAS

Fe2O3 Al2O3 SiO2 TiO2

No.
(%) (%) (%) (%)
1. 61,91 17,79 3,53 9,70
2. 59,16 18,81 4,22 8,91
3. 58,23 21,04 4,14 9,33

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 Extraction of Alumina from Bauxite Residue for Preparation ... Muchtar Aziz and Agus Wahyudi

T = 800°C

Iron Concentrate, %
Fe2O3
Value
Fe2O3
Recovery

Sintering times, hours

Figure 9. Iron concentrate from leaching residue of sinter at 800°C, separation by

magnetic of 1000 gauss

– Sulfatation of hydrated alumina with adding of Soda, Jurnal Teknologi Mineral dan Batubara,
ammonium hydroxide results in high grade of Vol.05, No.14, Mei 2009.
ammonium aluminum sulfate (NH4Al(SO4)2
.12H2O) crystals. Habashi, 1997. Handbook of Extractive Metallurgy,
Alkaline Processes , vol.II, p.1091-1092,
– Chlorination of hydrated alumina in stoichio- Wiley-VCH.
metric amount at mol ratio of OH/Al = 1.0 re-
sults poly aluminum chloride (PAC) which is Husaini, 2008. Penelitian Pendahuluan Pembuatan
adjacent quality to the first type of PAC. Tawas dari Bauksit Kijang, Jurnal Bahan
Galian Industri, Vol. 4 No. 10, April 2008.
– Through the soda-lime sinter process it can
also produce iron concentrate having grade of Magnus, Kvant and Stendahl Kjell, 1990. Process
66 % Fe2O3 with 40 % of recovery. for the preparation of polyaluminum com-
pounds, European Patent Application.

REFERENCES Padilla R. and Sohn H.Y., 1985. Sintering Kinet-

ics and Alumina Yield in Lime-Soda Sinter
Alp A. and Aydin A.O., 2002, The Investigation of Process for Alumina from Coal Wastes, Met-
Efficient Conditions for Alumina Production allurgical Transactions B, Vol 16B, June 1985
from Diasporic Bauxites, Canadian Metallur- – 385.
gical Quarterly, Vol 41, No.1, p. 41-46.
Sharif, 2005. Towards Zero Wastes,
Anonimous, 2010. Polyaluminium Chloride Tech- [email protected], CSIRO Mineral.
nology, [email protected].
Sutanto A., 2008. Hasil pengamatan mikroskopis
Aziz, M., Mutaalim, Amalia, D., and Wahyudi, A., sayatan tipis residu bauksit, Laporan Internal
2009. Pemrosesan Red Mud – Limbah research of West Kalimantan bauxite.
Ekstraksi Alumina dari Bijih Bauksit Bintan
untuk Memperoleh Kembali Alumina dan PAC, Taki Chemicals Co., Ltd.

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