JKAU: Eng. Sci., Vol. 20 No.2, pp: 29-41 (2009 A.D. / 1430 A.H.

Extraction of Alumina from Local Clays by

Hydrochloric Acid Process

A.A. Al-Zahrani and M.H. Abdul-Majid

Chemical and Materials Engineering Dept.,
Faculty of Engineering, King Abdulaziz University,
Jeddah, Saudi Arabia

Abstract. A bench work study was carried out to investigate the use of
kaolinitic clay containing 29.4% Al2O3 extremely abundant in Saudi
o
Arabia for the production of pure alumina by calcination at 700 C for
1h (recommended by previous investigators) then leached by
hydrochloric acid.
o
The effects of leaching temperature (25 C to boiling
temperature), period of activation (10-150 minutes), acid
concentration (1M 6M), particle size (8 to 200 standard Tyler
screen mesh), acid to clay weight ratio (4:1 to 15 :1ml acid/gm clay)
on alumina extraction were investigated.

The recommended leaching conditions are: 6 molar for acid

concentration at boiling conditions under reflux, one hour for
leaching time, 100 mesh standard Tyler screens for particle size of
calcined clay and 10 ml acid/gm clay for acid to clay weight ratio.
Leaching this local clay sample under these conditions resulted in
32% alumina extraction.

Local kaolinitic clay were calcined at temperatures varying

o o
between 400 C and 800 C at different calcination periods (5 to 120
minutes). The calcined clay was then leached with 3M HCl acid under
the above-recommended leaching conditions. The optimum
o
calcination conditions were 600 C and 1 hour for calcination
temperature and time period, respectively. The corresponding alumina
extraction from local clay sample is about 63%.

Keywords: Alumina extraction, Hydrochloric acid leaching, kaolinitic

clay, Calcination.

29
30 A.A. Al-Zahrani and M.H. Abdul-Majid

1. Introduction
The raw material for manufacture of alumina, i.e. bauxite has been
discovered in the Kingdom of Saudi Arabia only in limited amounts. It is
natural to look for the production of this important material through other
available resources of raw materials that contain high alumina and low
iron oxide content. One of the numerous aluminous raw materials
distributed on a large scale in the Kingdoms land that contains a high
percentage of aluminum oxide and low percentage of impurities is the
kaolinitic clays. It is thought as a suitable substitute for bauxite from
which alumina of high purity can be obtained.
Several sintering and acid-extraction processes have been
investigated for the production of alumina from kaolin and other clays.
The French Pechiney-Ugine Kuhlmann process treats clays and shales
with concentrated sulfuric acid. Hydrochloric acid is added during the
crystallization step to form aluminum chloride which crystallizes readily.
Much raw material must be handled in the process, because the clays and
shales have lower alumina content than bauxite[1]. Other methods involve
the treatment of clays with different mineral acids or the continuous
electrolysis of aluminum chloride[2].
It is reported in the literature that some of the more important
advantages of using hydrochloric acid over other acids for leaching
alumina are the ease of filtration of slurries, the ease of iron removal and
the insolubility of titanium dioxide, which is present in many clays. The
most serious problem connected with the use of hydrochloric acid is the
severe corrosion; however, the development of corrosion resistant
plastics and rubbers partially solved this problem so that the corrosion is
no longer a prohibitive factor[3]. Both hydrochloric and sulfuric acids
extract approximately the same quantity of alumina from each ton of
clay[4-7]. It has been reported also that the silica residue is easily separated
from the chloride solution, which filters rapidly, and a number of
procedures have been proposed for eliminating iron from aluminum
chloride solution[8, 9].
Bakr and El-Abd described in several papers the extraction of
alumina from Egyptian kaolin by hydrochloric acid leaching[10, 11].
Optimum conditions have been worked out in respect of the variables
involved such as fineness of kaolin, period and temperature of
calcination, concentration of hydrochloric acid, acid to clay ratio and
 Extraction of Alumina from Local Clays by Hydrochloric Acid Process 31

period and temperature of extraction. The production of a crude alumina

from clay was also investigated on a pilot plant scale[12]. Weston
described in several patents[13] the production of a purified alumina-silica
product and substantially pure aluminum chloride from iron-containing
bauxites, bauxitic clays, kaolinitic clays and mixtures thereof. The
substantially iron free alumina-silica products were made by mixing the
previous raw materials, agglomeration, calcining the mixture at
o
approximately 650-900 C and subjecting the calcined material to
differential chlorination stages to produce a substantially iron-free
product. The optimization of the crystallization process and concentration
of impurities was controlled by AlCl3 concentration in the feed solution,
HCl gas flow rate, temperature and concentration of phosphorus and
magnesium in the feed solution. Shanks[14] reported later that
improvements were made by decreasing the initial leaching acid
concentration from 25 to 20%, decreasing the leaching time 1 to 2 hour
to 15 to 30 min eliminating the solvent extraction step for iron removal
and eliminating the step to recover the aluminum content of the bleed-
stream circuit.

Ozdemir and Cetisli[15] studied the extraction kinetics of alunite in

sulfuric acid and hydrochloric acid in a batch reactor. The effects of
reaction temperature, acid concentration, particle size, calcination
temperature, calcinations time and acid/Al2O3 molar ratio on the
extraction process were investigated. The calcination temperature was the
most important parameter affecting the extraction process followed by
reaction temperature. Other work reported in the literature on the
extraction of alumina from clay by hydrochloric acid treatment include
the work of Ziegenbalg et al.[16, 17], Poppleton and Sawyer[18], Eisele et
al.[19, 20] and Shanks, et al.[21].

The aim of this paper is to investigate the possible manufacture of

alumina from local Saudi clays, which are extremely abundant in the
Kingdom, rather from the much scarcer bauxite. A bench scale study will
be carried out to investigate the extraction of alumina from local clay by
calcination and hydrochloric acid leaching of alumina. The effects of
leaching temperature, period of activation, acid concentration, particle
size acid to clay weight ratio and temperature and duration of calcination
on alumina extraction were investigated to recommend the most suitable
conditions.
32 A.A. Al-Zahrani and M.H. Abdul-Majid

2. Materials and Method

2.1 Materials
The clay sample selected for investigation was a kaolinitic clay
o o
obtained from Riyadh area (N: 24 00`36``, E = 47 44` 03``).
The chemical composition of the clay sample is given in Table 1.
The analysis of local clay was done at the Chemical & Materials
Engineering Department, College of Eng., KAU[22].
Table 1. Chemical composition of the local kaolinitic clay.

Compound Natural local clay (%)

SiO2 47.25
Al2O3 29.4
Fe2 O3 2.87
TiO2 1.17
MgO 0.35
CaO 0.59
K 2O 0.17
Na2O 2.11
MnO < 0.05
SO3 < 0.05
P2O5 < 0.05
L.O.I. 16.02

2. 2 Methods
2.2.1 Grinding
The average size of the diameter of the raw local clay sample was
about 2 to 3 inches. The clay sample was ground using a ball mill to 149
m (100 mesh). The ground clay sample was placed on the sieve, and
then mechanically shacked for 5 min. The oversize was further ground
followed by sieving on the same sieve. The procedures were repeated till
the entire clay sample passed through the sieve.
 Extraction of Alumina from Local Clays by Hydrochloric Acid Process 33

2.2.2 Calcination Experiments

Ground clay sample passing 100 mesh was subjected to calcination. A
o
muffle furnace (Carbolyte) with a maximum temperature of 1200 C was
o
used. The heating is carried out at 700 C for 1 h to activate the clay before
acid treatment, which is reported in some previous work to be the
recommended conditions for activation of local Saudi kaolinitic clays[22, 23].

2.2.3. Acid Leaching Experiments

Five grams of the calcined clay sample passing 100 mesh were
leached using 3M hydrochloric acid for different periods of time (10-150
min) and at different leaching temperatures (25C to boiling temperature)
using a constant temperature shaking water bath at a fixed shaking rate of
160 cycles/min and using boiling under reflux. By the end of leaching,
the resulting slurry was filtered to separate undissolved materials, washed
three times with 10 ml portions of distilled water. The filtrate and
washings were continued to a constant volume of 250 ml in a volumetric
flask. The resulting solutions were diluted, analyzed for aluminum ion
using solar MS Atomic Absorption Spectrophotometer[23].
The effects of leaching period, leaching temperature, and acid
concentration on alumina extraction were investigated.

3. Results and Discussion

3.1 Effect of Extraction Time and Leaching Temperature
The effects of leaching time and temperature on the yield of alumina
extracted from 100 mesh clay sample calcined at 700C for one hour
using 3M hydrochloric acid under different leaching temperatures
ranging from 25C to boiling under reflux at fixed acid to clay weight
ratio of 10 are shown in Fig. 1. The figure shows that the percent of
extraction of alumina from the clay is approximately constant after one
hour at all leaching temperatures. Also, It shows that a relatively large
increase in the percentage extraction of aluminum oxide is observed with
increasing leaching temperature from 25C to boiling temperature.
Therefore, a reaction time and temperature were selected to be one hour
and boiling temperature, respectively.
34 A.A. Al-Zahrani and M.H. Abdul-Majid

35

30
25 C
50 C
80 C
25
Boiling
% Extraction of Al 2O 3

20

15

10

0
0 20 40 60 80 100 120 140 160

Time of leaching (minutes)

Fig. 1. Effect of leaching time and temperature on alumina extraction at acid to clay weight
ratio of 1.

3.2 Effect of Acid Concentration

Results on the effect of varying acid concentrations from 1M to 6M
on dissolution of alumina are illustrated in Fig. 2. It indicates that
although alumina extraction increases with increasing acid concentration
up to a value of 3M, the percent of alumina extracted using an acid
concentration of 6M, however, decreases below that obtained at 3M acid
concentration. It is expected that the diffusion rates of Al+++ ions from
the solid to the solution increase as the concentration and diffusion of
hydronium ion rise, a maximum is reached at concentration of 3 M HCl.
The extraction rate at 6M HCl decreases. This may be due to the kaolin
structure collapsing at this concentration or may be due that Al+++ species
blocking H+ diffusion. Similar behavior was also observed in other
studies[18 21, 24].
Maximum alumina extraction observed from this specific local clay
was still in the range of 31-32%.

3.3 Effect of Acid to Clay Weight Ratio

Results on the effect of varying acid to clay weight ratio on
dissolution of alumina are illustrated in Fig. 3.
 Extraction of Alumina from Local Clays by Hydrochloric Acid Process 35

35

30

3
O25
l2
A 1 M
f
o
n
o 2 M
tic
ar
t 3 M
x
E
% 6 M
20

15

10
0 20 40 60 80 1 00 1 20 1 40 1 60
Tim e ( min u tes)

Fig. 2. Effect of leaching time and acid concentration on extraction on Al2O3 extraction at
acid to clay ratio weight ratio of 10 and boiling temperature.

35

30

25
Percentage extractionof Al2O3

20

15

ACR =4
ACR =6
ACR =8
10
ACR = 10
ACR =12
ACR =15

0
0 1 2 3 4 5 6 7
Acid concentration (M)

Fig. 3. Effect of acid to clay weight ratio on alumina extraction at different acid
concentrations.
36 A.A. Al-Zahrani and M.H. Abdul-Majid

The data presented indicate that increasing acid to clay weight ratio
from 4 : 1 to 8 : 1 increases the percentage of alumina extraction under
the same calcination and leaching conditions, followed by a slight
increase in the percentage of alumina extraction with increasing acid to
clay ratio to 10 : 1, and approximately no change in the percentage of
alumina extraction at higher ratios up to 15 : 1.

3.4 Effect of Particle Size of Calcined Clay

Figure 4 shows the effect of grain size of clay sample on the
percentage of aluminum oxides extraction. All samples were calcined at
fixed temperature of 700C for a fixed period of one hour. Then the
calcined samples were leached by 3M HCl using acid to clay weight ratio
of 10 : 1 for one hour at boiling conditions under reflux and varying the
mesh number of the clay sample over a wide range between 8 and 200
standard Tyler screen mesh. Figure 4 indicates that grinding the clay
samples beyond 65 mesh has no significant effect on the extraction of
alumina from the local clay sample. Therefore, a grain size of 100
Taylor mesh was selected for further work.
35

30

25
Perecntage extraction of Al2O3

20

15

10

0
0 50 100 150 200 250
Mesh No. (standard Tyler screens)

Fig. 4. Effect of particle size of calcined clay on alumina extraction using 3M HCl.
 Extraction of Alumina from Local Clays by Hydrochloric Acid Process 37

3.5 Effect of Temperature and Period of Clay Calcination

To investigate the effect of calcination temperature and time on the

extraction of alumina, clay samples were calcined at different
temperatures ranging from 400 to 800C, each for different periods of
time ranging from 5 to 120 minutes before leaching these 100 mesh
calcined clay samples for 1 our under reflux. Figure 5 shows that the
calcination temperature appears to be the most important parameter
affecting alumina extraction. Below a calcination temperature of 450C
represent a negligible extraction zone exist. An active zone exists
between 500 and 600C and another inert zone exists after about 650C.
The alumina extraction yields increase from 17.02% to 62.94% over the
range of 400 to 600C for a calcination period of 60 min. The decrease in
extraction beyond a calcination temperature of 600C may be attributed
to a total dehydration of clay samples at 600C and to the solid phase
transformation of alumina beyond 600C. For this reason, the extraction
yield of alumina continued to increase up to 600C after which, the yield
decreases. Similar behavior was also observed in previous studies[15, 24- 27].
These data also indicate that in the temperature range up to 650C,
alumina extraction yield increases with increasing calcination time,
whereas, at calcination temperatures higher than 650C, the alumina
extraction yield decrease with increasing calcination time. This may be
attributed to a partial sintering of clay subjected to larger periods of
calcination at higher calcination temperatures. Therefore, the data shows
that a calcination temperature of 600C for 1 h gives the optimum
conditions for alumina extraction from local clay samples. The
corresponding alumina extraction is 62.94%. Similar results were
observed by Ting[24].

4. Conclusion

Approximately 62.9% of alumina present in a local Saudi clay can

be extracted by calcination followed by a leaching step using
hydrochloric acid. The recommended extraction procedure is a first
step calcination at 600C for a period of one hour, followed by a leaching
step of the calcined clay after grinding and sizing to a 100 standard
Taylor screen. Leaching should be carried out using 3M solution of HCl
at boiling conditions under total reflux for a period of one hour using a
38 A.A. Al-Zahrani and M.H. Abdul-Majid

10 : 1 liquid to solid weight ratio. Leaching this local clay sample under
theses conditions result in 62.94% extraction of alumina.
70

60

5 min.
50 10 min.
20 min.
Perectage extraction of Al2O3

30 min.
60 min.
40
120 min.

30

20

10

0
0 100 200 300 400 500 600 700 800 900
Temperature of calcination ( oC)

Fig. 5. Effect of temperature and period of clay calcination on alumina extraction using
3M HCl.

References
[1] Barclay, A. and Peters, D., "New Sources of Alumina", Min. Cong. J., 62(6): 29-33 (1976).
[2] Austin, G. ,"Shreves Chemical Process Industries", 5th. Ed., McGraw-Hill, New York, 244-
250 and 355-359 (1984).
[3] Peters, F.A., Johnson, P.W. and Kirby, R.C., "Methods for Producing Alumina From Clay,
An Evaluation of Five Hydrochloric Acid Processes", U.S. Bureau of Mines R.I. No. 6133,
(1962).
[4] Tilley, G.S., Millar, R.W. and Ralston, O. C., "Acid Process for the Extraction of
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[6] Raghaven, S. and Gajam, S.Y., "Change in Porous Nature of Kaolinite with Hydrochloric
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[7] Schoenborn, N. and Hofman, H., "Reaction of Selected Clays with Hydrochloric Acid",
Freiberger Forschungshefte A, A616: 39-50 (1979).
[8] Park, K.Y., Jeong,J., Choi, Y.K. and Kang, T.W., "Kinetic Study on the Extraction of
Aluminum from Clay by Hydrochloric Acid", Hwahak Konghak, 30(4): 509-516 (1992).
[9] Sorensen, R.T., Sawyer, D.L. and Turner, T.L., "Alumina Miniplant Operations-
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 Extraction of Alumina from Local Clays by Hydrochloric Acid Process 39

[10] Bakr, M.Y. and El-Abd, M.A., "Extraction of Alumina From Egyptian Kaolins & Clays:
Part IV- Alumina Extraction by the Hydrochloric Acid Method", Indian Journal of
Technology, 7: 405-409 (1969).
[11] Ibid., "Extraction of Alumina From Egyptian Clays and Kaolins, Part IV Acid Process for
the Recovery of Alumina: Hydrochloric Acid Process", Sprechsaal Jahrg., 100(23): 412-418
(1967).
[12] Christensen, A.L., "Extraction of Alumina from Clay and Similar Materials by
Hydrochloric Acid Processes, Part I.", U.S. Dept. of Commerce, PB No. 13983 (1943).
[13] Weston, D., "Production of a Purified Alumina-Silica Product and Substantially Pure
Aluminum Chloride from Iron-Containing Bauxites, Bauxitic Clays, Kaolinitic Clays and
Mixtures Thereof, CAN. Pat. No. 109:8893, (1988).
[14] Shanks, D.E.,Ten-Cycle Bench-Scale Study of Simplified Clay-Hydrogen Chloride
Process for Alumina Production, U.S. Bureau of Mines R.I. No. 9544 (1995).
[15] Ozdemir, M. and Cetisli, H., "Extraction Kinetics of Alunite in Sulfuric Acid and
Hydrochloric Acid", Hydrometallurgy, 76(3-4): 217-224 (2005).
[16] Ziegenbalg, S. and Discher, G. , "Extraction of Alumina From Clay by Hydrochloric Acid
Process", Freiberger Forschungshefte (Reihe) A:7- 25 (1983).
[17] Ibid., "Investigations Into the Alumina Extraction from Clay by Hydrochloric Acid and
Sulfuric Acid Leaching", Light Metals: Proceedings of Sessions, AIME Annual Meeting
(Warrendale, Pennsylvania): 1119-1143(1983).
[18] Poppleton, H. O. and Sawyer, D. L., "Hydrochloric Acid Leaching of Calcined Kaolin to
Produce Alumina", Instruments and Experimental Techniques (English Translation of
Pribory I Tekhnika Eksperimenta), 2: 103-114 (1977).
[19] Eisele, J.A., "Producing Alumina from Clay by the Hydrochloric Acid Process, A Bench-
Scale Study", U.S. Bureau of Mines R.I. No. 8476 (1980).
[20] Eisele, J.A., Bauer, D.J. and Shanks, D.E., "Bench-Scale Studies to Recover Alumina
From Clay by a Hydrochloric Acid Process", Industrial & Engineering Chemistry, Product
Research and Development, 22(1): 105-110 (1983).
[21] Shanks, D.E., Thompson, D.C., Dan, G.L. and Eisele, J.A., "Options in the Hydrochloric
Acid Process for the Production of Alumina From Clay", Metallurgical Soc. of AIME, 2: 25-
33(1986).
[22] Al-Zahrani, A. A. and Abdel-Majid, M. H., "Production of Liquid Alum from Local Saudi
Clays", Final Report, Project No. 119 / 422, Scientific Research Council, KAU (2003).
[23] Thermo Elements, Absorption Spectrometry, Company Methods Manual, U.K.(2000).
[24] Ting, C.W., "Extraction of Alumina and Potash from Chinese Alunite by the Kalunite
Process", Research Bulletin, 8 (1952).
[25] Ozcar, M. and Sengil, I.A.,"Optimum Conditions for Leaching Calcined Alunite Ore in
Strong Sodium Hydroxide", Can. MEtall. Q 4: 249-255 (1999).
[26] Foisland, L.J., Wouden, M.L. and Harbuck, D.D., "Acid Sulfation of Alunite", U.S.
Bureau of Mines R.I. No. 9222 (1989).
40 A.A. Al-Zahrani and M.H. Abdul-Majid


 

   





     
    
     
        

 
       
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