Sequential Leaching For The Production of Alumina From A Nigerian Clay

Inte rnational Journal of Engineering Technology, Manage ment and Applied Sciences
www.ijetmas.com July 2015, Volume 3, Issue 7, ISSN 2349-4476
Sequential Leaching for the Production of Alumina from a

Nigerian Clay
OLAREMU, Abimbola George
Department of Chemical Sciences,
Adekunle Ajasin University Akungba Akoko,
Nigeria.
ABSTRACT
This work reports a process for synthesis of alumina from Nigerian kaolinite clay. Kaolin was transformed to meta-
kaolin by calcination at 800°C for 3h.Alumina powder was synthesized through extracting alumina from meta- kaolin
through the use of 2M sulfuric acid and meta-kaolin reactions and consequently precipitation in ethanol, which led to
form the aluminum sulfate(Alum). The precipitated aluminum sulfate was dried and calcined at 1000°C for 1h, which
resulted in the formation of Gamma (γ) alumina. The surface area of the synthesized alumina is 164 m2/g which is good
and comparable with the commercial alumina with surface area between 120 -200m2/g. It can therefore be concluded
that Gamma(γ )alumina had been synthesized, an assumption which was confirmed by the high surface area from BET,
highly ordered particle by TEM,and the compositional analysis by XRD,RAMAN and IR.
Keywords: Nigeria, Alumina, BET, XRD,RAMAN,IR,TEM
INTRODUCTION
Alumina is widely distributed in nature. Combined with silica and other minerals. It occurs in clays, feldspars
and micas. It is the major component of bauxite and occurs in an almost pure form as corundum (1).It is
commercially important and a major use is in the production of aluminum metal. It is also used for abrasives;
corundum and emery are widely used, as are artificially prepared alumina abrasives.It is also used in
ceramics,in pigments, and in the manufacture of chemicals. Alumina is widely used as an advanced ceramic
material due to its combination of physical, chemical and electrical properties. Its hardness and strength
withgood wear and chemical resistant at a very high temperature has made it a good choice forcritical
structural applications. The demand for alumina mainly comes from the electrical andelectronic sectors due to
its excellent dielectric and insulating properties. High purity aluminathat is used for high technical
applications are required to be of more than 95% purity withvery low sodium and iron content. In the
traditional processing method, the sodium impuritymainly comes from the used of sodium hydroxide whilst
iron is present in the bauxite mineral (2)
Pure alumina is used in making crucibles and other refractory apparatus.Hydrated alumina is used in mordant
dyeing to make lake pigments; it is also used in glassmaking, in cosmetics and in medicine as an antacid (1).
Alumina is an important material in catalysis(3-5), especially now when ordered mesoporous alumina (OMA)
can be made in a facile and reproducible manner (6).
Alumina is a white powder produced normally from bauxite ore through alkali leaching by the Bayer process.
More than 90% of the world’s commercial production of alumina is obtained by hydro chemical sodium
hydroxide extraction of bauxite using the conventional Bayer process.In this process it is uneconomical to
treat bauxite containing more than 7% reactive silica, due to excessive alumina and soda losses(7).Such
quality of bauxite depots are fairly rare and most of those available being controlled by world’s largest
aluminum manufacturing concerns.Many investigators have also tried to modify the Bayern process to utilize
raw materials other than Bauxite(8-14).Examples of non-bauxite raw materials include
laterites,clay,alunite,sillimanite,alusite,nepheline,fly ash,kyanite,mica and aluminous shales.
Although clay are abundant and inexpensive minerals,the studied processes remained uncompetitive with the
alumina extraction from bauxite using the Bayer process(15,16) for which reserves are sufficient for the next
50 years(17).
Clay are abundant minerals which consist of iron oxides,alumino-silicates and alkaline metal
oxides(9,11,15,18).The main contaminants of clays are quartz and mica (10-45% w/w) and iron oxide(1-10%
w/w).Kaolinite is a two layer silicate mineral that typifies the kaolin group, it may be represented by
103 OLAREMU, Abimbola George

Al2 O3 .2SiO2 .2H2 O(19).The structure is composed of a single silica tetrahedral sheet and a single alumina
octahedral sheet combined in a unit so that the tips of the silica tetrahedrons and one of the layers of the
octahedral sheet form a common layer. The structure units are held together in the basal plane by hydrogen
bonding between oxygen ions of the tetrahedral sheet and hydroxyl ions of the octahedral sheet (20).
Ozdemir and Cetisli 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, time
and acid/Al2 O3 molar ratio on the extraction process were investigated. The calcination temperature was the
most important parameter affecting the extraction process followed by reaction temperature (21).
Weston described in several patent s (22), 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 approximately 650-900o 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 magnes ium in the feed solution.
Shanks(23) 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. A
bench work study was carried out to investigate the use of kaolinitic clay containing 29.4% Al2O3 extremely
abundant in Saudi Arabia for the production of pure alumina by calcination at 700oC for 1hr then leached by
hydrochloric acid. The effects of leaching temperature (25oC 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 (24).Various mineral
acids(HCl,H2 SO4 ,H2 SO3 , andHNO3 ) for alumina extraction have been investigated(9,16,25,26,27,28).
The aim of this paper is to investigate the possible manufacture of alumina from local Nigerian clay which are
extremely abundant in Akoko land, South-western,Nigeria rather than scarcerbauxite or importation which is
seriously destroying or crippling the Nigerian economy highly regarded as the largest in Africa and 20th in the
world. A bench scale study is proposed to investigate the extraction of alumina from Akoko clay by
calcinations and sulfuric acid leaching of alumina.
2. EXPERIMENTAL
2.1. Synthesis
Kaolinite clay was sourced, prepared and characterized using a recipe that is based on previous report
(29).The kaolin powder was first screened to particles below 75 μm in size and calcined at 800 0 C for 3 hours
in an electric furnace to loosen the alumina components (30). Then, 18 g of the calcinedsample was added
with 300mL of a 2M sulfuric acid (H2SO4) solution in a flask fitted witha thermometer. The mixture of the
sample and acid was heated to a temperature of 800 Cand then maintained at that temperature range for 240
min and stirred with a magnetic stirrer.
After the mixture of the sample and acid had been leached, it was cooled to room temperatureand filtered to
remove the leach residue, which mainly consisted of silica. The filtered leachliquor was then added drop wise
into 600mL of ethanol again under stirring with a magneticstirrer. Ethanol was used as a precipitating agent
because Al3+ ions can be extracted fromethanol with high selectivity. The precipitates were washed again with
the ethanol, and thendried at 1000 C for 6 hours. Finally, the precipitates were calcined at 10000 C for 1 hour in
anelectrical furnace.
Note: The precipitate may be dissolved completely in the ethanol while agitating if the acid is in excess of the
ethanol.
2.2. Measurements and characterization
Nitrogen adsorption measurements were performed using micromeritics Tristar 3000V4.02 under liquid
nitrogen temperature where BET surface area and pore volume/size of the samples were automatically

calculated by the instrument using N2 isotherm and the results recorded on the computer attached to the
instrument. The sample had been previously degassed under vacuum at 200o C for 2hr prior to measurements.
The X-ray diffraction (XRD) analysis was carried out on a Panalytical X’Pert Pro diffractometer, employing
Cu Kα monochromatic radiation. All the patterns were collected at room temperature with steps of 0.02 o using
a range of 5 – 80o . The measurements were taken at room temperature (298 K), with scan rate of 2o min-1 and
0.02 steps and the patterns were recorded by the Broker-D8software.
The infrared spectra of the sample was collected using attenuated total reflection (ATR) module with a
Nicolet model 360 FTIR at 0.5 cm-1 nominal resolution. The spectra were recorded in the region of 4000 - 400
cm-1 .
Raman spectroscopy was used because its detection limits are below the 4nm (approx.) cut-off of crystallite
size for XRD and its ability to show bands that cannot be detected using FTIR. The Raman spectra were
recorded with Renishaw spectrometer equipped with invia Raman microscope RE 02, 514nm laser was
employed as the exciting source and the measuring parameter were set as follow; accumulation 10, exposure
time 20 and laser power between 75 %.
Transmission electron microscopy (TEM) images of the recovered sample were recorded on a TEM-JEOL
JEM-2000EX. (JEOL Ltd., Tokyo, Japan). The electrons were produced by a LaB6 crystal and accelerated up
to 200 kV. The TEM is capable of producing a beam diameter as small as 0.5 nm, with 0.19 nm resolution.
Images were recorded on a Gatan 794 CCD camera (Gatan Inc., Pleasanton, California, USA). A very small
amount of the sample was dissolved in isopropanol and loaded into a carbon coated metal grid which gives
preferred orientation and allows observation. Various magnifications were used to obtain suitable micrographs
of sample.
3. RESULTS AND DISCUSSION.

The textural properties of the synthesized alumina have been studied by N 2 sorption measurements. The type
IV shape of N2 adsorption/desorption isotherm and also the hysteresis loop in figure 1 prove the presence of
mesopores in the alumina structure. The pore size distribution curve is shown in figure 2.According to the
figure the alumina is consist of pores with uniform sizes which are mesoporous. The multipoint BET surface
area, total pore volume and the average pore size of the alumina are 164 m2 /g,1.21cm3 /g and 29.51nm
respectively. This was good when compared to the surface area range for commercial alumina support (120-
200m2 /g)
Clay4
900
800
Quantity Adsorbed (cm³/g STP)
700
600
500
400
300
200
100
0.0 0.2 0.4 0.6 0.8 1.0

p/p°
Figure 1.N2 adsorption isotherms for synthesized alumina

Clay4
0.08
0.07
dV/dw Pore Volume (cm³/g·nm)
0.06
0.05
0.04
0.03
0.02
0.01
0.00
-0.01
0 50 100 150 200
Pore Width (nm)
Figure 2.Pore-size distribution curve of synthesized alumina

The results of xrd analysis of the synthesized material confirmed the formation of alumina through comparing
with JCPDS 29-63(Alumina phase JCPDS file no 29-63: for characteristic peak of gamma phase of alumina at
2Ө).The pattern is shown in figure 3.In addition,the formation of alumina can be seen in the infrared
spectra(figure 4).Sohlbery et al.showed that alumina is known to have a spinel structure which exists over a
range of hydrogen contentt(31,32).
Figure3. X-ray diffraction pattern for synthesized alumina

The stronger broadening band 3800 -3000cm-1 occurs due to the hydrogen bond between the various hydroxyl
groups in the product.
0.5
0.4
0.3
A
0.2
0.1
0
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
wavenumber cm-1
Figure4. Infrared spectrum for synthesized alumina

18000
16000
14000
12000
Counts
10000
8000
6000
4000
2000
0 200 400 600 800 1000 1200
Raman shift / cm-1
Figure 5: Laser Raman Spectrum for synthesized alumina
The Transmission electron microscopic (TEM) images of the synthesized alumina which shows the particle
size are presented in figure 6a, b and c. The TEM confirms high ordering of the synthesized alumina.
Figure6a.Transmission electron microscopic image of the synthesized alumina
Figure6b.Transmission electron microscopic image of the synthesized alumina
Figure6c.Transmission electron microscopic image of the synthesized alumina

CONCLUSION.
Alumina is one of the most cost effective and widely used materials in the family of engineering ceramics.The
current investigation of the recovery of alumina from Nigerian kaolinite clay using sulphuric acid solution was
carried out on laboratory scale. Previously characterised clay in my laboratory was used.The clay was calcined
at 800oC which lead to the formation of meta-kaolin. Leaching with 2Msulfuric acid was then followed by
direct precipitation in ethanol which was a crucial step for synthesis of alumina. The final product was
characterized using BET,XRD,RAMAN,IR and TEM.It can therefore be concluded that Gamma(γ )alumina
had been synthesized,an assumption which was confirmed by the high surface area from BET, highly ordered
particle by TEM,and the compositional analysis by XRD,RAMAB and IR.
Acknowledgment.
I wish to acknowledge the effort of Stephen Olatundun, Mr.Adeyemo and Mr Bamidele for their effort and
assistance during the laboratory work in Adekunle Ajasin University, Akungba Akoko Nigeria and Mr. Oloye
Femi during the analysis in University of Aberdeen,UK.
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Inte rnational Journal of Engineering Technology, Manage ment and Applied Sciences

www.ijetmas.com July 2015, Volume 3, Issue 7, ISSN 2349-4476