Nigerian Journal of Engineering ~ Vol.16 No.

2, March 2010
Faculty of Engineering ISSN: 0794-4756
Ahmadu Bello University
Zaria, Kaduna, Nigeria

BENEFICIATION OF KANKARA KAOLIN

FOR ALUM PRODUCTION

L. Edomwonyi -Otu=, B. O. Aderemi and A.S. Ahmed

Chemical Engineering Department, Ahmadu Bello University, Zaria
(*Corresponding Author; email address:osasllaw@yahoo.com)
ABSTRACT
The investigation involved the beneficiation of Kankara kaolin clay to remove grits. free quartz and
other associated impurities. The beneficiated clay was activated by calcination at 7500C for 2hrs; it
was thereafter subjected to acid digestion to unlock the structural alumina out of the clay matrix to
form alum. About 91 % kaolinite fraction was recovered from Kankara kaolin after beneficiation, with
14.14 wt % loss 011 ignition. It had an effective size ofO.OOO3mm and a coefficient of uniformity of9.3
which is in conformity to literature expectations. The raw clay yielded 72.91% alum (in terms of% wt
of alumina extracted from the clay) while the fully beneficiated clay yielded 81.3Owt% alum. In
quality terms, only MgO content showed significant reduction (about 86.0%) via beneficiation in this
study.

Key words: Alum, Aluminum sulfate, beneficiation, dealumination, Kankara kaolin, kaolinite,
metakaolin,
applications (Kirk Othmer, 1997, and
www.wikipedia, 2008).
Introduction
The word alum is derived from its Latin
The traditional source of alum is bauxite (45-
generic form "alumen", which was applied to
65wt % alumina). However world bauxite
several astringent substances, most of which
deposits are vastly declining (Marstiller, 1978;
contained aluminum sui fate (Kirk Othmer,
Azom, 2008). In Nigeria particularly, there is
1997). Alum is commonly used in food and
no known commercial bauxite deposit.
pharmaceutical related industries as well as in
Nevertheless. respite is found in kaolin clay,
water treatment. It is also extensively used in
containing 33-39wt % alumina content and is
the manufacture of vegetable glues, p; _celain
abundantly available (RMRDC, 2(00).
cements, natural deodorants, tanning, dyeing,
Typical composition of kaolin deposits shows
fireproofing textiles and paper and in alumina
the presence of grits, free quartz and other
production for catalytic and refractory

27
Nigeria Journal of Engineering Vol.16 No. 2, March 2010

associated impurities (Ahmed, 1986; the intermediate coarse particles on the third
www.wikipedia, 2008), which needs to be day.
removed and the extent of which is determined
.by the intended final use of the alum thus A sample from the ::;50t-tm clay fraction
obtained. The process of improving on the (sample S) was taken at this stage before series
quality of a mineral ore is commonly called of decantation rounds on the slurry (::;50t-tm
beneficiation and it involves various clay fraction) to ensure near complete removal
procedures (www.wikipedia, 2008). of free silica, which are close to kaolin in
particle size distribution but seemingly heavier
Although several reports exists on alum in mass (Othmer, 1997). The kaolin fraction
production from Kankara kaolin (Aderemi obtained at this stage is referred to as fully
2002; Aderemi and Oludipe, 2000; Aderemi et beneficiated sample, marked Sample B. Prior
al, 2001, 2006), but no one has deliberately to analysis all the marked samples were dried
attempted to quantify the effect of at 120DC overnight to ease handling and attain
beneficiation on alum yield or quality. It is uniform moisture content. Subsequently, the
therefore the aim of this paper to report a fully beneficiated sample was analyzed to
systematic study of the effect of the raw determine its particle size distribution, this was
material beneficiation on yield and quality of in addition to the elemental analyses of the
alum via acid dealumination process. various beneficiated samples.

2.0 Materials and Methods Prior to the dealumination stage, the dried
Raw Kankara kaolin, procured from lumps of the kaolin samples were crushed in a
Kankara village, in Katsina state was crushed jaw crusher (Retsch KG 5657 HAAN), ball
using a mortal and pestle. It was then soaked milled into fine powder and sieved using a 212
in water (inside a plastic bucket) and properly t-tm sieve attached to a shaker. Consequently,
blunged to break up the small lumps and the the sieved dry kaolin powder samples were
colloidal suspension was allowed to stand for then placed into crucibles and calcined in a
three (3) days. During this period it was muffle furnace (Vecstar England, 0- 1lOOK) at
periodically stirred and fresh water added after 750°C for two (2) hours to yield the more
removing the previous day's water by reactive metakaolin (Aderemi and Oludipe,
decantation. This was to remove the soluble 2000).
impurities in the clay. Samples (Raw, dayl,
day2 and day3) of the clay were taken on a In a typical run, using the heat of mixing
daily basis before fresh water was added. The method to dealuminate kaolin, 50g of the
kaolin suspension was thereafter sieved twice metakaolin from the different stages of
using a 50 micron sieve in order to get rid of bcncfici.uion (raw. day I. day2, day3, S and B)
\I ,I' Illl".hlirl'd in« \ a conical flask and a
Edomwonyi et al Beneficiation of Kankara Kaolin for Alum Production

calculated amount of distilled water that will

bring the acid concentration
(Aderemi and Oludipe, 2000) was added and
to 60 wt %
Ah(S04h(aq) + 27H20(l)
Ah(S04h.27H20(s)
-. O°C

(3)

Alum
stirred. A specified quantity of 96wt% sulfuric
250°C
acid (5 folds stoichiometric requirement) was Ah(S04h.27H20 (s~
Ah(S04h.4H20(s) + 23HtO(g) -
measured and then added to the metakaolin
(4)
suspension in the conical flask and the reaction Alum (Partially dried alum)
left for about 30 minutes, after which
additional distilled water was then added to Two sets of commercial grade alums were
quench the reaction. The reaction mixture was procured from the open market in Sokoto City
filtered through a sinta glass filter. Prior to and were equally dried and analyzed in other
crystallization, the filtrate was diluted with to compare them to the sample alums
about 285cm3 of distilled water to enhance the produced.
ease of separation of the excess acid from the
alum by taking advantage of the freezing point 3.0 Results and Discussion
depression of sulfuric acid solutions on 3.1 Effect of beneficiation on kaolin yield
dilution (Weast, 1978). The filtrates were then and quality
cooled at temperature of OOCfor about 4 hours From the results of the gravimetric analysis
(Aderemi et al, 2001, 2006) for the alum to carried out, an average of O.91kg of dried
crystallize out of the mother liquor. beneficiated kaolin was obtained per kg of raw
Kankara kaolin, this could be due to the
The alum crystals were then dehydrated by rigorous sieving and decantation procedures.
heating at 250°C for 6 hours in an oven to ease This implies a high recovery rate of kaolin
handling and analysis by the Energy from its raw state and it is in agreement with
Dispersive X-ray Fluorescence machine (ED- results reported by Ahmed and Onaji (1987).
XRF; PANalytical, PW1660,XRA). Reactions The remaining mineralogical composition
1, 2, 3 and 4 state the essentials of the being montmorillonite, mica, quartz,
processes of calcination, dealumination, carbonaceous and soluble components. This
crystallization and partial dehydration result is also corroborated by the particle size
respectively. analysis carried out on the beneficiated

AlzShOs(OHMs)
+ 2HzO(g)
Kaolin Metakaolin
-.
7500e
Ah032SiOz(s)
(1)
Kankara kaolin which indicated an effective
particle size of 0.0003mm and a coefficient of
uniformity of 9.3 (Fig 1 referred). This which
ioo-c implies a high purity level kaolinite (Ahmed
Alz032SiOz(s) + 3H2S04(aq) -.
Ah(S04h(aq) + 2SiOz(s) + 3HzO(l)- (2) and Onaji, 1987) and has an
Metakaolin Acid improved/expected s.urface area that enhances
Silica
conversion yields (Othmer, 1997). This was

29
Nigeria Journal of Engineering Vol.16 No. 2, March 2010

further confirmed when on calcination to Increase in the surface area due to

metakaolin, a loss of 14.147 wt% was pulverization effect. Following the same
observed which is in good agreement with reasoning, further increment was attained after
stoichiometric expectation of 13.95% for pure sieving through 50llm sieve (point S on Fig.2
kaolinite (Grim, 1953; www.wikipedia, 2008) referred). Expectedly, point B (rigorously
and indicated a high conversion to metakaolin beneficiated kaolin) on Fig. 2 gave the highest
which is necessary for a tangible yield possible (81.30wt%) in this setup,
dealumination rate. possibly resulting from the fact that the fully
beneficiated clay has the highest alumina
Tablel shows the elemental composition of concentration and purity as corroborated by
the raw kaolin, beneficiated kaolin and Table 1 and Fig 1 respectively. It therefore
metakaolin from Kankara kaolin. It was implies that the yield of alum per mass of
observed that the alumina content increases metakaolin is a function of the pulverization
steadily with beneficiation, which suggests level and purity of the kaolin.
that, the goal of the beneficiation process
which is aimed at increasing the ratio of 3.3 Effect of beneficiation on alum quality
alumina to silica was achieved. Though the Table 2 shows the extent of beneficiation on
silica content is also seen to increase the quality of alum from Kankara kaolin. The
numerically, this was not in the same amount of impurities present as oxides is a
proportion with the alumina. This also implies reflection of the quality of the alum. It is
that the .materials removed during the interesting to note that silica (Si02), which was
beneficiation process are high silica containing the major setback in the attempt by the pioneer
minerals, basically, montmorillonite, mica and workers to make alum for water purification
quartz as reported by Ahmed and Onaji from kaolin in Nigeria, is below detection or
(1987). The ratio of the silica to alumina was altogether absent in this investigation (Table 2
observed to attain the literature value of 2 to 1 referred), indicating the high quality of the
for metakaolin, thus indicating full conversion alums developed in this work and its
of Kankara Kaolin to metakaolin at 750°C suitability for water treatment for public
(Grim, 1953; www.wikipedia, 2008). consumption (Harrison, 2004). This success,
we believed was a result of stringent measures
3.2 Effect of beneficiation on alum yield in the filtration step maintained in this work
Fig 2 shows the dependence of alum i.e. use of sinta glass filter instead of filter
yield on duration and extent of beneficiation. paper. It was observed also, that the major
It was observed that the percentage yield of oxide that was affected by the beneficiation
alum is relatively constant for the first two process is magnesium oxide (MgO), with
days of soaking and plunging and rose slightly about 85.97% reduction. This tremendous
on the third day signifying probably slight reduction in the M~() content is observed

30
Edomwonyi et al Beneficiation of Kankara Kaolin for Alum Production

between the alum from the raw kaolin and that described rigorous beneficiation step may be
from the sieved kaolin, which may not be inevitable though at additional cost chargeable
unconnected with the fact that most to the product.
magnesium compounds are insoluble in water
at room temperature (www.wikipedia, 2008). 3.4 Sample alum versus commercial alum
The presence of MgO deri ves from Table 3 shows the elemental composition of
magnesium suIfate (MgS04) and magnesium alums produced from Kankara kaolin in the
carbonate (MgC03) and are known to increase course of this investigation in comparison with
the hardness of water were the alum to be used two commercial alums obtained from the
for water treatment, which is undesirable for Sokoto central market. Silica and potassium
public consumption (Harrison, 2004). oxides are observed to be below detection
level while the sulfite (S03) contents are
The other oxides are not observed to change almost the same for all the alums. The calcium
much; nonetheless their concentrations are content of commercial alum 2 is twenty times
within recommended limit (SONINIS 554, that in sample alum, while the MgO content of
2(07). Potassium oxide (K20) is observed to commercial alum 1 is ten times that in sample
be significantly low or below detection in all alum. Also, the ferric content of commercial
the alums probably owing to its high solubility alum 2 is about six times that in the sample
index, which explains why it remained in the alum. It can therefore be clearly stated that to
mother liquor. The low iron content :s 0.5wt% get the same quality of alum as that most
in all the produced alum samples readily available in the open market today, one needs
commends them for metallurgical and not bother about the rigorous beneficiation
refractory applications.(Acquah et ai, 1999; process.
www.alibaba.com. 2008).
4.0 Conclusions
From these results, it can be deduced that the The following conclusions can be drawn from
use to which the alum will be put will the results of this work:
determine the extent of beneficiation demand. 0.91 kg of fully beneficiated Kankara kaolin
For general purpose and for most industrial was obtained per kg of raw Kankara kaolin,
uses, the rigorous beneficiation may be with an effective size of O.OO03mm and a
unprofitable due to the present low cost of coefficient of uniformity of 9.3 and
kaolin (lkg/N, Kankara Village, 2007), which 14.147wt% loss was observed after calcination
may make the 72% alum yield obtained from to obtain a metakaolin with silica to alumina
the raw calcined clay adequate. But for ratio of 2: I. The assay of alums obtained from
processes that demand high grade alums the open market compared more directly with
especially low concentrations of oxide the samples from unbeneficiated kaolin in this
impurities such as CaO, MgO etc, the investigation while 85.97wt% reduction in

31
Nigetria }iournal of Engineering Vol.16 No. 2, March 2010

magnesium, oxide (MgO) content of alum was from the raw kaolin. Thus leading to the
otmUnecli after beneficiation. Also the alums conclusion that the need for beneficiation
~c~! in: the course of this investigation cannot be based on yes or no basis because the
were' observed' ~, !ie' &il.ica~frett; l'he yield: of specific requirement dictates the level/extent
alum' obtained! from f,uU~ beneflictiated' Kankara of beneficiation to employ.
kaolilt' was found to be 8\38% higher. than' that

Aequah. F, Mensah. B, Obeng, Y. ~l999). An unpublished M.Sc thesis. Department of

Preducuon of alum from Awaso Bauxite. Chemical Engineering, Ahmadu Bello
P\lfMi~f in; the Ghana Engineer. University, Zaria.

Aderemi, 8'.0.: Kinetics ~20(2). Study on Grim, R'.E. (f953). Clay Mineralogy,
A1aminum, Sulphate Crystal> Gi'-owtn out of MCGIl3W-HillBook ce.
Inc., pp 46, 212.
Kankara Kaolin Dealumination Spent Add, -
A Spent Acid Recovery Process. Nig. J. of Harrison, J.F (2004), Water treatment
Eag. ];~1)27 - 34 fundamentals by Water quality association,
USA, pp 69-92"
~deremi', lB'..O; Oloro; B.F, Joseph, D; Oludipe,
]i, (200!l) Kinetics of the Dealumination of Kirk Othmer (1997); Encyclopedia of
Kankara Kaolin Clay, NJE vo1.9 Nol, pp 40- chemical technology. Wiley Interscience New
44. York. Vol3

A'-deremi, B.O. and, Oludipe, J.O:: Marstiller, C.M. (1978). "Aluminum Oxide
(2(i)()(i}):.Deaiuminationof Kankara Kaolin Clay (Alumina)" In: Kirk-Othmer (Ed.),
-Ji)evelopment. of Governing Rate Equation. Encyclopedia of Chemical Technology, Wiley
Nig. J. of Eng. 8~2) 22-30. Interscience New York, vol. 2, pp 219-240.

Aderemi, B.O; Ahm~d; A.S; Abdul B.D Raw Material Research and Development
(2006). Production of alum from Kankara Council (2000), Raw Materials and Consumer
clay. JNSChE 21 (1,2) pp 12(}'124 Industries in Nigeria, www.rmrdc.org.

Ahmed, K.S and Onaji, P.B (1987). The effect SONINIS, 554. (2007). Water treatment and
of beneficiation on the Properties of some water quality standard in Nigeria. By Standard
Nigerian refractory clays, JNSChE 6(2) 119- Organization of Nigeria and related agencies
129 in Nigeria.

Ahmed, K.S. (1986). Development of Weast, R'C, ed (1978). CRe Handbook of

phosphate bonded fireclay refractory castables.
An M.Sc thesis. Department of Chemical Chemistry and Physics, CRC Press Inc. 58 ed,
Engineering, Ahrnadu Bello University, Zaria.
pp-262, D-67.
Azom.com (2008). Alumina - The Types of
Commercially Available Grades,
Azom.com.pty. Ltd. www.alibaba.comlaluml2008

Edomwonyi-Otu, L.C, (2008). Effect of www.wikipedia.com/Alum/2008

beneficiation and salting agent on the yield
and quality of alum for Kankara kaolin clay.

32
 Beneficiation of Kankara Kaolin/or Alum Production
Edomwonyi et al

11. (11IIII)
, ~A ~
r , I ----,
..,., .,
100
1'\

'"
o •.•
"'- ~a§ •
1'\
Cl" et.""
•
CI"~

100

M
90 I 9U 90

10) - In
10

10D ..• 10

t.OI ,. u. ..
60
/
!!I
.~ S3
./
SO ,. I'SO
!
~ 40 I, .. 40 40
•
C
o
~ 30
:. - JQ 30

~t'i 20 20

10 I IU 10
~ ~
0
0.0001 0.001 0.01 0.1 1.0 10 100
Panitle Size (mm)

CLAY

~ffer:.T\v~ ~fk~ (Dlo):, o 0003 ir'11\

G~~HICrENT OF UNIFO~Mlry (2 Co \::

Co,o J
"3
Figure 1: Particle size analysis for beneficiated Kankara kaolin

33
Nigeria Journal of Engineering Vol. 16 No. 2, March 2010

90 -_. - - -- _._--- -_._------

85·

80

'0"
~ 75

~ 70

~ 65

60
,

55 -I

50 -'-------~---------------------------'
RAW DAY 1 DAY 2 DAY3 s B
EXTENT OF BENEFICIATION

Figure 2 Variation of alum yield with extent of beneficiation of Kankara kaolin

=
Where S sieved through 50p.m sieve after 3 days of soaking; B = rigorously beneficiated kaolin;
RAW = raw calcined kaolin; DAYl, DA Y2, DAY3 = clays soaked in water for 1, 2, 3 days
respectively before calcination

T a bl e 1 El ementa composmon 0f iciate dk ao liman d meta kao rm

raw an db ene fici
SAMPLES Si02 Al203 CaO Fe203 MgO K20 Na20 Ti02 Si02: Ah03

Raw 45.10 33.4l 0.343 0.555 1.49 0.693 0.Ol6 O.lOO 2.295

Kankara

kaolin

Beneficiated 47.48 36.80 0.325 0.562 1.27 " " I~ , 0.050 0.066 2.179

kaolin I
-
Metakaolin 49.40 41.56 0.289 0.483 I I: 0.-1: - (I.m8 0.067 2.0203

(750oC12hr)

34
Edomwonyi et al Beneficiation of Kankara Kaolin for Alum Production

Table.2: V ..
- -- - -------- - f al
- -------- - r
------- 'h
---- -------- -f benefici------. - ---
OXIDES IN WT %
Time(Days) Si02 S03 K20 CaO Fe203 MgO CuO Na20 Cr203 NiO
Raw kaolin NO* 74.57 NO 0.17 0.13 1.96 0.049 0.095 0.008 001
OAY I NO 71.92 0.04 0.20 0.14 1.21 0.060 0.055 0.01 0.015
OAY2 NO 67.40 0.01 0.20 0.195 1.68 . 0.045 0.08 0.01 0.01
OAY3 NO 70.50 0.04 0.24 0.165 1.68 0.045 0.11 0.015 0.013
S NO 70.61 NO 0.24 0.25 0.29 0.105 0.085 NO 0.Ql
B NO 69.61 0.275NO 0.190.13
0.125 0.06 0.01 0.02
ND*= Not detectable S=alum from sieved kaolin, Bealum from fully beneficiated kaolin

Table.3 C f th litv of - - -- - d
----- - --- ----- 'al al
----- ---.-- --
ALUMS AI203 Si02 S03 K20 CaO Fe203 MgO CuO Na20 Cr203 NiO
Sample alum 19.00 NO 70.01 NO 0.20 0.13 0.275 0.06 0.13 0.01 0.02
Commercial 19.60 NO 69.60 NO 0.25 0.11 2.86 0.05 0.13 0.017 0.007
alum 1
Commercial 23.02 NO 71.70 NO 3.68 0.85 0.41 0.06 0.21 0.02 NO
alum 2
Alum from 18.02 NO 73.10 NO 0.16 0.12 1.96 0.05 0.10 0.016 0.01
raw kaolin
*ND = Not detectable

35