Minerals Engineering 15 (2002) 1191–1192

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Technical Note

Purification of north Brazilian kaolin by selective flocculation

F. Larroyd, C.O. Petter, C.H. Sampaio *

Mineral Processing Laboratory, Federal University of Rio Grande do Sul, P.O. Box 15021, Porto Alegre 91501-970, Brazil
Received 21 May 2002; accepted 23 August 2002

Abstract
The main kaolin deposits in north Brazil present are contaminated with colored titanous impurities. Conventional beneficiation
processes do not completely remove TiO2 . The difficulty in separation is mainly due to the ultra-fine size of the minerals.
This work presents a study of an alternative kaolin purification method based on selective adsorption of soluble polymers. In the
process, flocs were generated by interaction of anionic polyacrylamide with titanous impurities and were separated from the kaolin
suspension through sedimentation.
Ó 2002 Published by Elsevier Science Ltd.

Keywords: Flocculation; Industrial minerals

1. Introduction 2. Results and discussion

The main kaolin deposits in the world, located in
Georgia State (USA) and in the Amazon region, north
of Brazil, contain titanous impurities. The optic quality
(brightness) of the kaolin produced in these regions
depends directly on the beneficiation process used to
remove these impurities.
Selective flocculation has been studied for more than
30 years. Very good results were obtained at laboratory
and bench scale (Yoon and Shi, 1986). The flocs are
generated by interaction of a flocculant polymer on one
mineral, while other minerals stay in suspension.
The kaolins used in this work came from the north of
Brazil. Prior to the tests the samples were submitted to
dispersion, removal of coarse material, centrifugation
and magnetic separation. A pulp with 30% solids was
prepared at a controlled pH and dispersants were added.
The products were analyzed by X-ray fluorescence for
TiO2 content.
Two different anionic polymers were tested: Super-
flocâ A-100 and Superflocâ A-150. The concentrations
of negative charges tested were 10% and 50%.
The rate of sedimentation and flocs compaction were
studied with the use of a Turbiscanâ.
*
Corresponding author.
E-mail address: sampaio@ufrgs.br (C.H. Sampaio).
0892-6875/02/$ - see front matter Ó 2002 Published by Elsevier Science Ltd.
PII: S 0 8 9 2 - 6 8 7 5 ( 0 2 ) 0 0 1 8 1 - 4
The polymer used in this work was a polyacrylamide,
partially hydrolyzed. This flocculant, also called a co-
polymer, consists of a combination of amide and carb-
oxylic groups with polar and nonpolar affinity respec-
tively. The ionic charge is calculated by the percentage
of monomer units that are hydrolyzed. Usually they are
formed by sodium acrylate.
According to Lee et al. (1991), the adsorption of
anionic polyacrylamide is controlled by hydrogen bonds
between amide groups and hydrolyzed metallic sites
present on the mineral surface.
The effect of pH and polymer type on efficiency and
mass recovery of the selective flocculation were studied.
In the pH range studied (from 7 to 11) the polymer
SFA-150 with high anionic charge (50%), was shown to
be inefficient in removing the TiO2 present in the kaolin.
The titanous impurities were significantly removed by
the use of polymers with weak anionic charges (10%) in
alkaline medium. At the most favorable condition
(pH ¼ 10), the TiO2 content fell from 1.39% in the bulk
sample to 0.952% in the selectively flocculated product
(Fig. 1). Sodium hexametaphosphate concentration was
around 2.8 Kg/t. This concentration provides the ideal
kaolin dispersion with the maximum suspension fluidity
and with an appropriate dispersant.
A study was performed aimed at providing the
highest removal of anatase with a high kaolin mass re-
covery. The tests were carried out at high concentration
1192 F. Larroyd et al. / Minerals Engineering 15 (2002) 1191–1192
Fig. 1. Influence of polymer ionic charge and medium pH on the TiO2
removal.
. . . . . . . .
Fig. 2. Kaolin mass recovery and TiO2 content for different ionic
ambients.
of hexametaphophate and at pH 10. In each ionic am-
bient, characterized by a specific dispersant concentra-
tion, a study was carried out at different concentration
of the polymer SFA-100 (ambient 1: 2.8 g/Kg of hexa-
metaphosphate; ambient 2: 3.8 g/Kg; and ambient 3: 4.8
g/Kg).
The curves shown in Fig. 2 indicate that the efficiency
of the selective flocculation method in removing anatase
depends basically on the suspension ionic ambient
which, in turn, depends on the chemical dispersant
concentration. A significant improvement in the process
selectivity is observed at high hexametaphosphate and
polymeric flocculant concentrations.
Ionic concentration of the medium also influences the
sedimentation rate of the contaminant flocs (ambient 1:
2.02 mm/min; ambient 2: 2.75 mm/min; and ambient 3:
5.21 mm/min).
Kaolinite and anatase, in the presence of polyphos-
phate anions, and at alkaline pH, have negative surface
charges. According to Shaning and Attia (1987) and
Orumwense (1994), at pH values between 9 and 11
metallic sites on mineral surfaces hydrolyse. In this case,
the flocculation induced by the adsorption of an anionic
polymer on a mineral surface with a negative charge can
be attributed essentially to hydrogen bonds.
The ionic ambients produced with high concentra-
tions of chemical dispersants (from 3.8 up to 4.8 Kg/t)
have been shown to be very effective in removing ana-
tase in kaolins.
Preferential interaction of the polymeric functional
groups with the titanous mineral surface can be ex-
plained due to the higher number of adsorption metallic
sites in comparison to kaolinite. In the kaolinite the
active sites, basically formed by atoms of Al, are re-
stricted to the lateral kaolinite surface (about 10–20% of
the total surface), while on the anatase surface, the sites
are found on almost all of the mineral surface.
3. Conclusions
Selective flocculation appeared to be an efficient
method for removing titanous impurities from north
Brazilian kaolin.
The separation of kaolinite-anatase was possible in
. alkaline medium, with the use of a weak anionic poly-
acrylamide of high molecular weight.
The efficiency of the selective flocculation method in
removing anatase depends on the suspension ionic am-
bient and on the chemical dispersant concentration.
The ionic concentration of the medium influences the
sedimentation rate of the contaminant flocs.
Hydrogen bonds seem to control the adsorption
mechanism of the polymeric functional groups with the
anatase particles.
The intensity of the repulsive forces arising from
charges of the same sign controls the selectivity of the
flocculation process.
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