Value Addition of China Clay by the Removal of Titanoferrous Minerals 71

Value Addition of China Clay by the Removal of

Titanoferrous Minerals
P. Raghavan*, Sathy Chandrasekhar*, S. Ramaswamy* and N. Suresh**
*Regional Research Laboratory, CSIR, ** Dept . of Fuel & Minerals,
Govt. of India, Trivandrum, India Indian School of Mines, Dhanbad, Jharkhand

ABSTRACT: Kaolins or china clays are naturally-occurring earthy materials predominantly containing the
mineral kaolinite, Al2O3 2SiO2 2H2O. The material is characterized by unique properties and is used for a
number of applications. Impurity minerals normally present in kaolin are quartz, various iron oxides and
sulphides, titanoferrous minerals etc. By removing or reducing these, the brightness, which is the most
important parameter for the beneficiated clay, can be enhanced to acceptable levels. Out of all these
impurities, the colouring titanoferrous minerals pose problems for removal.
This paper describes the laboratory and micro-pilot plant investigations carried out on Mamuara clay from Kutch,
Gujarat for the removal of titanoferrous minerals and hence to improve the brightness so that the clay satisfies
international specifications for paper coating. The techniques employed are size classifications, selective
flocculation, Super-Conducting High Gradient Magnetic Separation (SCHGMS) and flotation as single operation or
in combinations. While raw clay measured a brightness of 70.3% ISO, a combination of size classification,
SCHGMS and flotation increased the brightness to 85%. The titania content reduced to 0.35% from 2.3% (raw
clay). The overall clay recovery is 43%. The clay is just at the brim of the international specifications for coating
clays as far as brightness is concerned.

1. INTRODUCTION colouring impurity is titanoferrous minerals.

Kaolin or china clay is naturally-occurring earthy
material predominantly containing the mineral
kaolinite, Al2O3 2SiO2 2H2O. The material is
characterized by unique properties such as
colloidal particle size, thin platelet shape, high
brightness, excellent opacity etc. Although most
important in paper making, kaolin is used
extensively in paint, rubber, plastic, fertilizer, ink,
ceramics, cement, insulators, fiberglass, pharma-
ceuticals, cosmetics etc. The international
specifications for coating clays prescribe a
minimum brightness value of 85% ISO.
China clay is available in most parts of the
world. The global production stands at 44.4
million tons by the year ending on March 2006 as
reported by US Geological Survey Mineral
Resources Program. ‘The total Indian reserves is
estimated to be 1525 million tons as on April
2000. Annual Indian production for the year
2005-06 is about 1.1 million tons (IBM, 2006)’.
Impurities normally present in kaolin are
quartz, various iron oxides and sulphides,
titanoferrous minerals, mica etc. The main
While coarse and fine titanoferrous minerals can
be removed by settling and centrifugal operations,
the ultrafine particles can be removed by Super-
Conducting High Gradient Magnetic Separation
(SCHGMS), (reverse) froth flotation and selective
flocculation either singly or in different
combinations. While selective flocculation results
generally in low clay recovery, both SCHGMS
and flotation have found success commercially
with many clays around the Globe. Again, quite
often, discrete particles of iron-containing anatase
is found to be adhering to the kaolinite particles
and smaller the anatase particles, the more they
aggregate with the kaolinite (Chandrasekhar et al.,
2006).
Several investigators (Shi, 1986; Kumar et al.,
2001 etc.) report on the separation of coloured
minerals from china clay by selective flocculation
of titanoferrous minerals using a high molecular
weight polymeric flocculent. The brightness
enhancement achieved is about 3-8 units a low
clay recovery of 60-75%. SCHGMS is a versatile
method for the removal of iron containing
72  Mineral Processing Technology (MPT 2007)
impurities from china clay and especially for Particulars Characteristics
titanoferrous minerals. A number of references are (i) Colour Off-white
available for the same (Watson, 1994; Raghavan (ii) pH 6.9
et al., 1997 etc). Highly successful results are (iii) Particle size analysis
reported and it is a fact that presently most of the Size, μm Wt.%
modern china clay processing plants in the world >45 12
employ SCHGM separators for raising clay <45, >10 09
brightness. Similarly, numerous references <10, >5 07
(Cundy, 1969; Raghavan et al., 2004 etc.) can be <5, >2 14
<2 58
cited for the removal of titanoferrous impurities
(iv) Brightness, %ISO 70.3
from china clay by froth flotation.
(v) Sp. Gravity 2.5
The present paper discusses the investi- (vi) Chemical analysis
gations carried out for the removal of titano- Constituent Wt.%
ferrous minerals from Mamuara china clay by Al2O3 37.9
employing techniques such as size classifications, SiO2 45.5
selective flocculation, super-conducting high TiO2 02.3
gradient magnetic separation and high shear pre-
Fe2O3 00.9
treatment-assisted flotation during its processing
F. Carbon <0.1
studies.
(vii) LOI,% 14.1
(viii) Mineral Phases by XRD:
2. MATERIALS AND METHODS Kaolinite, Anatase, Quartz

2.1 Clay Samples and Reagents 2.2 Equipments

The representative raw clay sample was collected
from Mamuara mines, Kutch in the State of
Gujarat, India. The material for the beneficiation
study was prepared by crushing all the lumps
below 10 mm size and blending. The clay was
characterized by physical, chemical and
mineralogical methods and salient results are
given in Table 1. The data reveals that the titania
content (TiO2) in raw clay, which is a measure of
titanoferrous minerals, is 2.3%. This is relatively
high. The mineral phases identified by XRD are
kaolinite, anatase and quartz. The raw clay
measured a brightness of 70.3% ISO. The titania
content in the product of beneficiation at
appropriate stages which is termed as ‘product
titania’ is taken for all comparisons.
Reagents used for the investigations are
sodium silicate, calgon, sodium carbonate,
sodium meta silicate, polyacrylate (AN103P) and
accumer 9420 as general dispersants, Aero +
promoter 6493 and 6494 as collectors and Nalco
9601, 7763, 9903 and 3416 and superfloc
100PWG and 100CB as selective flocculents.
Table 1: Characterisation of raw clay
Laboratory and micropilot equipments such as
Clay Plant [30 Kg./batch; Edward & Jones (now
USF), UK], Hydrocyclone Test Rig (Richard
Mozley Ltd, UK), Fahrenwald flotation cell
(1 Kg./batch; Ohta Kikai Seisakusho Co. Ltd,
Japan); laboratory 6T/54 (6 tesla) SCHGM
separator [Outokumpu Technology Inc.] were
used for the test work. SCHGMS tests were
carried out at Carpco pilot test centre at Langley,
Berkshire, UK while all other experiments were
carried out at RRL, TVM. Standard measuring
cylinders were used for selective flocculation
studies. Brightness was measured using Colour-
touchTM Model ISO spectrophotometer and XRD
patterns were generated by X’pert Pro of
PANalytical, Holland with Ni filtered CuKα
radiation. Standard wet chemical method was
adopted for chemical analysis.
2.3 Procedure
The operational sequence for the removal of
coarse and fine titanoferrous minerals along with
other impurities are blunging, screening, 2 inch
stub cycloning, 2 inch standard cycloning, one
Value Addition of China Clay by the Removal of Titanoferrous Minerals
inch cycloning and 10 mm cycloning. The
overflow solids of 10 mm hydrocyclone is termed
as Final Size-Classified Mamuara Clay (FSCMC)
which contains all particles below 5 μm. Selective
flocculation, froth flotation and SCHGMS were
independently carried out on FSCMC. Later on,
froth flotation was carried out on the product of
SCHGMS.
3. RESULTS AND DISCUSSIONS
Beneficiation studies involve two major activities.
Initial size classifications to remove the coarse
and fine titanoferrous minerals including other
coarse impurities and later on, operations to
remove ultrafine titanoferrous minerals so as to
enhance the brightness and other optical
properties of the clay.
3.1 Removal of Coarse and Fine
Titanoferrous Minerals and other
Impurities
Coarse and fine titanoferrous minerals and other
impurities (>5 μm) are removed by blunging,
screening and a series of hydrocycloning. The
sample was blunged after adding sodium silicate
or accumer 9420 and was screened to eliminate
the fraction above 300 μm. The undersize slurry
of the screen is subjected to a series of centrifugal
separations using 2 inch stub, 2 inch standard,
1 inch and finally 10 mm hydrocyclones. The
overflow slurry of the preceding cyclone (after
adjusting for pulp density) forms the feed to the
next lower diameter cyclone. FSCMC analysed
1.6% titania and recorded a clay recovery of 56%.
Brightness improvement with all these operations
is in the order of 3.2 units.
3.2 Removal of Ultrafine Titanoferrous
Impurities
Important processes and their combinations
carried out for the removal of ultrafine titania
minerals are (i) Selective flocculation (ii) Froth
flotation (iii) SCHGMS and (iv) SCHGMS
followed by Froth flotation.
3.3 Selective Flocculation
73
FSCMC which analysed 1.6% TiO2 was subjected
to selective flocculation tests with seven number
of selective flocculents for titanoferrous impurities.
Nalco 9601 was found to give the maximum
brightness for the dispersed phase (clay portion).
Further optimization showed that a dosage of
10 ppm of this reagent (w.r.t. dry feed clay) gives
the optimum brightness of 77.2% ISO with a unit
operation (U.O.) clay recovery of 76.5%. The
product clay analysed a titania value of 1.3%.
3.4 Froth Flotation
FSCMC was subjected to a series of flotation tests
using oleic acid (four-membered chelating agent)
with or without an activating metal ion. Later on,
calcite carrier was also added. The brightness
enhancement was relatively low, hence, a five-
membered chelating agent, hydroxamate, was
used. The brightness improvement was in the
order of about 3.2 units (from 73.5 to 76.7%).
However, even this could not take the product
clay brightness to above 85% ISO. The product
titania is 1.35% and the U.O. clay recovery
obtained is 82.5%. Since desired brightness was
not achieved, FSCMC was subjected to SCHGMS.
3.5 SCHGMS
SCHGMS with a field intensity of 3 tesla and,
later on, 5 tesla were carried out. While a two pass
operation gave a brightness of 78.1% for the
former one, the brightness shot up to 83.4% when
the field was increased to 5 tesla under similar
conditions. The product titania with 6 tesla
machine came down to 1.06% with U.O. clay
recovery of 92%. Still the target of 85% was not
achieved.
3.6 Froth Flotation on SCHGMS Product
In order to get further reduction in titania value,
the product of SCHGMS was subjected to froth
flotation under different shear frequency
conditions for the pre-treatment. Enhanced titania
removal was observed as shear frequency
increases. At optimized conditions, the product
titania reduced to 0.35% with U.O. clay recovery
of 86.4%
74  Mineral Processing Technology (MPT 2007)
The product clay attained a brightness of 0.35%. The overall clay recovery is
85%ISO. The value is just at the brim of the about 43%.
international specification for paper coating clays. (ii) Both selective flocculation
Thus with size classifications, SCHGMS and and froth flotation of size-classified clay
froth flotation, the product titania could be resulted only in marginal separation of
reduced to 0.35% from a raw clay assay of 2.3% titanoferrous impurities hence limited
with an overall clay recovery of 43%. Total enhancement of brightness.
brightness enhancement is in the order of 14.7 (iii) Even with two-pass (5
units (from 70.3 to 85%). tesla) SCHGMS followed by high shear
pretreatment-assisted flotation, the
3.7 Relationship between Titania brightness achieved is only at the brim
Content and Clay Brightness of international specification for coating
clays i.e., 85%, hence further
A plot of brightness V/s product titania (Fig. 1) upgradation for use of Mamuara clay as
shows the inverse proportionality wherein the high grade hydrous paper coating grade
brightness of the clay increases as product titania clay is to be looked into.
reduces. The higher slope in the middle portion
of the curve indicates that SCHGMS is the
most effective technique for the removal of 5. ACKNOWLEDGEMENT
titanoferrous impurities from Mamuara clay
whereas the brightness increase for flotation is the Authors are thankful to Prof. T.K. Chandrashekar,
lowest. Director, RRL, TVM for giving permission to
present this paper.

86

84 REFERENCES
Brightness, % ISO --->

82

80
[1] Chandrasekhar, S., Vogt, V., Raghavan, P. and
78
Gock, E., 2006. Possibility of recoating of
76
impurities on product kaolin during froth
74
flotation—HRTEM-EDS study: Proc. Int.
72
Seminar on Mineral Processing Technology-
70
2006, Allied Publishers, New Delhi.
0.0 0.5 1.0 1.5 2.0 2.5
[2] Cundy, E. K., 1969. Processing of clay: U.S. Pat.
Titania, wt. % ----->
No. 3 450 257.
[3] IBM Web site, Dec. 2006; Indian Bureau of
Mines, Nagpur, India.
Fig. 1: Relationship between product titania [4] Kumar, G.V.S.S., Menon, S.K., Agrawal, Y.K.
and clay brightness and Vora, S.B., 2001. Selective flocculation
separation of iron and titaninum from Kutch
4. CONCLUSIONS kaolins (India); Indian Journal of Engineering
and Material Sciences, Vol. 8, pp. 170-176.
(i) The removal of [5] Raghavan, P., Chandrasekhar, S., Vogt, V. and
titanoferrous impurities from Mamuara Gock, E., 2004. Separation of titanoferrous
clay could be achieved through a impurities from kaolin by high shear pre-
combination of size classifications, treatment and froth flotation: Applied Clay
SCHGMS and high shear pretreatment- Science, Vol. 25, pp. 111-120.
[6] Shi., 1986. Method of beneficiating kaolin clay
assisted flotation so as to enhance the
utilizing ammonium salts: U.S Pat. No. 4 604 369.
brightness from 70.3 to 85%. The final
[7] Watson., J.H.P., 1994., Status of superconducting
product analysed a titania content of magnetic separation in the minerals industry.,
Minerals Engg., Vol. 7, No. 5/6 pp. 737-746.