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Abstract
Kaolin available in Deopani, Assam of northeastern region of India was characterized by FTIR, XRD, DTA and by wet
chemical analysis methods. The major impurities in the clay are quartz and siderite. Wet sieving of the clay by 53-Am sieve
removes almost all the quartz and a major amount of Fe bearing impurities. The iron content of the clay may be reduced further
by treating with wet high intensity magnetic separator (WHIMS) or leaching with organic acids. The effectiveness of various
leachants follows the order: Oxalic>Oxalic + EDTA>Malonic>Citric acid. Almost all the nonstructural iron may be removed at
room temperature by using 0.4 M oxalic acid solution. The leached clay may find use as a ceramic raw material and filler
material for paper and other materials.
D 2003 Elsevier B.V. All rights reserved.
Keywords: Kaolinite; Clay; Beneficiation; Iron leaching; Oxalic acids; Ceramic clay; Paper filler
1. Introduction
Kaolinitic clay is a versatile industrial mineral. The
oldest known use of the clay is as a ceramic raw
material. Presently, the clay also finds application as a
coating and filler pigment for paper, as a filler for
paint, rubber, insecticide, formulation of medicine,
cosmetics, etc. The main characteristic, which determines the utility of the clay for various applications, is
its purity. Pure kaolinite (Al2O32SiO22H2O) is white
in colour and its chemical composition is 46.54%
SiO2, 39.50% Al2O3 and 13.96% H2O (Grimshaw,
94
95
96
97
Table 1
Oxide composition (%) of Deopani kaolin and its beneficiated products
Sample
SiO2
Al2O3
Fe2O3
TiO2
CaO
MgO
SO24
LOI
Crude clay
53 Am fraction
Black material
53 Am, nonmagnetic
53 Am, magnetic
A
B
58.44
47.20
27.47
45.04
23.92
45.15
45.35
19.11
35.75
5.04
38.67
33.50
38.45
38.31
9.48
2.86
47.32
1.10
20.94
1.17
1.01
0.90
8.54
0.70
8.13
0.66
0.57
0.54
0.17
0.38
7.11
10.98
12.23
5.12
12.65
11.05
13.45
13.75
(A and B) Oxalic acid-treated (0.2 and 0.4 M wrt. iron content) fine fraction.
Fig. 3. FTIR spectra of kaolin. (A) Crude clay. (B) Black materials.
(C) Magnetic fraction of 53-Am fraction. (D) 53-Am fraction.
515 and 992 jC, respectively. These peaks are however very weak indicating presence of large amount of
impurities in the clay. The pattern also shows a weak
endothermic inflexion at 433.5 jC accompanied by a
weight loss peak in the DTG curve, suggesting
presence of small amount of other types of minerals
in the clay sample. The XRD pattern of the crude clay
(figures not shown) shows sharp peaks at d = 7.14,
due to kaolinite and
4.35, 3.57, 2.28, 1.67 and 1.54 A
98
Table 2
FTIR band assignments of Deopani kaolin and its beneficiated
products
Assignments
OH vibration
CO3 vibration
mas, Si O Si
m, Si O
Al...O H
ms, Si O Si
m, Si O
AlVI O Si
Si O
Band (cm 1)
3694, 3653, 3620
1400 (b)
1110
1033, 1007
937, 916
794, 754
694
538
469, 428
and
of the clay, weak peaks at d = 9.83, 3.19 A
due to the presence of
at d = 2.68, 2.49 and 4.16 A
small amounts of mica and goethite and/or hematite,
respectively.
The black material is rich in Fe2O3 ( f 47.32%),
SiO2 (27.47%), Al2O3 (5.04%). Besides, it contains
CO32 and SO42 , etc. The FTIR spectrum of the
black material exhibits a strong band at 1420 cm 1
and another two weak bands at 865 and 736 cm 1
(Fig. 3). The intensities of these bands decrease on
acid treatment, indicating the bands due to carbonatebearing minerals. The DTA pattern of the black
material (Fig. 4) exhibits weak endothermic peaks at
568 and 530 jC due to quartz and siderite and
exothermic peaks at 444 and 485 jC due to pyrite
and carbonaceous materials, respectively. The XRD
pattern of the material (figure not shown) shows
prominent peaks due to quartz (d = 3.34, 2.28, 2.13,
) and siderite (d = 2.79, 1.74, 1.73 A
) and weak
1.38 A
),
peaks due to disordered kaolinite (d = 7.11, 3.54 A
) and mica
goethite and/or hematite (d = 4.18 A
).
(d = 9.83 A
3.2. Beneficiation of the clay
Fig. 2 reveals that the 53-Am fraction separated
by wet sieving constitute about 50% of the crude clay
and 97% of the 53-Am fraction may be obtained as
a nonmagnetic fraction by WHIMS treatment. The
53-Am and the nonmagnetic fraction on acid leaching followed by fractionation by dispersion cum
settling method generates about 45 49% fine fraction
( < 4 Am).
The SiO2 (47.20%) and Fe2O3 (2.86%) contents of
the 53-Am fraction are considerably less and Al2O3
99
Table 3
Iron content in the beneficiated clay (fine fraction) after treatment
with different leachants
Leachants
Fe2O3 content
(%)
Oxalic acid
Citric acid
Malonic acid
Oxalic + EDTA
1.00
1.30
1.25
1.04
Table 4
Effect of shearing rates, times and oxalic acid concentration on removal of iron from Deopani kaolin and its nonmagnetic fraction
Acid concentration
(Fe2O3:oxalic acid) (M)
Shearing
rate
Shearing
time (h)
Medium
Fine
1.0:0.0
1.0:0.2
1.0:0.4
1.0:0.0
1.0:0.2
1.0:0.4
1.0:0.0
1.0:0.2
1.0:0.4
1.0:0.2a
1.0:0.4a
Low
Low
Low
High
High
High
High
High
High
High
High
1
1
1
1
1
1
12
12
12
12
12
3.63
3.48
3.34
3.38
2.75
2.61
3.37
2.66
2.60
1.69
1.64
2.60
2.32
2.27
2.52
1.85
1.77
2.64
1.64
1.53
1.59
1.49
2.52
2.12
1.60
2.21
1.31
1.23
2.17
1.17
1.00
1.03
1.00
(0)
(4.13)
(7.99)
(0)
(18.64)
(22.78)
(0)
(21.07)
(22.85)
(0)
(10.77)
(12.69)
(0)
(26.59)
(29.76)
(0)
(37.88)
(43.04)
(0)
(15.87)
(36.51)
(0)
(40.72)
(44.34)
(0)
(46.08)
(53.46)
Coarse = 53, + 10 Am fraction. Medium = 10, + 4 Am fraction. Fine = 4 Am fraction. Shearing rate: low: f 270 rpm, high: f 14,000 rpm.
a
Nonmagnetic fraction.
100
20
10 2
53 Am fraction
98.57 88.66 70.77
53 Am, nonmagnetic fraction
98.03 85.81 67.83
Oxalic acid leached fine fraction
100.00 100.00 99.73
Oxalic acid leached medium fraction 100.00 97.47 77.81
Oxalic acid leached coarse fraction
98.93 62.41 31.21
27.87
27.23
79.32
16.74
6.20
Fractiona
Brightness
(ISO) (%)
1.0:0.0
coarse
medium
fine
coarse
medium
fine
coarse
medium
fine
66.6
73.1
80.0
72.0
78.9
85.0
73.0
79.5
87.0
1.0:0.2
1.0:0.4
Fig. 7. Thermoanalytical curves of leached kaolin: () fine
fraction; (- - -) medium fraction and (--) coarse fraction.
101
Table 7
Technical properties of processed Deopani kaolin for utilization as a ceramic raw materials
Characteristics
Fineness ( + 44 Am in %)
Loss on ignition (% by wt)
Al2O3 content (% by wt)
Fe2O3 content (% by wt)
TiO2 content (% by wt)
Fe2O3 + TiO2 content (% by wt)
Water of plasticity (%)
Shrinkage
Dry shrinkage (%)
Fired shrinkage (%)
Particle size distribution (%, max)
>25 Am
>10 Am
< 2 Am (min)
Fired characteristics at 1350 jC
Colour
Deopani kaolin
Grade I
Grade II
Grade III
0.5 (max)
13.0 (min)
37.0 (min)
0.8 (max)
0.7 (max)
1.5 (max)
32 (min)
1 (max)
12 (min)
34.0 (min)
1.0 (max)
0.8 (max)
1.8 (max)
35 (min)
2 (max)
10.5 (min)
32.0 (min)
1.5 (max)
1.0 (max)
2.5 (max)
38 (min)
0.44
12.23
35.50
1.70
0.90
2.60
31.20
0
13.75
38.31
1.00
0.57
1.57
36.50
1.20
12.65
38.67
1.10
0.70
1.80
32.30
6 (max)
16 (max)
7 (max)
17 (max)
8 (max)
18 (max)
3.50
14.50
1.80
13.40
2.50
13.50
7.31
29.23
27.87
Black spot
Cream
0
0.27
79.32
meet
white
9.83
32.17
27.23
meet
white
5
7
10
15
20
25
70
65
60
Should be free from black specks/spot and cracks.
Pink
white
white
(A) 53 Am fraction. (B) Oxalic acid-treated (0.4 M wrt. iron content) fine fraction. (C) 53 Am fraction (nonmagnetic).
Table 8
Technological properties of processed Deopani kaolin for utilization as a filler material in paper, rubber, plastic and paint industry
Characteristics
Particle size
>53 A (max)
>10 A (max)
<10 A (min)
LOD
LOI (max)
Matter soluble in HCl (max)
Matter soluble in water (max)
Fe2O3 (max)
Whiteness
pH of the extract
MnO (max)
Filler in papera
0.8%
5.0%
75.0%
2.0% (powder)
14.0 15.5%
2.50%
0.50%
0.60%
80 85%
4.5 7.5
0.013%
1.0%
15.0%
60.0%
14.0 15.5%
2.50%
0.50%
0.75%
4.5 7.5
(A) 53 Am fraction. (B and C) Oxalic acid-treated (0.2 and 0.4 M wrt. iron content) fine fraction.
a
Indian Standard Specifications, IS: 505, 1978.
Deopani kaolin
A
1.54
27.41
70.59
1.05
13.05
2.60
0.40
1.70
75.5
6.5 7.0
0.009
0
0.27
99.73
1.49
13.45
2.10
0.42
1.17
85.0
5.0 5.5
0
0.21
99.79
1.68
13.75
1.80
0.44
1.00
87.0
5.0 5.5
102
4. Conclusions
Deopani kaolin mainly contains kaolinite, quartz as
the major mineral with siderite (FeCO3) as the major
iron-bearing impurity. Wet sieving of the clay below
53 Am removes almost the entire quartz and considerable amount of iron. Further treatment of the clay
with WHIMS generates clay required for use as a
grade II and III ceramic raw material as described in
Indian standard specifications. The iron content of the
clay may be further reduced with improvement of the
technological properties by leaching with organic
acids. Oxalic acid was found to be the best leachants
amongst the investigated organic acids. Preliminary
evaluation of the technological properties indicate that
the oxalic acid treatment can improve the quality of the
clay, which meets almost all the requirements for grade
I ceramics and filler material as described in Indian
standard specification. Further study is necessary to
establish the process parameters for generation of
better quality of products.
Acknowledgements
The authors are grateful to the Ministry of Coal and
Mines, Department of Mines, Government of India,
New Delhi for financial grant and State Directorate of
Geology and Mining, Government of Assam for
providing the kaolin sample. The authors are also
grateful to Indian Bureau of Mines, Nagpur, India for
extending WHIMS and XRF facilities and to Dr. R.K.
Barua, Scientist and Mr. P. Khound, Technical
Assistant of this laboratory for recording the XRD
patterns and FTIR spectra, respectively. The authors
are also thankful to Dr. R.N. Mishra, Retd. DDG, GSI,
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