Purification of relatively low grade kaolin using

physical separation and reverse flotation

Mehdi Sedigh, Javad Vazifeh Mehrabani and Hamed Haghi
School of Mining Engineering, College of Engineering, University of Tehran, Iran

ABSTRACT
In this investigation, the possibility of physical separation methods such as attrition scrubbing,
hydro-cycloning and also reverse flotation were investigated for silica and calcite removal from
relatively low grade kaolin. The head sample was provided by the Iran China Clay Company and
the major oxides contained in the head sample were Al2O3, SiO2, CaO and Fe2O3 with grades of
15.07%, 71.05%, 4.35% and 0.52% respectively. The liberation degree of calcite and iron impurities
from kaolin particles were over 80% for particles finer than 210m and 53m respectively. Attrition
scrubbing tests were carried out with scrubber cell of the conventional Denver flotation cell model
D-12. Laboratory scale hydro cyclone was applied for the beneficiation of kaolin. Attrition
scrubbing tests with control screen of 106m did not achieve the desirable yield for purification of
this kaolin sample, but hydro cyclone experiments resulted in better results. Hydro cyclone with
2.54 cm diameter used and the only variable was the cyclone inlet pressure ranging from 68.65kPa
to 98.07kPa. The best inlet pressure was found to be 68.65kPa. Based on the optimized condition,
Al2O3 and CaO amount in the hydro-cyclone overflow was 23% and 1.47% respectively. However
weight recovery of the overflow in each cyclone experiment was less than 30% and multi stages of
hydro-cyclones would have to be applied for higher weight recovery and better yield. All of the
flotation tests were carried out in the conventional Denver flotation cell model D-12. Reverse
floatation tests for calcite removal were carried out under alkali pH based on full factorial design of
variables in 2 levels including one center point. The three parameters tested were collector dosage
(gr/ton), pH and depressant dosage (gr/ton). The collected data from flotation tests were analyzed
and optimized collector and depressant dosage were 1000 gr/ton and optimized pH was 8.5. Under
the above mentioned conditions, calcite removal was about 75% and CaO content in the final
product was reduced from 4.35% to 1.33%. However calcite removal will increase to more than 83%
if the feed particle size in flotation tests is reduced from 210m to finer than 53m. Finally after
optimization, the best working condition and possible flow sheet were developed.

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INTRODUCTION
Kaolin is a global industrial mineral primarily used as (1) a pigment to improve the appearance and
functionality of paper and paint, (2) a functional filler for rubber and plastic, (3) a ceramic raw material,
and (4) a component for refractory, brick, and fiberglass products. Other lower-volume uses for kaolin
include chemical manufacture, civil engineering, agricultural applications, and some pharmaceuticals
(Pruett & Pickering, 2006; Kogel, 2014). All these applications are the result of favorable properties in
Kaolin such as natural whiteness, fine particle size, non-abrasiveness, and chemical stability (Murray,
1961). Two basically different processes are used to refine kaolin and remove major impurities. The
simplest process is called air flotation or the dry process. The properties of the finished product depend to
a large extent on those properties inherent in the crude kaolin. In the dry process operation, a deposit
must be chosen with desirable properties of color and relatively low content of grit (particles coarser than
44m). The crude kaolin is transported to the mill where the large chunks are reduced to about egg size
by roll crushers. The crushed kaolin is fed into rotary dryers and then into air floating equipment. The
latter usually consists of a pulverizing unit and an air separator. The fine particles are transported to
collecting chambers and the coarse particles are fed back into the pulverizer. Dry processing yields a
product of relatively low cost (Murray, 1961; Kogel, 2014) and product can be shipped in packed bags or
bulk to the customer (Murray, 2007; Kogel, 2014). The second process used to produce kaolin is much
more complex and is called wet process or kaolin washing process. Kaolin particles are dispersed in water
after it is mined. The first step after dispersion is the removal of the coarse grit (>44m) by settling
procedures and vibrating screens. The resultant de-gritted slurry is fed into centrifuges to separate the
kaolin into fine, intermediate, and coarse particle size fractions. These fractions can be chemically
bleached to remove some coloration caused by iron impurities. The kaolin is then dewatered through a
filtration process, dried in either rotary, apron or spray dryers and prepared for shipment. This process is
used to produce highly refined kaolin having controlled properties (Murray, 1961; Kogel, 2014).
The largest known deposit of kaolin in Iran is Zonouz located near Marand city (northwest of Iran) which
is extracted and processed by Iran China Clay Company. The reserve of this mine is estimated about 33
million tons. Kaolin production from Zonouz mine is about 200000tpa (EAOIM, 2006).
Run of mine (ROM) is fed to crushing plant that consists of two stage crushers; jaw and cone crushers. The
crushed minerals below 4 cm, produced in the crushing plant, are homogenized using stacker and re-
claimer then in the grinding stage the particle size of minerals are reduced to less than 200m by Pfeiffer
vertical roller mill (VRM). Then produced powder in the VRM is discharged and mixed with water.
Processing in wet stage consists of washing and sizing by screw classifier and four stages of hydro-
cyclone clusters. In this stage, coarse particles and siliceous impurities are removed. The over flow of the
final hydro cyclone cluster is thickened and dewatered as a final high quality product. This product is
changed to noodle type and then packed into one ton bags. In Figure 1 a simple flow sheet of Zonouz
kaolin plant is presented.
The product of this plant is used in ceramic industry. It should be mentioned that silica content in the final
product is higher than appropriate yield for using in paper production. Other impurities such as iron
oxides are a little high in order to be used as pigments. Fortunately, the amount of TiO2 is very low in
Zonouz kaolin deposit. Another important impurity which it should be reduced to improve the quality of
ceramics, is calcite.

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In this investigation, different experiments were designed and carried out using attrition scrubbing,
hydro-cycloning and froth flotation processes, in order to remove calcite and silica impurities from
relatively low grade kaolin sample (nominated as ZK2 sample) which contains higher amount of calcite
and iron impurities in comparison with current feed of available processing plant.

Figure 1 flow sheet of Zonouz kaolin plant

SAMPLE CHARACTERIZATION AND MINERALOGY

After receiving the sample from the Zonouz plant and preliminary preparation, a representative sample
prepared for chemical analysis. The results were compared with average reported results of quality
control laboratory in plant and presented in Table 1. It should be noted that HSCA analysis is considered
for all of calculations. According to these results and reference to available standard of quality control,
CaO grade is too high and should be reduced to desirable amount (less than 1.5 %) in final product.
Detailed mineralogical studies including investigation of thin and polished sections (up to 37 m) were
carried out. X-Ray diffraction (XRD) analysis was used and compared with chemical analyze and X-Ray
fluorescence (XRF) results. The following results were obtained from mineralogical investigations:
XRD analysis indicated that Quartz and Kaolinite are major minerals while small amounts of Calcite,
Muscovite, Illite and Dolomite were recognized as minor minerals in the samples.
Major impurities were carbonates (Calcite & Dolomite), Quartz, Muscovite, opaque minerals (such as
Goethite, Limonite and Pyrite) and semi-transparent minerals.
For 70% liberation of iron impurities, reduction of particle size up to 53m is essential.

3
 Almost all of quartz particles were liberated at 37m but micro-crystalline quartz was still present in
the sample; therefore milling and sizing by hydro-cyclone will not be sufficient for complete removal
of quartz.
More than 75% of carbonates will be liberated by milling and size reduction of particles below 200m.
Other impurities such as feldspar and pyrite were negligible and finer than 200m and were liberated
completely. Therefore, if necessary, high intensity or high gradient magnetic separation could be
employed to remove pyrite and other iron impurities.
Table 1 Results of chemical analysis for head sample

Oxides Grade (%)

Sample
Al2O3 Fe2O3 CaO SiO2
HSCA 15.07 0.52 4.35 71.05
ACAR 14.50.6 0.70.15 4.01 73.01.5
HSCA: Head Sample Chemical Analysis
ACAR: Average Chemical Analysis reported by Q&C Lab. for ZK2 sample

LABORATORY TESTS

Attrition scrubbing tests

Attrition scrubber was used for possible removal of surface coating and staining from particles. This could
lead to better liberation of clays from surface of silica particles and at the same time improve removal of
iron oxide and hydroxide from the particles surface (Haghi, Noaparast & Ghorbani, 2008).
In this stage four experiments were designed and carried out according to Table 2. Pulp solid percent and
rotor speed of scrubber in these tests adjusted to 70% (by weight) and 1300rpm, respectively. Size control
was applied by 106m sieve. Attrition scrubbing tests were carried out by scrubber cell of conventional
Denver flotation cell model D-12. Comparing the results of the second and the fourth tests are shown in
Table 2 indicating that, decreasing the scrubbing time from 60min to 30min, lead to 50% reduction in
powder production while, Fe2O3 content was not changed significantly in the remained fraction on control
sieve. Addition of sulfuric acid to the tests caused increasing the powder production while no
considerable differences in oxide grades obtained.
Accordingly, control of scrubber output by screen is not desirable and obviously it is better to use hydro-
cyclone with cut size of 38m or finer in closed circuit. Unfortunately continuous implementation of these
tests was not possible in laboratory scale and it should be carried out in pilot tests.
Table 2 Results of attrition scrubbing tests

Test Particle Size Time H2SO4 Weight Oxide Grades (%) Remained on or Passed
Number m min (%) (%) Fe2O3 Al2O3 SiO2 CaO From Control Sieve

44.9 0.43 14.17 70.10 5.23 Remained

1 < 2380 60 -
55.1 0.60 16.14 72.20 2.46 Passed
35.4 0.46 13.83 68.91 5.86 Remained
2 106-2380 60 -
64.6 0.62 15.87 70.77 3.30 Passed

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 55.4 0.41 14.63 71.01 4.25 Remained
3 106-2380 30 20
44.6 0.53 16.09 69.60 2.87 Passed
65.8 0.48 14.93 81.69 2.87 Remained
4 106-2380 30 -
34.2 0.51 16.53 71.43 2.81 Passed

Hydro cyclone tests

Simple flow sheet tests

In this stage some experiments were carried out by laboratory hydro cyclone. Feed particle size and
hydro-cyclone inlet pressure were the variable parameters. The experimental condition and their results
are presented in Table 3. The required feed for hydro cyclone was milled in a dry laboratory rod mill.
Based on the results presented in Table 3, the best calcite removal condition occurred in the test number 3
where the CaO content decreased from 4% to 1.5% in the overflow. In all hydro cyclone tests, Al 2O3 grade
in the overflow increased. Although, calcite removing and increasing Al 2O3 grade occurred in the hydro
cyclone overflow, increasing the grade of Fe2O3 was observed in the overflow considerably. In addition,
weight recovery in overflow stream was relatively low and about 20% in all above tests.
Comparison between test numbers 3 and 4 shows that increasing inlet pressure from 68.65 kPa to 98.07
kPa resulted in negative effect on weight recovery and significant increase of CaO content from 1.47% to
1.98% in final product while there was a little improvement in quality (Al2O3 recovery and brightness)
which is not desirable. Tests number 1 and 3 showed that reducing feed particle size by more milling time
has negative effect on product quality, too. Test number 5 shows that by scavenging the underflow of test
number 4 in hydro-cyclone, the final product weight recovery improved from 18.6% to 25.6% without big
loss in product quality.

Effect of regrinding underflow stream

Regrinding of the underflow stream would causes positive effect for achieving better yield (weight
recovery) without significant loss of quality in final product. The flow sheet of multi-stages hydro-cyclone
including regrinding of first stage underflow and its relevant results is presented in Figure 2 and Table 4,
respectively. In this test, distribution of CaO, Al 2O3, SiO2 and Fe2O3 in overflow was 17.14%, 46.61%,
30.61% and 42.80% respectively. This flow sheet can be useful for increasing the Al2O3 recovery. The
retention time in regrinding mill was set at 4.5 minutes.

Table 3 The Results of hydro cyclone tests

Test d90 Pressure Weight Oxide Grades (%) Brightness Overflow or

Number m kPa (%) Fe2O3 Al2O3 SiO2 CaO (%) Underflow

20.9 0.88 22.38 63.85 2.24 84.4 Overflow

1 150 68.65
79.1 0.61 13.41 72.41 4.71 76.8 Underflow
19.7 0.89 23.10 62.50 2.14 84.8 Overflow
2 150 98.07
80.3 0.58 13.31 72.58 4.74 79.0 Underflow
3 210 68.65 19.9 0.84 22.83 64.10 1.47 84.7 Overflow
5
 80.1 0.54 13.22 72.74 4.40 84.0 Underflow
18.6 0.90 23.43 62.93 1.98 85.1 Overflow
4 210 98.07
81.4 0.53 13.65 72.06 4.82 79.8 Underflow
7.0 1.15 22.44 64.20 1.79 79.4 Overflow
5 (I) 98.07
74.4 0.54 12.54 72.60 4.96 78.3 Underflow
25.6 0.97 23.16 63.28 1.93 83.5 Overflow
6 (II) 98.07
74.4 0.54 12.54 72.60 4.96 78.3 Underflow
(I) : Feed: Underflow of test 4
(II) : Feed: Mixing of overflows in test 4 and 5

Figure 2 Flowsheet for multi-stages of hydro-cyclone with regrinding of first underflow

Table 4 Results of multi-stages hydro-cyclone with regrinding of first stage underflow

Sample Grade (%) Recovery (%)

Weight (%)
Type Al2O3 Fe2O3 CaO SiO2 Al2O3 Fe2O3 CaO SiO2
Feed 100.00 14.89 0.57 4.12 72.22 100.00 100.00 100.00 100.00
O1 23.00 22.15 0.76 1.99 65.01 34.22 30.58 11.12 20.70
U1 77.00 12.72 0.52 4.75 74.38 65.78 69.42 88.88 79.30
O2 10.27 17.96 0.68 2.41 69.67 12.39 12.22 6.01 9.91
U2 66.73 11.91 0.49 5.11 75.10 53.39 57.20 82.86 69.39
O1+O2 33.27 20.86 0.74 2.12 66.45 46.61 42.80 17.14 30.61

Flotation tests
Flotation is a useful method for removing impurities such as calcite and iron oxides from industrial
silicate minerals. Review on the calcite removal by the flotation showed that one of the best and available

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collectors for calcite flotation is oleic acid or one of its ammonium salts that occurs in alkali pH. In these
conditions sodium silicate addition is necessary for depressing Kaolin (Abd El-Rahiem et al., 2008). In this
method, conditioning time and rotor speed have important effects on calcite removal in reverse flotation.
For example in order to achieve more than 70% calcite removal, minimum required conditioning time is
above 10 minutes (Abd El-Rahiem, Selim & Abdel-Khalek, 2009). Conditioning in acidic medium for
appropriate elimination of iron impurities by flotation using petroleum sulfonate as a collector is required
(Haghi et al., 2010). This process is not suitable due to acid consumption more than 64.75kg HCl per ton of
dry kaolin for pH adjustment.
Nine Flotation experiments were carried out in 2.5 liter Denver laboratory flotation cell. Reverse floatation
tests for calcite removal were carried out on alkali pH based on full factorial design and variables were in
two levels including one center point. Three designed parameters were collector (oleic acid) dosage (g/t),
pH and depressant (sodium silicate) dosage (g/t). The experimental conditions and their results are
presented in Table 5. Regarding to flotation results, increasing sodium silicate from 500g/t to 1000g/t
decreased kaolin loss in froth zone while increasing pH from 8.5 to 10.5 indicated negative effect on the
calcite removal. Also filtration and dewatering at higher pH was very difficult. In addition, based on the
flotation results presented in Table 5, with increasing collector addition in the flotation tests iron oxides,
calcite and siliceous were collected in froth zone and removed considerably; thus the result of test
number 6 is better than other flotation tests. In the optimum flotation conditions of 1000g/t sodium
silicate, 1000g/t Oleic acid and pH=8.5 (test number 6) 75% of calcite was removed and CaO amount of
final product was reduced from 4.35% to 1.33% while Kaolin loss was only 6.93 %.
Reducing flotation feed particle size from 210m to particles finer than 53 m resulted in improvement of
calcite removal up to 83% while only 13.8% kaolin was lost in froth zone. The frothing time of these tests
was 5 minutes. More frothing time and addition of frother and fuel oil caused to remove 90% of calcite
and reduce the grade of CaO to 0.6%, but the Kaolin loss in froth zone increased to 35%. Thus the
optimum conditions for maximum impurities removal and minimum Kaolin loss in frothed stream were:
Particle size distribution: 80% finer than 53m (D80= 53m);
pH = 8.5;
Collector dosage: Oleic acid 1000g/ton;
Depressant dosage: Sodium silicate 1000g/ton;
Frothing time: 5 minutes.
Above conditions caused reduction of CaO grade from 4.33% to 0.9% and removing 83% of calcite in final
product, while Kaolin loss in froth zone was only 13.8%. In Table 6, the results of other tests that carried
out at optimum conditions with different frothing time and addition of fuel oil are presented.

Table 5 Results of flotation tests

Factor Factor Factor Impurities Removal

Concentrate Grade (%) Brightness
A B C Al2O3 (%)
Test
Oleic Sodium Loss
Number
Acid pH Silicate Al2O3 Fe2O3 CaO SiO2 (%) (%) Fe2O3 CaO SiO2
(g/t) (g/t)
1 500 8.5 500 15.52 0.49 2.74 72.83 86.8 5.87 13.87 42.43 6.31

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2 1000 8.5 500 14.81 0.49 4.01 72.04 84.8 14.23 17.76 19.54 11.50
3 500 10.5 500 15.90 0.47 3.53 71.63 85.0 10.81 14.13 22.91 4.22
4 1000 10.5 500 15.84 0.48 2.73 71.76 87.0 1.07 13.12 40.93 4.94
5 500 8.5 1000 15.44 0.47 1.55 74.82 87.5 9.22 19.92 68.43 6.70
6 1000 8.5 1000 16.98 0.46 1.33 74.08 87.9 6.93 26.93 74.75 13.88
7 500 10.5 1000 15.64 0.46 1.98 73.68 86.8 8.26 21.80 59.76 8.26
8 1000 10.5 1000 16.24 0.47 2.43 73.01 86.2 11.18 16.29 48.26 4.82
9 750 9.5 750 15.10 0.48 2.81 73.11 86.6 4.95 12.44 38.72 2.39

Table 6 Flotation tests results in optimum conditions

Frothing Additional Impurities Removal

D80 Concentrate Grade (%) Brightness Al2O3
Duration Agent (%)
Loss (%)
m min - Al2O3 Fe2O3 CaO SiO2 (%) Fe2O3 CaO SiO2
200 5 - 16.98 0.46 1.33 74.08 87.90 6.93 26.93 74.75 13.88
53 5 - 15.84 0.50 0.90 75.93 82.10 13.81 21.15 83.03 12.37
53 6 Fuel Oil 15.51 0.52 0.67 76.34 81.50 34.73 36.58 90.23 31.86
Flotation Feed 15.07 0.52 4.35 71.05 83.50 - - - -

CONCLUSION
In Zonouz kaolin deposit the grade of Al2O3, SiO2, CaO and Fe2O3 were 15.07%, 71.05%, 4.35% and
0.52% respectively. TiO2 grade was negligible. Almost all of CaO content was in the form of
carbonates due to presence of calcite in sample. Major iron oxides impurities were hematite,
limonite and pyrite.
Due to existence of quartz in ore with bigger Hardness (H= 7) and its difference with other minerals
such as Kaolinite (H=2), calcite (H=3) and iron oxides (H = 4-6), it is assumed that attrition scrubbing
could be a part of processing method, but with control screen of 106m on scrubber outlet
considerable results are not achieved. It should be mentioned that application of attrition scrubber
would be useful in closed circuit using hydro-cyclone with finer cut size (even less than 37m).
Using hydro cyclone at P = 68.65 kPa and D80 = 210m, the grade of CaO in overflow as concentrate
reduced to less than 1.5%. Applying these conditions, the grade and weight recovery of Al2O3 was
22.8% and 30.0 % respectively. By regrinding underflow stream of first hydro-cyclone and feeding
to second hydro-cyclone the grade of CaO in overflow as concentrate reduced to 2.1%. In this test,
the grade and recovery of Al2O3 was 20.9% and 46.6% respectively.
Flotation at D80= 53m, pH= 8.5, 1000g/ton oleic acid as collector and 1000g/ton sodium silicate as
depressant with 5 minutes frothing caused reduction of CaO grade from 4.33% to 0.9% and 83% of
calcite removal while Kaolin loss was only 13.8%.

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 A primary flow sheet was proposed based on results of all tests and presented in Figure 3.

Figure 3 proposed flow sheet for processing of relatively low grade kaolin

ACKNOWLEDGEMENTS
Authors of this paper would like to express their special thanks to Iran China Clay Company not only for
chemical analysis of samples but also their kind support within this study. Also kind support of mineral
processing laboratory of university of Tehran is gratefully acknowledged. It should be mentioned that
participation of presenting author will be supported by university of Tehran and Clay Minerals Group
(CMG) of The Mineralogical Society of Great Britain and Ireland.

REFERENCES
Abd El-Rahiem, F. H., Hassan, M.S., Selim, K.A., Abdel-Khalek, N.A. (2008) Evaluation and Beneficiation of Syrian
Kaolin for Different Industrial Applications, The Journal of Ore Dressing, Vol. 10(19), pp. 34-41.

Abd El-Rahiem, F. H., Selim, K.A., Abdel-Khalek, N.A.(2009) Some Parameters Affecting Beneficiation of Fine Kaolin
Particles, The Journal of Ore Dressing, Vol. 11(21), pp. 1-8.

East Azarbaijans organization of industries and mines (EAOIM), deputy of mine affaires and explorations (2006), The
outlook for East Azarbaijan province mines (in Persian), Iran.

Haghi, H., Noaparast, M., Ghorbani, A. (2008) Reduction of Iron Content from Silica Sand by Scrubbing Process,
Proceedings of the XI International Mineral Processing Symposium (IMPS2008), Belek, Turkey, pp 259-267.

Haghi, H., Noaparast, M., Ghadyani, A., Ghorbani, A. (2010) Reduction of Iron Content from Shenin Silica Mine by
Reverse Flotation Proceedings of the XII International Mineral Processing Symposium (IMPS2010), Nevsehir,
Turkey, pp 465-474.

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Kogel, J.E. (2014) Mining and Processing Kaolin, Elements, Vol.10 (3), pp.189-193.

Murray, H., H. (1961) Industrial Applications of Kaolin, Proceedings of 10th National Conference on Clays and Clay
Minerals, Austin, Texas, USA, pp. 291-298.

Murray, H., H. (2007) Applied clay mineralogy: occurrences, processing and applications of kaolins, bentonites, palygorskite
sepiolite, and common clays, Developments in Clay Science, Vol. 2, Elsevier.

Pruett, R.J., Pickering, S.M. (2006) Kaolin, Industrial Minerals & Rocks: Commodities, Markets, and Uses, 7th Edition, (Eds:
Kogel, J.E., Trivedi, N.C., Barker, J.M. and Krukowski, S.,T.), SME, pp. 383-399.

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