SELECTION AND OPTIMIZATION OF SYNTHETIC FLOCCULANT FOR HIGH

RATE DECANTERS (DEEP CONE THICKENERS)

Raghavan PKN2*, Bamrah H1, Kshatriya NK2 and Dasgupta S1
1
Alumina Refinery, 2 Research & Development and 3Head Plant-1
Bharat Aluminium co. Ltd.,
(A Unit of Vedanta Resources plc,)
BALCo Nagar, Korba – 495684, Chhatisgarh State, INDIA
Abstract
Synthetic flocculants have come to play a prominent role in improving the operation of various systems in Alumina
Refinery. They are used for improving settling and filtration characteristics of mud in settlers, washers and thickeners
prior to disposal, and also to improve overflow liquor clarity and mud compaction. This paper describes the results of the
Laboratory scale trials of various synthetic flocculants and establishes the best Flocculant for the Deep Cone Thickener
(DCT). Preliminary screening tests were conducted for selection of the flocculants that gave best results with respect to
good quality flocs, rapid settling rates (in the range of 10-15m/h) and better mud compaction. The screened flocculants
from reputable suppliers were then assessed for suitability under plant conditions. The flocculant trails have shown that
the flocculants play a crucial role in the mud dewatering. Flocculated red mud was observed to have better filterability, lower
cake moistures and lower solid losses in filtrate with appreciable reduction in soda loss through the mud. A comparison
of the experiments for a similar trial done for a conventional settler is also given.

1. Introduction
In the Bayer process, flocculants are used to aid the separation of
the red mud from the liquor, as well as to maximize the recovery
of alumina and soda from the red mud in the washer circuit.
The use of synthetic flocculants can also help in enhancing the
production rates.
Acrylamide sodium acrylate and hydroxymated polymers have
gained importance as flocculants in the mineral processing
industry. They have largely replaced the historically used
flocculant like starch. The major advantage of these synthetic
flocculants over natural ones is they are cheap, water soluble
and can usually be tailored (composition and Molecular weights)
to meet the specific applications
The most recent type of hydroxymated flocculants (Hx) can
accommodate a variety of process conditions. They vary in the
degree of functionalization and molecular weight, but generally
the removal of suspended solids increase molecular weight.
However, higher settling rates are achieved at lower Hx product
numbers, therefore, a compromise molecular weight is needed
to optimise both settling rates and overflow clarity.
The hydroxymated polyacrylamide polymers are available in the
emulsion form and offer the following advantages:
• they replace both the polyacrylate and starch to provide
exceptional clarities with high settling rates,
• better underflow densities,
• more consistent operation of the settlers / DCTs, improved
filtration rates of the overflow liquor.
The inclusion of the hydroxymic acid functional group in the new
generation polymers provides a very strong attachment of the
polymer to the mud particles. This strong attachment makes
these materials significantly more efficient than the polyacrylates
in capturing the fine particles and also generates large flocs
which are more resistant to breakage.
1.1 Role of Flocculant in Red Mud Settling
Polyacrylate containing carboxylic groups or acrylate / acrylamide
based copolymers induce very high rate of settling and mud
compaction. However, flocculants of this type cannot produce
desired liquor clarity, making the use of starch required as well.
Hydroximated flocculants containing carboxylic and amide groups
simultaneously induce good settling rates and improve liquor
clarity, but require high dosing rate. Hydroxamated flocculants
also have positive impacts on liquor filterability, mud rheology,
thickener life and lime consumption. In the recent years, many
plants have adopted their use in combination with a traditional
polyacrylate polymer (Jean, 2004). The exact type of floc will
depend on the refinery and the bauxite source (Kini, 2000). For
example, in India, there are four varieties of bauxite, viz;
(i) East Coast Bauxite which is highly Gibbsitic and soluble at
low temperatures and atmospheric pressure,
(ii) West Coast Bauxite with low Boehmitic and Diasporic
content which can be digested at 145°C at 5atm,
(iii) Central Indian Bauxite which is Boehmitic which needs high
temperature and pressure,
(iv) Gujrat Bauxite being Diasporic in nature, requiring very
high temperatures and pressures (320°C). The flocculants
required for each system are different.
1.2 Factors influencing Flocculant type in Deep Cone
Thickeners
The flocculant activity of red mud and its settling behaviour is
influenced by:
• the polymer molecular weight, the polymer composition,
• mode of application,
• effect of alkalinity.
The most common method of disposal of Bayer red mud
generated is by pumping the material to large settling ponds
where waste disposal is permissible. In general, the rheological
behaviour of mud residue is not only affected by solids loading,
particle morphology and particle size distribution, but also
by particle interactions (Frost, 2007). These interactions are
influenced by chemical factors such as presence of flocculants /
de-flocculant agents. High molecular weight anionic polyacrylates
are commonly used for the flocculation of bauxite residue in DCT.
For mud washing, a mixture of acrylate and non-ionic acrylamide
is often used. Most of the published literature on the flocculants
for red mud settling is related to the behaviours of the material

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 in conventional settlers, while very limited work exists on how
the behaviour is affected in DCTs. The high-supersaturated
aluminate liquor discharged from digestion must safely pass
clarification before reaching precipitation. The main concerns in
clarifications are;
(i) reversion in the DCT and mud washers,
(ii) scaling of polishing filter leaves,
(iii) high soda losses through red mud,
(iv) high hydrolysis loss, after passing through the sand
separation.
The digestion slurry is fed to DCTs for separation liquor and
mud. The underflow passes through the mud washers where
reversion can occur. The use of DCTs in combination with the
washers reduces liquor to mud contact time and so a reductions
reversion rates, and the soluble soda loss. Synthetic flocculants
like polyacrylate along with starch were used in conventional
settlers. Laboratory scale trials were conducted with an aim to
get 10-15m/h settling rate and acceptable overflow clarity for the
DCT.
1.3 Inadequate DCT sizing
While changing from conventional settler operation to a DCT
operation, it is almost impossible to prepare a representative
DCT feed sample and design a DCT based on the necessary
tests. As a result, there always exists a degree of uncertainty in
getting DCT design. This can lead to a loss in production. Instead
of purchasing new equipment, the use of suitable flocculants
(alone or in combination) can often solve the problem.
This paper describes the effects of various flocculants for settling
of red mud generated from the digestion of Central Indian
bauxite. An attempt has been made to compare the performance
of flocculants for conventional settler with that for the Deep Cone
Thickeners.
2. Experimental
The bauxite was digested at high temperature (235-240°C) and
high pressure (30-35atm). This was carried out in a series of
autoclaves with recuperative heating system. Slurry flashing is
done in series of flash tanks. The flashed slurry is diluted and
then sedimentation is carried out by flocculant. The diluted
slurry from plant was collected for experimental work.
2.1 Flocculants Preparation
A stock solution of 1% of hydroxamated flocculant was prepared
in 10g/L NaOH in distilled water and diluted further to obtain a
working solution of 0.1%. Working solution of 0.1% of polyacrylate
was prepared in industrial water.
2.2 Settling Test for Optimum Dosage:
Conventional jar settling tests in hot water baths was the first test
used for selection of flocculant, optimization of concentration
and doses regimes (single or split). The diluted slurry after
desanding was poured into marked cylinders (1 Liter) and stored
in a constant water bath (97-98°C). The slurry was mixed and the
hydroxamated flocculant was added in two portions with mixing
(50:50). In the case of codosing, the polyacrylate flocculant
was added first, the slurry was allowed to stabilize and then the
hydroxamated flocculant was added. Fifty milliliters overflow was
withdrawn, 15 minutes after flocculant was added and then
filtered using a previously weighed suitable membrane filter
paper for determination of overflow clarity. The compact volume
was recorded after 30 minutes. The entire slurry was vacuum
filtered to get total solid content.
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AQW2008_Proceedings_FINAL-1-120.65 65
3. Results and Discussion
3.1 Selection of Flocculants
The results of laboratory tests evaluating the effectiveness of
various flocculants were evaluated over a range of dosage levels.
The best settling rates were obtained by hydroxamated floc 3
and polyacrylate A, relative to volumes dosed (178g/T mud and
64.9g/T mud respectively). It was observed that irrespective of
the type of flocculant, the mud was highly sensitive to variations
in dosage.
The polyacrylate gave higher settling rate at higher dosage, but
with poor overflow clarity. This trend reversed for hydroxamated
flocculants (Figure 1) which showed poor settling rates but good
clarity. The tests were targeted at ascertaining the order of
magnitude of the dosage required to achieve a minimum settling
rate of about 10-15m/h under the DCT conditions. The settling
characteristics of the polyacrylate with different dosages are
shown in Table 2. The settling rates vary from slurry to slurry
even though the variations in the caustic concentration and the
feed solids are minimal. This may be due to the changes in mud
rheology at different caustic concentrations and feed solids. The
effects of polyacrylate concentration and dosing method are given
in Table 3, while the performance of hydroxamated flocculants in
combination with polyacrylate is shown in Table 4.
It was found that the flocculants which performed the best
for conventional settlers did not meet the minimum criteria of
settling rates required for the DCT.
Based on laboratory tests, following can be summarized:
(1) The required dosage of polyacrylate flocculant was lower
than hydroxamated flocculant to achieve the same settling
rates.
(2) Depending on the specific flocculant used, a settling rate
of 15m/h could be achieved if the hydroxamated flocculant
was dosed at approximately 145g/T mud (Table 1 and
Figure 1). However, for the polyacrylate to achieve the same
settling a dosing rate of 80 157g/T was required (Table 2
and Figure 2).
(3) Table 3 shows that a concentration of 0.05% of polyacrylate
gives better results than 0.1% concentration. Split addition
and mixing of flocculants improve settling rate but not
clarity.
(4) Polyacrylate flocculant increased the settling rates but
reduced overflow clarity, whereas this trend was reversed
using hydroxamated flocculant (Figure 3 and Table 4).
(5) There was no improvement in overflow clarity on increasing
the ratio of hydroxamated flocculant in the combined
flocculant doses and settling is better than the polyacrylate
fraction is above 50% (Table 4 and Figure 4).
(6) The hydroxamated / polyacrylate combination leads to a
significant decrease in hydroxamated flocculant consumption
(Table 5).
(7) It was observed that the settling is very uneven in early
stages, with no clear mud interface for polyacrylate.
However, hydroxamated flocculant required no induction
time and gave a very sharp interface from the beginning of
settling with very clear liquor above the interface.
4. Conclusions
From this work, the following overall conclusions can be
observed:
(1) The dosages of hydroxamated flocculant required to achieve
a settling rate of 15m/h settling was in the range of 155-
192g/T mud with corresponding overflow clarities of 125-
192mg/L.
(2) The dosage of polyacrylate flocculant required to achieve a
settling rate of 15m/h was in the range of 80-157g/T mud
with corresponding overflow clarities of 132-145mg/L.
65
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 (3) The dosages of combined polyacrylate / hydroxamated
flocculant required to achieve 15m/h settling rate was
approximately 123.3g/T mud (polyacrylate 66.3g +
hydroxamated 58g and overflow clarity was 100mg/L).
These results indicate that for identical settling rates, the
flocculant mixture (hydroxamated and polyacrylate) provides
suitable overflow clarity with lower overall dosages volumes, than
if either flocculant was used individually.
In the pilot plant scale trials conducted with a flocculant
combination of 66.3gm of polyacrylate and 58gm of hydroxamated
for a settling rate of 15m/h, we could observe an overflow clarity
in the range of 80–100mg/L without starch addition. Filterability
of the overflow liquor was enhanced which resulted in reduction
in the filtration time of the aluminate liquor. Further, the mud
compaction was also better due to the change in mud rheology
due to the addition of the mixed flocculants. The soluble soda
loss calculated for the filtered red mud was found to be 11kg/
T of alumina from 15kg/T of alumina (obtained in conventional
settlers with mud raking mechanism where the flocculants used
are to get a settling rate of 3–5m/h) with better flowability. It
could also be observed that due to the change in the mud
rheology, red mud filtration rate was enhanced. This is expected
to give a substantial improvement in the Red Mud filtration in the
Plant Scale.

Table 1. Screening of Flocculants Table 2. Mud Settling Characteristics with Polyacrylate

Type of Flocculants Flocculants Settling Rate Overflow solid Feed Solid - 59g/L, Na2O of Slurry – 142.4g/L
Dosage g/T m/h mg/L
mud Type of Flocculant Settling Overflow Compaction
Flocculants Dosage g/T Rate m/h solid mg/L ml
Hydroxamated 1 178 6.6 166 mud

222 10.6 162 Polyacrylate “A” 50.8 No Settling - -

289 34.8 204 84.7 1.14 - -

Hydroxamated 2 178 4.9 140 118.6 3.42 71 220

222 13.0 116 169.4 20.7 132 190

267 116 106 Polyacrylate “A” 64 5.44 65 200

Hydroxamated 3 133 9.2 234 80 15.2 145 175

155 20.8 132 96 19.35 148 180

178 26.1 116 Polyacrylate “A” 127.7 3.90 132 280

Polyacrylate “A” 38.9 14.65 135 153.2 11.39 145 260

64.9 41.89 195 191.5 29.19 160 240

90.9 68.4 247

Polyacrylate” B” 64.9 9.12 110

77.9 11.56 124

Table 3. Effect of Polyacrylate Flocculant concentration and dosing system

Flocculant Dosage Flocculant con. % Dosing Settling Rate m/h Overflow solid mg/L Compaction ml Remarks
g/T mud

80 0.1 Single 15.2 145 175 Na2Oc – 147.1g/L

80 0.05 Single 23.24 141 180 Feed Solid – 62.5g/L

80 0.1 Split(50:50) 31.38 147 160

80 0.05 Split(50:50) 39.69 144 160

153.2 0.1 Single 11.39 145 260 Na2Oc – 148.7g/L

153.2 0.05 Single 17.39 138 250 Feed Solid – 78.3g/L

153.2 0.1 Split(50:50) 37.31 148 230

153.2 0.05 Split(50:50) 21.37 140 250

127.1 0.1 Single 3.90 132 280 Na2Oc – 148.7g/L

127.1 0.1 Split(60:40) 10.36 135 260 Feed Solid – 78.3g/L

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 Table 4. Mud Settling Characteristics of Hydroxamate with combination of Polyacrylate
Type of Flocculants Flocculants Dosage Settling Rate m/h Overflow solid mg/L Compaction ml Remarks
g/T mud

Hydroxamated - 1 173 3.4 264 280 Na2Oc – 149.2g/L

192 14.9 192 235 Feed Solid – 104g/L

PA + Hydroxamated - 1 38+87 5.4 190 260

67+48 6.7 166 240

48+77 10.3 190 230

48+96 16.1 176 250

Hydroxamated - 1 108.1 2.09 92 - Na2Oc – 140.8g/L

135 12.82 200 130 Feed Solid – 74g/L

162 13.68 126 200

189 20.5 90 190

243 22.8 - 180

PA + Hydroxamated - 1 67.5+67.5 17 94 200

27+108 9.8 118 210

40.5+67.5 13.68 126 200

Hydroxamated - 1 99.5 5.00 224 180 Na2Oc – 145.4g/L

165.8 18.65 138 160 Feed Solid – 60.3g/L

182.4 25.65 98 150

PA + Hydroxamated - 1 49.7+49.7 3.80 150 190

82.9+82.9 36.00 76 150

66.3+49.7 12.82 106 160

66.3+66.3 17.8 102 160

66.3+74.6 24.1 180 170

74.6+66.3 28.6 92 160

49.7+66.3 10.5 158 170

Table 5. Consumption of Hydroxamate and Polyacrylate combination

Type of Flocculants Flocculants Dosage Settling Rate Overflow solid Compaction ml Remarks
g/T mud m/h mg/L

Hydroxamated - 3 166.6 18.65 138 160

Hydroxamated - 3 183.3 25.65 98 150

Na2Oc – 145.4g/L
66.6+66.6
Polyacrylate A + Hydroxamated - 3 17.8 102 160
(133.2) Feed Solid – 60g/L
75+66.6
Polyacrylate A + Hydroxamated - 3 28.6 92 160
(141.6)

80 35

70 30
SR m/hr

60
25
PA
SR m/hr

50
20
Trial -3
40 Trial -1
Trial -2
15
30 Hydroxymated
10
20

5
10

0 0
0 20 40 60 80 100 120 140 160 180 200 0 50 100 150 200 250
Dosage (gm/T) Dosage (gm/T)

Figure 1. Performance of Hydroxamated and Polyacrylate with different Figure 2. Performance of Polyacrylate Flocculant
dosage

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 240

Hydroxymated Polyacrylate
220
OF Clarity mg/ llt

200

180

160

140

120

100
5 10 15 20 25 30 35 40 45 50 55 60 65 70
SR m/hr

Figure 3. Effect of Settling rate on Overflow Clarity with Polyacrylate &

Hydroxamate

180

170

160
Trial - 1
150

140

130
OF Clarity mg/ llt

120 Trial - 2
110

100

90

80

70

60

50

40 45 50 55
% Fraction of PA Dosage

Figure 4. Effect of Polyacrylate fraction dosage on overflow clarity in a

combination dose (Polyacrylate + Hydroxymate)

Acknowledgements
The authors are thankful to the management of Bharat Aluminium
Company Limited, Korba, India, for granting permission for
presenting this paper. The authors would like to thank Mr.
Pramod Suri, CEO, Aluminium Business, Vedanta resources plc.,
India, Mr. Gunjan Gupta, CEO, BALCO – Korba, India and Mr.
Sharad Kumar Goel, Head, plant-1, BALCO – Korba, India for
their encouragement during the course of this work.

References
Frost, Ray and Pejcinovic, Nik and Nguyen, Tai, “ Effect of surfactants on Bauxite residues suspensions, viscosity”, Colloids and Surfaces A: Physicochemical
and Engineering Aspects, 292 (1), 2007, pp 21-26.
Jean – marc Rousseaux, Benoit Cristol, Stephane Torsiello, “Combination of hydroxamated and Polyacrylamide based flocculants for settler performance
improvements in ADG Alumina refinery”, Light Metals, (2004), pp 15-20.
Kini, A.D, Misra, B.p., Raja, S.M., “Effect of Synthetic Flocculants on Settling and Filtration of Red Mud”, Symfloc (2000), India, pp 145-156.
Lathouras, M., Avotins, P.V., “The Role of Hydroxamated Polyacrylamide Flocculants in the Bayer process”, Symfloc, (2000), India, pp 59-69.

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