Mineral.s Enl,,ineering, Vol 14, No. 11, pp.

1 5 0 5 - 1 5 1 1 , 2001
Pergamon © 2001 E l s e v i e r Science Ltd
All rights reserved
0 8 9 2 - 6 8 7 5 / 0 1 / $ - see front matter
08924875(01)00163-7

ADVANCES IN MINERAL FLOCCULATION*

M.J. PEARSE, S. WEIR, S.J. ADKINS and G.M. MOODY

Ciba Specialty Chemicals, PO Box 38, Bradford, West Yorkshire, BD12 0JZ, United Kingdom
E-mail mike.pearse @cibasc.com
(Received 30 July 2001," accepted 8 September 2001)

ABSTRACT

The use o f a new floeculant t3,t~e (the Unique Molecular Architecture (Ciba ® UMA ®) flocculant) led
to dose efficient sedimentation of a predominantly china clay suspension. For a specified
sedimentation rate the supernatant turbidity and sediment volume were lower when the Unique
Molecular Architecture .flocculant was used compared to a standard flocculant. In addition the
Unique Molecular Architecture flocculant was robust in terms of the desirable performance to
changes in substrate - flocculant mixing and flocculant concentration. Dose efficient sedimentation
was also achieved by the dual flocculant addition qf a pure polyaco,lamide (non ionic floceulant)
Jbllowed by an anionic flocculant. © 2001 Elsevier Science Ltd. All rights reserved.

Names marked with ® are registeredtrade marks

Keywords
FIocculation; dewatering; gravity concentration.

INTRODUCTION

The mineral processing industry, in general, has put greater demands on solid-liquid separation equipment
in recent years. This trend has been partly due to environmental considerations and partly due to technical
and cost efficiencies. An example of this trend is the wider use of 'high-rate' thickeners, in which high
solids settlement rates are utilised, essentially giving smaller diameter units. This, in turn, has led to the
development of improved, high-performance flocculants.

General trends in tile development of flocculants over recent years have been identified (Weir and Moody,
2000 and Mohammed et al., 2000). For mineral processing applications, particularly sedimentation, one of
the identified trends was the use of increased molecular weight flocculants. During the conventional
polymerisation process used in the manufacture of flocculants, polymers with a range of molecular weights
are produced. So more precisely, the recent trend has been to increase the average molecular weight of the
distribution of flocculant molecules. This trend is unlikely to continue. By varying the molecular weight
distribution, molecular architecture and chemical composition, a myriad of flocculant entities can be
produced. Certain of these flocculants are referred to as having Unique Molecular Architecture (UMA ®)
(Pearse, 2000). The performance evaluation of such a flocculant type is discussed here. Flocculant
chemistry is reviewed elsewhere (Moody, 1994).

*Prcsented at MEGS '01, Fahnouth, UK, June 2001

15(/5
1506 M.J. Pearse et al.

Often two polyelectrolytes are used in combination to bring about desirable flocculation. Typically, these
dual treatments employ counter ionic species, be it a combination of anionic flocculant and cationic
polymeric coagulant (Peng and Lu, 1998) or anionic and cationic flocculant (Moody and McColl, 1997).
Detailed here is the synergistic sequential use of non ionic and anionic flocculants.

EXPERIMENTAL

Materials

Flocculants (Ciba Specialty Chemicals, UK) are supplied as powders. Representative 0.5g portions of the
powder were placed in a glass jar, 5cm 3 of acetone were added to form a slurry, to which 95cm ~ of
deionised water were added. The jar was sealed securely with a screw top lid and the mixture was then
shaken vigorously by hand and tumbled, on a rotating wheel (at approximately 30rpm) for 2 hours to
generate a homogeneous 0.5% (w/v) stock solution. The stock solution was diluted to 0.05% (w/v) by
taking a known volume of 0.5% solution and quantitatively mixing with an appropriate volume of
deionised water and used for flocculation tests. A solution concentration of 0.05% was used unless stated
otherwise. The Unique Molecular Architecture flocculant was compared to a flocculant made by a standard
process, both flocculants were 22% sodium acrylate : 78% acrylamide copolymers.

SPS china clay (Imerys Minerals Ltd, UK) was mixed with tap water such that a suspension of 4% (w/v)
was formed. Sodium chloride was added to the suspension at a level of 2g/din 3. For the testing of Unique
Molecular Architecture flocculants, 10% bentonite (based on weight of china clay) was added to the
suspension. Each suspension was thoroughly mixed and left to age overnight.

Flocculation

Flocculation tests using Unique Molecular Architecture flocculants were conducted by taking 500cm ~
representative aliquots of clay suspension and placing in 500cm 3 graduated measuring cylinders. An
appropriate aliquot of polymer solution was immediately added via a syringe and flocculation induced by
cylinder inversions. This process was conducted using flocculant solutions at concentrations of 0.025,
0.050, 0.075 and 0.100% (w/v) and using 2, 3 or 4 cylinder inversions.

Flocculation tests using sequential dosing were also conducted using 5 0 0 c m ~ aliquots of china clay
suspension. This time the suspension was placed in a ldm ~ beaker and an appropriate amount of 0.05%
(w/v) flocculant solution added via a syringe. Flocculation was induced by the use of a laboratory mixer (3
blade marine impeller, of approximate diameter of 3.5cm, at a speed of 1000rpm). The mixing proceeded
for 5s and to the agitated suspension a second amount of flocculant solution was rapidly added via a
syringe and mixing continued for a further 15s. In the instances where only a single flocculant solution was
added the mixing time was 15s. The flocculated suspension was immediately transferred to a 500cm 3
measuring cylinder.

Assessment of flocculation efficiency

The sedimentation rate of the flocculated suspension was determined by recording the time taken for the
'mud line' (solid - liquid interface) in the 500cm 3 cylinder to pass between a depth of 3cm and 8cm from
the suspension surface.

The flocculated suspension was allowed to stand, quiescently, for a period of 10 minutes and the sediment
volume was recorded. Also after 10 minutes a sample of the supernatant liquid was removed and its
turbidity measured.
 Advances in mineral flocculation 1507

RESULTS AND DISCUSSION

Unique Molecular Architecture (UMA®) floceulants

The results of flocculation testing with the UMA® product are presented as contour plots of responses (i.e.
flocculant dose for a sedimentation rate of 20cm/min, supernatant turbidity and settlement volume) as a
function of the variation in cylinder inversions and flocculant solution concentration. Variation in cylinder
inversions is effectively altering the level of substrate - flocculant mixing. To fully understand flocculant
performance, it is important to alter the level of mixing, since on full scale applications the level of mixing
will be site specific (e.g. dependent on pipe diameter, pipe length, feed flow rate and feed characteristics).
Similarly the flocculant concentration will vary from site to site, being dictated by, for example, dose
requirement, available dose pump capacity and available space for situation of the flocculant solution
preparation and storage tanks.

The flocculant dose required for a sedimentation rate of 20cm/min for the standard flocculant and the
Unique Molecular Architecture flocculant is shown in Figure I. At most conditions of cylinder inversions
and flocculant concentration the Unique Molecular Architecture flocculant is more dose efficient than the
standard flocculant to achieve the same degree of sedimentation rate. This is especially true at conditions of
low mixing (i.e. between 2 and 3 cylinder inversions). From further consideration of the results presented in
Figure 1, the Unique Molecular Architecture flocculant is more consistent in the level of sedimentation rate
achieved under the varying conditions.

• 5 "\ #' ,/
©

4.5
>
e-
'4.5
3

i
4
" 5 ...........
¢-

3.5

2 3.. , I i , , i i i i
0.0 5 0.°5. °.075 0., 0.025 0.05 0.075 O. 1

Flocculant Concentration (% w/v)

Fig. 1 Flocculant dose (rag/l) required for a sedimentation rate of 20cm/min (standard flocculant left side
and Unique Molecular Architecture flocculant right side).

Figure 2 shows the supernatant turbidity following flocculation and subsequent sedimentation at 20cm/min,
with the standard flocculant and the Unique Molecular Architecture flocculant. For any specific set of
conditions (i.e. number of cylinder inversions or flocculant concentration) the Unique Molecular
Architecture flocculant renders a lower supernatant turbidity. This is especially significant when one
considers, from Figure 1, the flocculant dose required to give a sedimentation rate of 20cm/min is typically
lower for the Unique Molecular Architecture flocculant.

Figure 3 shows the sediment volume achieved with the standard flocculant and the Unique Molecular
Architecture flocculant, from a fixed sedimentation rate of 20cm/min. For all like for like conditions of
mixing (i.e. cylinder inversions) and flocculant concentration, a lower sediment volume was obtained with
the Unique Molecular Architecture flocculant.
 1508 M . J . P e a r s e et al.

0
250

> 300

gO0

~tS0

0.025 0.05 0.075 O. 1 0.025 0.05 0.075 0.1

Flocculant Concentration (% w/v)

Fig.2 Supernatant turbidity (FTU) from a sedimentation rate of 20cm/min (standard flocculant left side
and Unique Molecular Architecture flocculant right side).

155
o 17o
7. 18o
;>
_= 3
' 190 165
200 160
210
220 175
230 170
1'10
2 25O I , I 2 1@0 , ~ , I , ~ J ~ [ J L L ,
0.025 0.05 0.075 0.1 0.025 0.05 0.075 0.1

Flocculant Concentration (% w/v)

Fig.3 Sediment volume (cm ~) from a sedimentation rate of 20cm/min (standard flocculant left side and
Unique Molecular Architecture flocculant right side).

Sequential addition of non ionic flocculant followed by anionic flocculant

An initial premise was made that the sequential addition of non ionic and anionic flocculants, for tile
treatment of mineral substrates would be worthy of investigation. This premise was based on the possibility
of the two flocculant types interacting with substrate particles by different adsorption mechanisms. An
initial test was conducted (results not shown) using three sequential addition strategies, the relative order of
flocculant dose efficient sedimentation rate performance being : Non ionic followed by anionic > anionic
followed by anionic > anionic followed by non ionic. This initial encouraging result for the dose efficient
performance of non ionic floccutant tbllowed by anionic flocculant was further tested with reference to
several dual flocculant sequential additions (see Figure 4). It should be noted that the sequential additions
were made in a 1:1 ratio and all flocculants would be considered of 'high' molecular weight. From Figure 4
it is clear that the most desirable flocculant combination is that of non ionic flocculant followed by anionic
flocculant, in terms of flocculant dose efficient sedimentation rate. This finding is the subject of a patent
application (Weir, 200 I).
 Advances in mineral flocculation 1509

1,m

26 170
E i

E ~oc
v ro

z ,01 P
,oi
i
E

0 5 1o 15 20 25

Total Flocculant Dose (mg/1)

-. ~ - - N o n ionic ---m-- Anionic ...A... CalJonl¢

I~ - - Non ior~c folbwed by non i~nic + Non ionic [oRowed by ~ n i c • N on b t ~ fallawed by cationic
]
I * Ankx,,k: fo gowed by anionic ~ Anionic ~ l o w e d by cationic ~- C ationic followed by non bnic
i - . . o - Cationic followed by anionic . A .. Cationic Ib[owed by cationic

Fig.4 Sedimentation rate data fl>r several flocculant sequential additions (the flocculant dose is split 1:1 ).
Also shown are single additions of non ionic, anionic and cationic flocculant. NB. Solid symbols
and dotted line for single additions, solid symbol and continuous line for non ionic pretreatment,
open symbol and continuous line for anionic pretreatment and open symbol and dotted line for
cationic pretreatment.

Figure 5 shows the effect of the pretrcatment anionicity when the second treatment is a 47% anionic
content flocculant. The most dose efficient sedimentation rate is achieved when the pretreatment is non
ionic. Even a small (i.e. 4%) level of anionic content present in the pretreatment flocculant causes the dose
efficient performance to be reduced dramatically. However, when increasing anionic content beyond 4%,
no obvious trend emerges between flocculant dose efficiency and pretreatment flocculant anionicity.

120 ,- . . . . . . . .
!
i

°- ,
/1,

~I

~¢- r

e-

E 2o ................... ~;~............ ÷ " i ...... ".......

o
15 25 35 45

Total Flocculant Dose (rag/I)

[ * Nonlonk • 4%Anbni= .* 7%Aroma . . [5%Anionici

i . . - o - - 2 2 % Ar~,nlc ---t,-.- 3 0 % A r ~ n i ¢ ---+--- 4 7 0 A r m ~

Fig.5 Sedimentation rate data for several pretreatment flocculant anionic contents (i.e. percentage
sodium acrylate in the copolymer). The flocculant dose is split 1:1 and the second treatment is a
47% anionic content flocculant. NB. Higher levels of flocculant anionic content are shown with
dotted lines.

Figure 6 shows the effect of the cationicity of the pretreatment flocculant, when the second treatment is a
47% anionic content flocculant. The most desirable dose efficient performance is obtained with the non
15 I0 M J. Pearse et al.

ionic pretreatment llocculant. As the level of flocculant cationicity increases the level of dose efficient
sedimentation rate decreases.

Consideration of the data presented in Figures 5 and 6 highlights the high purity requirement for the
pl'etreatment flocculant when used in this dual treatment system.

12o ,- . . . . .

E
v 80

6O

• . : o°

E
°~

0
15 2-5 3.5 4.5

Total Floeculant Dose (mg/l)

* Nonlonic - 2%Cationic ~ 5% Cationic ---o-.. 15%Cationic ---o---20%Cationic]

Fig.6 Sedimentation rate data for several pretreatincnt flocculant cationic contents (i.e. percentage
methyl chloride quaternised dimethyl amino ethyl acrylate in the copolymer). The flocculant dose
is split 1:1 and the second treatment is a 47% anionic content flocculant. NB. Higher levels of
flocculant cationic content are shown with dotted lines.

Figure 7 shows the effect of altering the second treatment flocculant ionicity, when the pretreatment is a
non ionic llocculant. The flocculant dose efficiency improves as the level of second flocculant anionic
content increases, reaching a minimum dose requirement with 30% anionic content. If the second treatment
is cationic the dose efficiency is less desirable than the sequential addition of non ionic followed by non
ionic.

The results presented here, for the sequential dosing of non ionic flocculant followed by anionic flocculant
deal only with sedimentation rate. Benefits in terms of supernatant clarity and sediment volume
niinimisation are part of an on going line of research.

CONCLUSIONS

A new type of flocculant, referred to as a Unique Molecular Architecture flocculant, shows dose efficient
and robust sedimentation, turbidity removal and sediment compaction performance over a span of substrate
- flocculant mixing conditions and flocculant solution concentrations, when compared to a conventional
llocculant of identical anionic content.

The sequential use of non ionic flocculant followed by anionic flocculant leads to total flocculant dose
efficient sedimentation. The purity of the non ionic flocculant is critical for the effective use of this dual
flocculant system.
 Advancesin mineralflocculation 1511

110 --

100
e. anionic
o~
E 9o 47% and 30% //@~ 22% and 15% anionic

// / 7% and 4% anionic
~ 6o
e-
~ 5o
°~

e-

E
°~
,,~ 20 2%, 5%, 15% and
20% Cationic

2 3 4 5 6 7

Total Flocculant Dose (mg/l)

Fig.7 Sedimentation rate data for several second treatment flocculant anionic and cationic contents. The
flocculant dose is split 1"1. The pretreatment is a non ionic flocculant.

REFERENCES

Mohammed, A., Weir, S. and Moody, G. M., Flocculants : Development trends. Filtration and Separation,
2000, 37(8), 24-27.
Moody, G. M., Pre-treatment chemicals. In Proc. Selection and Scale-Up Jbr Solid~Liquid Separation,
Filtration Society 30 *l~Anniversa©' Symposium. Birmingham, 1994, pp. 9-29.
Moody, G. M. And McColl, P., Novel dewatcring aids for the pressure belt filtration of mineral slurries. In
Proc. Fihech Europa. D~sseldorf, 1997, pp. 393-406.
Pearse, M.J., Flocculant performance is enhanced by the Unique Molecular Architecture approach, World
Mining Equipment, 2000, 24(9), 60.
Peng, F. F. And Lu, Z., Polymer flocculation and coagulation for sedimentation of copper flotation tailing.
Minerals and Metallurgical Processing, 1998, 15(1), 14-20.
Weir, S., Flocculation of mineral suspensions by non ionic and anionic flocculants, Patent Application No.
GB 0029077.5, 2001. Publication date anticipated in 2002.
Weir, S. and Moody, G. M.. Trends in the development of llocculants as aids to solid/liquid separation. In
Proc. World Filtration Congress 8. Brighton, 2000, 2, pp. 1223-1226. Subsequently published in :
Journal of The Filtration Society, 2001, 1(4), 11-12,

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