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74 (2004) 85 – 90
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Abstract
This paper presents experimental data on using both flocculants and surfactants for aggregation and flotation of fines. The
work has been performed with water suspensions of two oxides, ZnO and MgO. Conventional flotation collectors (sodium
oleate (SOL), sodium dodecyl sulphate (SDS) and cetyltrimethylammonium bromide (CTAB)) were used. Commercial high
molecular weight polymers (MAGNAFLOC 1440, MAGNAFLOC E-10 and MAGNAFLOC 351) were the flocculants used.
Adsorption isotherms of surfactants adsorbing onto the two oxides were determined at natural pH. Adsorption density was the
greatest with sodium oleate. Zeta potential measurements indicated that addition of the cationic surfactant caused a positive
increase of the zeta potential. The positive zeta potential of MgO decreased with increased anionic surfactant concentration. A
decrease in stability indicated that the ZnO suspension pretreated with anionic surfactants caused the formation of larger flocs
when the cationic flocculant (MAGNAFLOC 1440) was added. Similar observations were obtained for a MgO suspension
pretreated with anionic surfactants and reacted with the nonionic flocculant, MAGNAFLOC 351. The negative charged
collector (SDS) appears to be good collector for ZnO floc flotation when hydrophobic flocs are created by the combination of
SDS and either cationic or nonionic flocculants.
D 2003 Elsevier B.V. All rights reserved.
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doi:10.1016/j.minpro.2003.09.007
86 Z. Sadowski, I. Polowczyk / Int. J. Miner. Process. 74 (2004) 85–90
Hydrophobic flocculation arises as a result of zeta potential measurements with surfactants, the
hydrophobic interaction between hydrophobic par- oxide suspensions were conditioned for 24 h to allow
ticles and an oppositely charged or nonionic floccu- the adsorption equilibrium.
lant. The separation of the hydrophobic flocs can
then be achieved using froth flotation (Song and Lu, 2.3. Adsorption study
2000).
The object of this present paper was to investigate Adsorption isotherms were determined in the
the interaction between surfactant and polymer and following manner: A suspension containing 0.5 g
the effect of these interactions on aggregation and of solid in 50 ml of surfactant solution was taken at
flotation of fine particles. natural pH and shaken for a definite time (8 h) to
attain equilibrium. Then the suspension was centri-
fuged and a supernatant was analyzed for remaining
2. Experimental procedure surfactant. A colorimetric method (Fowler and
Steel, 1968) was used to determine the residual
2.1. Materials and reagents surfactant concentration. The adsorption isotherms
were then obtained by plotting the amount of
ZnO obtained from Huta Olawa (Poland) was adsorbed surfactant as a function of equilibrium
used in this study. This material has a medium concentration.
particle size of 0.115 Am and a BET surface area
of 5.75 m2/g. MgO was purchased from Ubichem 2.4. Stability of suspensions
Limited, Hampshire, UK. The BET nitrogen specific
surface area of this sample was found to be 8.4 m2/ Stability or flocculation of oxide suspensions was
g. The mean particle size of MgO was found to be investigated by simple sedimentation measurement
0.88 Am. using an Andreassen pipette. The concentration of
Sodium dodecyl sulphate (SDS) used was suspension in these experiments was 1.25 g/cm3. The
obtained from BDH. Sodium oleate (SOL) and results of the sedimentation tests were reported in
cetyltrimethylammonium bromide (CTAB) were also terms of stability (S), which is defined as
used. Sodium oleate was supplied by Riedel-de Haën
(Germany).
W0 Wt
The flocculants used in the study were polymer S¼
reagents obtained from Allied Colloids, Bradford, W0
England (MAGNAFLOC 1440 cationic polymer,
MAFNAFLOC E-10 anionic polymer, MAGNA- where: W0 represents the weight of solids in a
FLOC 351 nonionic polymer). All reagents were used sample at the initial time t = 0. Wt represents the
without any further purification. same after 3 min.
Zeta potentials of oxide particles in the presence of Column flotation experiments were carried out in a
surfactants were determined from electrophoretic mo- glass column of 2.6 cm in diameter and 55 cm in
bility measurements. The NICOMP380 ZLS Zeta- height, fed with fine particles at the bottom. A stirrer
meter was used for the measurement of zeta bar magnet rotated on the bottom during flotation. A
potential (calculated using the Smoluchowski equa- suspension of hydrophobized fines was prepared in a
tion). Measurements were made in triplicate and the beaker and pumped to the column. The flocculant
average zeta potential values were reported as results. solution was led in the column at the opposite side.
The ionic strength was maintained at 10 3 M using Compressed air was introduced into the column
KCl. All zeta potential measurements were carried out through the glass porous membrane. The gas flow
at 20 jC. The pH of suspension was not adjusted. For rate during flotation was maintained at 64 cm3 min 1.
Z. Sadowski, I. Polowczyk / Int. J. Miner. Process. 74 (2004) 85–90 87
3. Results and discussion the case of SDS addition, zeta potential of MgO was
positive at low surfactant concentrations and became
The zeta potentials of investigated powders in the negative in the high concentration range (10 2 M).
presence of the different concentrations of surfactants On the other hand, the negative value of zeta potential
are shown in Fig. 1A and B. All measurements were of ZnO decreases with an increase in surfactant (SDS)
performed in 10 3 M KCl electrolyte concentration. concentration. With cationic surfactant addition
The isoelectric points of ZnO and MgO, found from a (CTAB), the positive values of zeta potential increase
literature, were 8.95 and 12.4, respectively (Parks, for both oxides when the surfactant concentration
1965; Yoon et al., 1979). increased.
The addition of sodium oleate causes an increase of Surfactant adsorption isotherms for the investigat-
negative values of zeta potential for both oxides. In ed oxides at natural pH are shown in Fig. 2A – C. The
high adsorption density of SOL may be a result of
both zinc and magnesium oleate precipitation. There-
fore, the adsorption values of sodium oleate appear
higher than for other investigated surfactants. The
cationic surfactant (CTAB) exhibits higher adsorption
on ZnO due to electrostatic attraction between the
negative surface and positively charged surfactant.
Both anionic surfactant isotherms for magnesium
oxide exhibit a high affinity behavior. This can be
also explained by an electrostatic attraction between
the positively charged magnesium oxide surface and
anionic surfactant.
The effects of surfactant concentrations on the
stability of oxide suspension are presented in Fig.
3A and B. The relationship between sedimentation
rate (stability), the size of agglomerate and the ad-
sorption isotherms of surfactants were observed. In
the ZnO case, a small concentration (10 5 M) of
anionic surfactant causes a decrease of suspension
stability. At pH=11 CTAB adsorption onto the MgO
surface is low and is in agreement with the high
stability observed during the Andreasen pipette
experiments. The low adsorption of cationic surfactant
observed in this study may be due to the electrostatic
repulsion between the surfactant and the MgO surface.
The aggregation process depicted in this study can
be divided into two steps: (1) adsorption of surfactant
on the oxide particles and (2) addition of flocculants
for surfactant – polymer complex creation. The aggre-
gates size may be expected to vary with the conditions
of both surfactant and polymer addition.
The orientation of the polymer –surfactant complex
on the particle surface should be relevant in interpret-
ing both the stability and flotation. In order to inves-
tigate the influence of surfactant –polymer interaction
Fig. 1. The effect of surfactants concentration on zeta potential of on the behavior of oxide suspensions, the stability of
oxide particles (A—ZnO, B—MgO). suspension was measured. The results obtained from
88 Z. Sadowski, I. Polowczyk / Int. J. Miner. Process. 74 (2004) 85–90
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Laskowski, S.J., Ralston, J., 1992. Colloid Chemistry in Mineral
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Rubio, J., Hoberg, H., 1993. The process of separation of fine
(Magnafloc 351) was used. Good flotation recovery
mineral particles by flotation with hydrophobic polymeric car-
of the flocs was obtained with an anionic collector rier. Int. J. Miner. Process. 37, 109 – 122.
(SDS) in the presence of both cationic and nonionic Sadowski, Z., 1994. A study on hydrophobic aggregation of calcite
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Song, S., Lu, S., 2000. Theory and applications of hydrophobic
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