Colloids and Surfaces

A: Physicochemical and Engineering Aspects 209 (2002) 15 26

www.elsevier.com/locate/colsurfa

Separation of oil from water by dissolved air flotation

A.A. Al-Shamrani a, A. James a,*, H. Xiao b
a
Department of Chemical Engineering, En6ironmental Technology Centre,
The Uni6ersity of Manchester Institute of Science and Technology UMIST, P.O. Box 88, Manchester M60 1QD, UK
b
Department of Paper Science, En6ironmental Technology Centre,
The Uni6ersity of Manchester Institute of Science and Technology UMIST, P.O. Box 88, Manchester M60 1QD, UK

Received 13 September 2001; accepted 13 December 2001

Abstract

Synthetic industrial effluent was prepared by stabilising low concentrations of oil (Catenex 11, Shell, UK) in
aqueous dispersion with a non-ionic surfactant (Span 20) and dissolved air flotation (DAF) was used to clarify this
wastewater. Operating parameters including saturator pressure, recycle ratio, and air to oil ratio, were investigated to
find conditions that would enhance the efficiency of the DAF separation. The zeta potential of the emulsion droplets
and flocculated oil droplets was determined and aluminium sulphate and four different cationic polyelectrolytes were
used to destabilise the system. Measurements indicated that a saturator efficiency of about 90% was achieved and it
was found that increasing the working pressure of saturator had less effect in the separation of oil droplets than
increasing recycle ratio. Optimum conditions for separation are obtained with an air to oil ratio of 0.0075
corresponding to a recycle ratio of 10%. The zeta potential measurements indicate that oil droplets are negatively
charged between pH 5 and 10. In addition the zeta potential measurements of flocculated oil droplets were found to
depend strongly on the concentration of the polyelectrolyte. Although an inversion of the oil droplets charge was
observed even at very low polyelectrolytes concentration. The polyelectrolytes were ineffective in enhancing the
separation. This effect can be related to the structure of the polyelectrolytes and to the adsorption mechanism. In
contrast, when aluminium sulphate was used it was found that it is important to decrease the magnitude of zeta
potential in order to decrease electrostatic repulsion so that the emulsion was destabilised prior to flotation. Under
these conditions DAF yields near complete oil separation even at moderate working pressure and recycle ratio when
the oil droplets are destabilised. 2002 Elsevier Science B.V. All rights reserved.

Keywords: Emulsion; Demulsification; Flocculation; Flotation; Industrial wastewater; Zeta potential

1. Introduction

Dissolved air flotation (DAF) is a process for

* Corresponding author. Tel.: + 44-161-200-4368; fax: +
44-161-200-4399.
E-mail address: alec.james@umist.ac.uk (A. James).
removing suspended particles from liquid by
bringing the particles to the surface of the liquid.
Air is dissolved at high pressure in a saturator,
and microbubbles are formed when water is re-

0927-7757/02/$ - see front matter 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 7 - 7 7 5 7 ( 0 2 ) 0 0 2 0 8 - X
16 A.A. Al-Shamrani et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 209 (2002) 1526
leased in the flotation cell at atmospheric pres-
sure. The microbubbles become attached to the
particles increasing their buoyancy and allowing
them to rise to the surface. Three operating
configurations have been described for DAF sys-
tems [1]. These are:
(a) Full-flow pressure flotation, where the influ-
ent is pressurised and then released in the
flotation tank where the bubbles are formed.
This is commonly used for particles, which do
not need flocculation but require large vol-
umes of air bubbles.
(b) Split-flow pressure flotation, where part of the
influent are pressurised and directly intro-
duced to the flotation tank. This is employed
in applications where suspended particles are
susceptible to the shearing effects of pressure
pump, also where suspended particles are at
low concentration and thus have a low air
requirement.
(c) Recycle-flow pressure flotation, where a por-
tion of treated wastewater is pressurised and
recycled to the flotation tank. This is gener-
ally employed where coagulation and floccu-
lation are needed and the flocculated particles
are mechanically weak. Recycle-flow pressure
flotation is used more often than the others
for applications including oil removal [2,3].
In the latter configuration small air bubbles of
less than 100 mm are formed when air saturated
recycle water is injected into the flotation tank
through needle valves or specially designed noz-
zles. The bubble formation process is a two step
process, first nucleation and the growth [4]. The
first step commences spontaneously after the pres-
sure reduction at the nozzle and the bubble nuclei
are produced in the super-saturated water. After
the excess air in the saturated water is transferred
from the dissolved to the gas phase, the second
step of bubble growth begins. During this step,
the total air volume remains constant but bubbles
grow due to coalescence and the decrease in the
hydrostatic pressure as they rise through the flota-
tion tank [5].
The production of microbubbles is considered
to be important as the rising velocity of the
bubbles is less than for larger bubbles. This en-
sures a longer residence time in the flotation tank
allowing more opportunities for collisions be-
tween bubbles and particle. In order to produce
microbubbles in the flotation tank, saturator pres-
sure of 400600 kPa are recommended [6]. Also,
the recycle flow, or the saturated water flow must
be high enough to provide a rapid pressure drop
and to prevent back flow and bubble growth in
the vicinity of the injection system.
The concentration of the supplied air bubbles
resulting from mixing the pressurised recycle flow,
or the saturated water flow, with the influent
wastewater affects bubbleparticle collisions and
consequently the removal of the bubbleparticle
agglomerates. This is considered to be an impor-
tant design and operating parameter in the DAF
process [7,8]. The air supplied for the DAF pro-
cess applications can be described in terms of the
recycle ratio, the mass concentration of the air
released in flotation, the air bubble volume con-
centration and the number concentration of air
bubbles [6].
Work by Zabel [9] and previously Hyde et al.
[10] has suggested that the highest possible effi-
ciency in most air saturator systems is about 90%
of the theoretical saturation. This is attributed to
the observation that air is a mixture of gases
consisting primarily of nitrogen and oxygen. The
latter gas has higher solubility than former and
dissolves more rapidly to produce a nitrogen-en-
riched atmosphere inside the saturator. At equi-
librium, the saturator air is composed of
approximately of 88.5% nitrogen and 11.5% oxy-
gen causing a reduction by about 9% in the
dissolution of air compared to 100% saturation
with atmospheric air [11].
After considering the number and size of bub-
bles in batch operations, determined from video
micrographs, it has been concluded that the aver-
age diameter of bubbles is constant regardless the
size of the pressure reduction orifice and as long
as the saturator pressure is greater than 392 kPa
this also has no influence on the size of bubbles
produced when it was over [12]. In addition, in a
study on saturation performance, Bratby and
Marais [8] found that it is difficult to saturate the
water fully at pressures less than 350 kPa. These
authors report that full saturation was achieved at
pressures greater than 350 kPa in a 55 cm deep
 A.A. Al-Shamrani et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 209 (2002) 1526
saturator packed with 25 mm Rasching rings.
They also found that the type of valve, the degree
of the turbulence in flotation chamber and the
concentration of particulate nuclei in the dilution
water had a negligible effect on the precipitation
of air from solution. However, their conclusions,
with respect to valve type, are in disagreement
with those of Rykaart and Haarhoff [4] who
compare the diameter of bubbles produced in
valves with internal bends and tapers. These au-
thors suggest that valve geometry have significant
effects on bubble size. Mean bubble diameters of
49.4 and 29.5 mm being observed, respectively for
each type of valve.
Recognising that small bubbles are required for
an efficient separation process, since large bubbles
create hydraulic disturbances whilst rising to the
surface and also decrease the net surface area, it
has been suggested that the optimum bubble size
for most DAF systems is approximately 50 mm
[13,14]. Other work involving measurements of
bubble size distributions for DAF systems has
indicated that bubbles achieve a steady state size
between 10 and 100 mm with the mean bubble
diameter being around 40 mm. This steady state
size is thought to depend on the saturation pres-
sure, recycle flow rate and nozzle geometry. In
addition the mean bubble diameter has been ob-
served to decrease as the saturation pressure and
the recycle flow rate through the nozzle increased
[15].
The quantity of air available for the DAF
process is controlled by both the saturator pres-
sure and the amount of recycled or saturated
water. In water treatment applications, experi-
ments where the recycle ratio and pressure are
varied showed that the final water quality was
only dependent upon the total quantity of air
introduced to the system and not upon the indi-
vidual values of the pressure or the recycle flow
[9]. This author concluded that the best practical
way to control and vary the amount of air sup-
plied is through the recycle ratio.
Edzwald et al. [6] examine the air requirements
for the treatment of three different types of water
contaminated with dissolved organic carbon
(DOC), clay and algae. These authors show that a
recycle ratio of 8% at a saturator pressure of 483
17
kPa with 70% saturator efficiency, corresponding
to bubble volume and number concentrations of
about 4600 ppm and bubble number concentra-
tion of 1.2 105 bubbles, respectively, is sufficient
to successfully treat all three types of water. In
addition, while DAF has been shown to be an
effective treatment process for water containing
low-density particles and for low turbidity water.
It has also been used widely for thickening acti-
vated sludge [1621]. In contrast to these numer-
ous applications, there are relatively few
investigations into the treatment of emulsified oils
using DAF [3].
Coagulation and flocculation are very impor-
tant as a pre-treatment process for DAF and an
essential requirement for efficient flotation [20]. It
has been reported that the flotation process de-
pends strongly on the charge of the particles and
bubbles and that the maximum rate of flotation
can be achieved when the zeta potential of the
particles is zero [14,22]. Chemical pre-treatment of
oil water emulsions, demulsification, is based on
the addition of chemicals that destroy the protec-
tive action of the emulsifying agent, overcoming
the repulsive effects of the electrical double layers
to allow the finely-sized oil droplets to form larger
droplets through coalescence [23,24]. To this end
the main objectives of the present work are to
optimise the operation parameters to enhance the
efficiency of DAF in separation of oil droplets
from a synthetic wastewater and to improve the
understanding of separation mechanism in terms
of zeta potential measurements. In this study the
synthetic wastewater was prepared by stabilising
oil droplets using a non-ionic surfactant and the
aluminium sulphate and four different polyelec-
trolytes were used as destabilising agents.
2. Materials and methods
A bench scale DAF unit (Capital Controls,
Oxfordshire, UK) was used. The unit, as shown in
Fig. 1, consisted of an oil-free air compressor; a
9-l stainless steel unpacked saturator vessel and a
1.5 l flotation cell. The unit was designed so that
rapid mixing, flocculation and flotation can be
carried out in the same vessel. The cell was
18 A.A. Al-Shamrani et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 209 (2002) 1526

equipped with a needle valve through which air- aluminium sulphate (Analar, BDH Chemicals
saturated water was injected; in addition there Ltd., Poole, UK), sodium hydroxide (SLR, Fisher
were two sampling points and a drain. Scientific, UK). A solution of 2 g l 1 of alu-
The in organic chemical coagulant used was minium sulphate was prepared daily for experi-

Fig. 1. Schematic diagram for the DAF unit.

 A.A. Al-Shamrani et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 209 (2002) 1526
mental use. Four cationic polymers (Ciba Chemi-
cal, UK) with various molecular weight and
charge density were used. The high molecular
weight polymers used are Hydrocol 882 and 864
in which the former is low charge density and the
latter is high charge density. On the other hand,
the low molecular weight polymers used are Hy-
drocol 852 and 1142 in which the former is low
charge density and the latter is high charge den-
sity. A solution of 0.5 g l 1 of polymers was
prepared weekly for experimental uses and kept in
refrigerator at 5 C for a maximum of 1 week.
Hydrochloric acid (Analar, Fisher Scientific,
UK) was used to adjust pH to desired values;
while 0.1 M sodium hydroxide was used to main-
tain the pre-adjusted pH value during the coagu-
lation stage and 1 mM sodium chloride (SLR,
Fisher Scientific, UK) was used to maintain ionic
strength.
A solvent refined petroleum distillate manufac-
tured from crude petroleum oil (Catenex oil 11,
Shell, UK), was used to prepare wastewater sam-
ples. The non-ionic surfactant, sorbitan monolau-
rate, Span 20 with 8.6 HLB (Sigma Aldrich Ltd.,
Dorset, UK), at a concentration of 0.3% by
weight to produce stable emulsions. The desired
amount of oil in the synthetic wastewater, 1630
ppm, was added to 1 l of de-ionised water and
mixed at 18 000 rpm in a blender (Fisher Scien-
tific, UK) for 4 min. It has been found that
blending for 4 min using 0.3% Span 20 produces a
stable, high turbidity emulsion [25].
The conditions in a typical DAF system where
a recycle stream of clarified water is saturated
before being injected to the flotation tank were
simulated by adopting the following procedure.
The saturator was two-thirds filled with de-ionised
water, connected to the compressor, pressurised
to the desired working pressure and shaken vigor-
ously for 2 min to ensure that the air was more or
less completely dissolved. The pressurised water
was allowed to stand for 5 min before shaking
again. This procedure was repeated until the pres-
sure did not fall after shaking. At this stage the
recycle water had a turbid milky appearance and
as there was no further fall in pressure it was
assumed that at this point the water should be
saturated. In order to maintain the level of dis-
19
solved air, the saturator was shaken repeatedly
after every water injection to the flotation cell.
The pressure regulator on the inlet line from the
compressor ensures that the working pressure is
maintained. The saturator efficiency was deter-
mined using a procedure similar to that of Henry
and Gehr [21] and Shawwa [26].
Flocculation and flotation experiments were ex-
ecuted as follows: after pH adjustment, 1 l of the
synthetic wastewater was introduced to the flota-
tion cell and the wastewater was subjected to high
shear by mixing rapidly at 200 rpm for 1 min. The
required amount of aluminium sulphate or poly-
mer under investigation was added at the start of
the rapid mixing period and this operation was
followed by a period of slow mixing at low shear
(20 rpm) for 15 min.
At the end of the low shear period, the mixer
was switched off and the air-rich water from the
saturator was injected into the flotation cell in
quantities approximate to the required recycle
ratio and at the desired working pressure. The
volume of air-rich water was monitored using a
calibrated scale attached to the side of the flota-
tion cell. The cell contents were left for 7 min so
that flotation could proceed before samples were
taken for analysis.
Measurement of the zeta potential and diameter
of oil droplets was made using a Zeta-Sizer 3000
HS (Malvern Instruments, UK). Five and 10
replications were made for zeta potential measure-
ments and size determination, respectively and
mean values were obtained from these results. The
zeta potential of oil droplets as a function of pH
was measured after emulsification and before the
addition of flocculent or coagulant. For these
measurements the emulsion was diluted and the
ionic strength was kept constant at 10 3 M NaCl,
while the pH was adjusted using sodium hydrox-
ide or hydrochloric acid solutions. Same proce-
dure was adopted for zeta measurement for
flocculated oil droplets, where samples were col-
lected after flocculation and before flotation pe-
riod and submitted for zeta potential
measurement.
Samples of clarified water were collected from
below the float layer at the upper sampling point
in the flotation cell and about 8 cm above the
20 A.A. Al-Shamrani et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 209 (2002) 1526

base for analysis and appropriate dilutions were

made where necessary. The turbidity of the sam-
ple that can be used to determine the oil concen-
tration [27,28] was measured in units of NTU
(Nephelometric Turbidity Units) on a turbidity
meter (WPA TU1100, UK). In addition, follow-
ing previous work [37], a spectrophotometer (UV/
Vis/VIR Spectroscopy, Perkin Elmer, UK) was
used to produce a calibration curve to determine
oil concentration. The calibration curve was ex-
tensively tested with numerous samples of vary-
ing, but known concentration, a correlation
coefficient of 0.99 was recorded.

3. Results and discussion Fig. 2. Experimental and theoretical mass of air released as a
function of saturation pressure at 19 C. (Theoretical curve
taken from Ref. [20].)
In order to investigate the effects of saturator
pressure, recycle ratio and the air to oil droplets
ratio on DAF performance, aluminium sulphate Almost same trend is observed when 50 mg l 1
was used as the destabilising coagulant for oil aluminium sulphate is used, that is the residual oil
droplets at three different dosages specifically: 20, concentration decreases from 426 ppm at 50 psi to
50, and 100 mg l 1. The flotation time was fixed 209 ppm at 80 psi, also the residual turbidity
at 7 min and the system was maintained at pH 8 decreases from 261 NTU at 50 psi to 123 NTU at
as this has been found to be optimal [25]. 80 psi saturator working pressure. The outcome is
For accurate measurement of the quantity of
different when 100 mg l 1 aluminium sulphate is
air injected into the flotation cell it was necessary
used as there was a significant reduction in resid-
to determine the saturator efficiency. Four trials
ual oil concentration and turbidity even at low
were carried out and the averaged results indicate
a final saturation of 88%. The amounts of air that
can be released at 88% efficiency compared to the
theoretical of 100% predicted by Henrys law at
the different working pressures investigated are
presented in Fig. 2.
The quantity of air that can be introduced to
the flotation cell can be varied by changing the
saturator working pressure or the recycle ratio or
both. In order to investigate the effect of the
saturator working pressure on DAF performance
a recycle ratio of 1:10 was adopted. Results pre-
sented in Figs. 3 and 4 show that at 50 psi and
using 20 mg l 1 aluminium sulphate, the oil
concentration can be reduced from 1630 ppm and
turbidity of 975 NTU to 788 ppm and 458 NTU,
respectively. These figures gradually reduced with
increased saturation pressure to reach 508 ppm oil
concentration and 300 NTU residual turbidity Fig. 3. Residual oil concentration as a function of saturation
when 80 psi was used in the saturation. pressure.
 A.A. Al-Shamrani et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 209 (2002) 1526 21

Fig. 4. Residual turbidity as a function of saturation pressure.

Fig. 5. Residual oil concentration as a function of recycle
ratio.
saturator pressures where 94.5 and 94.2% removal
efficiency for oil and turbidity, respectively were
achieved at 50 psi. Increasing working pressure to
It is evident that the removal of oil droplets
80 psi results in 99.3 and 98.8% removal efficien-
cies for oil and turbidity, respectively. stabilised by Span 20 can be obtained at 100 mg
The second parameter that plays an important l 1 and 10% recycle ratio, whilst increasing the
role in quantity of air released to the flotation cell recycle ratio above 10% result negligible improve-
is the recycle ratio. To determine the optimum ment in residual oil concentration and residual
recycle ratio a constant saturator pressure of 80 turbidity. This ratio is much less than that
psi was used and recycle ratios in range of 2 20% recorded by Zouboulis and Avranas [3] in their
were employed. Samples of clarified water were
taken for analysis at each recycle ratio interval.
Results presented in Figs. 5 and 6 show a sharp
reduction in residual oil concentration and turbid-
ity at all aluminium sulphate dosages investigated
when 8% recycle ratio is employed. Using 20 mg
l 1 aluminium sulphate, the oil concentration and
turbidity decrease from 1630 ppm and 975 NTU
to 527 ppm and 306 NTU, respectively followed
by a further slight reduction obtained by increas-
ing the recycle ratio, the residual oil concentration
and residual turbidity reach 388 ppm and 229
NTU, respectively at a recycle ratio of 20%. The
same trend was observed when 50 mg l 1 alu-
minium sulphate was used where oil concentra-
tion and turbidity were reduced to 209 ppm and
123 NTU when 10% recycle ratio was employed.
Further reductions were observed at increased
recycle ratio. Fig. 6. Residual turbidity as a function of recycle ratio.
22 A.A. Al-Shamrani et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 209 (2002) 1526
Fig. 7. Percentage of oil removal as a function of the air to oil
droplet ratio.
study of the treatment of an oil in water emulsion,
stabilised by Tween 80, by coagulation and DAF.
Another important design parameter is the ra-
tio of air to dispersed particles, that is oil droplets
in the present case where DAF depends in this
ratio. Fig. 7 shows batch flotation performance as
a function of the ratio of air to oil droplets. It is
noted that an air to oil ratio of around 7.410 3
is considered as an optimum value for good DAF
performance, especially when oil droplets are neu-
tralised by a high dosage of aluminium sulphate,
typically 100 mg l 1, where maximum floccula-
tion and coalescence of oil droplets can be
achieved. This value is relatively low compared to
others previously reported [1]. This may be be-
cause destabilised oil droplets need a relatively
low volume of pressurised air to enhance the
flotation process.
The emulsion was prepared at pH 3.6 and the
zeta potential of the oil droplets in the prepared
emulsion was 59.9 9 3.8 mV. This relatively
high zeta potential can be expected to produce
sufficient electrostatic repulsion between oil
droplets to maintain the stability of the system.
Fig. 8 shows the zeta potential measurement of oil
droplets as a function of pH in the presence of 1
mM NaCl. The results demonstrate clearly that
oil droplets stabilised by non-ionic surfactant,
Span 20, are negatively charged over the entire
pH range investigated as shown in Fig. 8. The
results also show that the magnitude of negative
zeta potential increases gradually with pH to
reach its maximum (n= 105.9 mV) at pH 9
followed by a slightly reduction at pH 10 (n=
100.5 mV). The negative charges are thought to
result from adsorption of hydroxyl ion at the
oil water interface [29].
Measurements indicate that, in the initial emul-
sions, oil droplets are approximately 407 nm in
diameter, which is clearly in the colloidal range of
particle size and suggests that for the emulsions
investigated, the separation performance of DAF
is related to the physico-chemical properties of the
system.
The zeta potential of air bubbles was not mea-
sured in this work. However, literature indicates
that air bubbles have a large negative zeta poten-
tial [12,30,31]. This implies that the electrostatic
repulsion makes attachment of a bubble to oil
droplets unlikely unless the oil droplets are chem-
ically treated. Thus, it is important to decrease the
electrostatic repulsion barrier in oil emulsion sys-
tems under investigation prior to flotation. In
agreement with this, it is noted that adding alu-
minium sulphate to reduce the magnitude of the
zeta potential of oil droplets appears to be a
crucial factor in DAF performance of such emul-
sion systems. By contrast, increasing saturator
pressure, recycle ratio and air to oil ratio do not
Fig. 8. Zeta potential of the stabilised oil droplets before
flocculation as a function of pH.
 A.A. Al-Shamrani et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 209 (2002) 1526 23

play the same significant role as altering coagulant

dosage.
It is evident that the flotation of oil droplets
that is stabilised by Span 20 depends on the
physico-chemical properties of the system. That is
chemical pre-treatment of an oil emulsion is based
on the addition of chemicals that destroy the
protective action of the emulsifying agent and to
over come the repulsion effect of the double layer
and allow the oil particles to form larger drops
[23,24]. The maximum rate of flotation is obtained
when 100 mg l 1 of aluminium sulphate is used
and it is expected that the zeta potential of the oil
droplets is reduced and the charge is brought to
neutralisation suggesting that coagulation and
Fig. 9. Residual turbidity and flocculated zeta potential as a
flocculation are very important as a pre-treatment function of Hydrocol 852 concentration at pH 7 (", zeta
process for DAF and an essential requirement for potential;
, residual turbidity).
efficient flotation.
On the other hand, addition of polyelectrolyte all concentrations used. Similar behaviour is ob-
to increase oil removal efficiency by flotation can served in Figs. 11 and 12 for high molecular
be attributed to different mechanism: flocculation weight polyelectrolytes (Hydrocol 882 and 884).
of the oil droplets, reduce electrostatic repulsion Here the zeta potential of flocculated droplets
between the air bubble and oil droplet and in- becomes positive even at very low polyelectrolyte
crease oil droplet hydrophobicity [27]. The zeta concentration, however the flotation performance
potential measurement of prepared oil emulsion was negligible.
indicate that oil droplets are negatively charged, Elsewhere, this effect has been attributed to the
so to compare flotation performance using differ-
adsorption of an excessive amount of polyelec-
ent polyelectrolyte to performance of flotation
trolytes onto oil droplets surface, which can cause
using different inorganic salts presented in our
both steric and/or electrostatic restabilisation [2].
previous work [25], cationic polyelectrolytes were
chosen in this work.
Results for low molecular weight polyelec-
trolytes Hydrocol 852 and 1142 are presented in
Figs. 9 and 10. It is noticeable that the magnitude
of the zeta potential of oil droplets is reduced
from its initial value 73 mV at pH 8 to 6.3
mV when 0.1 mg l 1 Hydrocol 852 was used.
This figure increased by increasing Hydrocol 852
doses where positive zeta potential registered
when 0.5 mg l 1 was used. Zeta potential in-
creases by increasing Hydrocol 852 doses to reach
+ 25 mV when 5 mg l 1 was used. In case of
Hydrocol 1142 positive zeta potentials were regis-
tered even at low concentration where it can be
noticed from Fig. 9 that the zeta potential was
+26 mV when 0.1 mg l 1 of Hydrocol 1142 was Fig. 10. Residual turbidity and flocculated zeta potential as a
used. But as can be seen there was no noticed function of Hydrocol 1142 concentration at pH 7 (", zeta
reduction in turbidity for both polyelectrolytes at potential;
, residual turbidity).
24 A.A. Al-Shamrani et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 209 (2002) 1526
Fig. 11. Residual turbidity and flocculated zeta potential as a
function of Hydrocol 882 concentration at pH 7 (", zeta
potential;
, residual turbidity).
In order to check this assertion, supplementary
experiments were conducted using very low con-
centrations of polymer (much lower than those
presented in Figs. 8 11) and again no separation
was observed. In addition, it has been reported
that oil separation by flotation is strongly depen-
dent on the zeta potentials of both the oil droplets
Fig. 12. Residual turbidity and flocculated zeta potential as a
function of Hydrocol 864 concentration at pH 7 (", zeta
potential;
, residual turbidity).
and air bubbles and flotation performance in-
creased by reducing the negative charge on oil
droplets [31]. However, the charge of the oil
droplets was alerted by inorganic salts rather than
polyelectrolyte. According to that and DLVO ap-
proach, collision between air bubble and posi-
tively oil droplets should take place, which might
result in some oil separation, but this was not
observed as can be seen for flotation performance
in the previous demonstration (Figs. 8 11).
Other workers [32] have noted that since double
layer thickness depends markedly on the ionic
strength and increasing ionic strength reduces the
double layer thickness and also reduces the
polyelectrolytes stability and leads to efficient
flotation. Elsewhere it has been observed that as
ionic strength increases interparticle repulsions be-
tween polyelectrolytes decrease [33] and in addi-
tion, it has been found that desorption of highly
charged polyelectrolytes on oppositely charged
surfaces is very slow in low ionic strength solution
[34]. In order to test these observations, the con-
centration of NaCl was increased from 10 3 to
10 2 M to reduce the double layer thickness so
that the attractive forces would predominant and
then allow agglomeration of oil droplets. Further
experiments involved the addition of CaCl2 at a
concentration of 10 2 M in the presence of 10 3
M NaCl before the addition of the high molecular
weight and high charge density polyelectrolyte
(Hydrocol 864) at different concentrations. In
these experiments no clarification observed sug-
gesting that double layer compression is not sig-
nificant factor for the polyelectrolyte tested.
Oil droplet flocculation was seen when alu-
minium sulphate was added and visible large flocs
were observed. While standard double layer the-
ory qualitatively explains improvements in clarifi-
cation produced by aluminium sulphate, it does
not appear to explain the lack of improvement
when the polyelectrolytes were used. Additional
explanation is required. Although, little is known
about the effects of adding polymers to surfac-
tantwateroil systems [35,36], it seems that this
effect can be interpreted following the ideas of
Nikolov et al. [37] who state that according to
DLVO theory cationic polyelectrolyte adsorbs at
the negatively charged oilwater interface and
 A.A. Al-Shamrani et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 209 (2002) 1526
forms a mixed layer with the adsorbed non-ionic
surfactant, resulting in lowering the stabilising
barrier produced by the pre-adsorbed non-ionic
surfactant layer. This suggests that the floccula-
tion destabilisation mechanism involves the
physico-chemical interfacial properties of the
mixed layer which change the tangential inter-
molecular interactions that cause a change in the
adsorbed layer strength. These changes in the
mixed layer can only be achieved when flocculants
have both high diffusivity and good surface activ-
ity, which might not be true for the polyelec-
trolytes that have been chosen in the current
work. Another interpretation for these negative
results regarding polyelectrolytes might be that
the polyelectrolytes used in this work dissolve in
the non-ionic surfactant, Span 20. It has been
reported that some polyelectrolytes can be soluble
in a non-ionic surfactant lamellar phase [35]. An-
other suggestion is that the addition of polymer
results in an increases in the surface elasticity [36]
which in turn increase the continuous phase film
stability against rupture. This might also explain
the stability of oil droplets against flotation in-
spite of the reduction in oil droplets zeta
potential.
In addition, the ineffectiveness of oil droplet
aggregation and flotation induced by cationic
polymer could also be attributed to the character-
istics of the polymers. All polymers used in this
work are polyacrylamide-based copolymers con-
taining quaternary ammonium groups, which are
water soluble and very hydrophilic in nature.
Adsorption of the polymer on oil droplets indeed
increases the zeta-potential and renders them
cationic. But on the other hand, the polymer
layers prevent the hydrophobic interaction from
being effective. Both charge interaction and hy-
drophobic attraction appear to be important in
the current system, particularly because the air
bubble is claimed as one of the most hydrophobic
materials. Moreover, the hydrophobic interaction
is mainly a long-range force [38], compared with
van der Waals attraction. Hydrophilic polymer
layer on oil droplets will cause deterioration in the
hydrophobic attraction among oil droplets and
between oil droplets and air bubbles. This effect
might become even more significant for the poly-
25
mers with high molecular weight since the thick-
ness of polymer layer is very likely beyond the
range of hydrophobic attraction. Conventional
bridging mechanism for the flocculation of fine
solids by high molecular weight polyelectrolytes
seems invalid in the current system. Synergy be-
tween charge interaction and hydrophobic attrac-
tion appears to be crucial.
From the above, it is seen that charge reversal
alone does not mean that oil droplets will floccu-
late, because the adsorption of polymer could
alter oil water interfacial properties, which will
prevent oil droplet coalescence.
4. Conclusions
The destabilisation of oil droplets using alu-
minium sulphate has been conducted with differ-
ent coagulant dosages at optimum pH of 8 in
order to determine air requirements for DAF. The
zeta potential measurements indicate that oil
droplets are negatively charged over a range of
pH and its magnitude is large enough to stabilise
oil droplets. The negative zeta charge could be
contributed from the adsorption of hydroxyl ion
on the surface of the oil droplets where some pH
dependence was observed.
Measurements of dissolved air content indicate
that about 90% saturator efficiency can be
achieved. The performance of DAF for separation
of oil water emulsion can be improved within
certain limits by increasing working pressure
where micro-bubbles can be produced. The recy-
cle ratio of about 10% at high working pressure
remove almost all oil content when oil droplets
are chemically destabilised at 100 mg l 1 alu-
minium sulphate prior to flotation. It was found
that an air to oil ratio of about of 0.0075 is
enough for good DAF performance. This value is
relatively low compared to previous findings [1]; it
may be that destabilised oil droplets need rela-
tively low volume of pressurised air to enhance
the flotation process.
Although negative results reported with all
polyelectrolytes investigated, it was found that
DAF yields nearly complete oil separation even at
moderate working pressure and recycle ratio when
26 A.A. Al-Shamrani et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 209 (2002) 1526
oil droplets destabilised using aluminium sul-
phate. Relatively poor separation was observed
when low aluminium sulphate dosage was em-
ployed, even at high working pressure and recycle
ratios only about 72% oil removal efficiency was
achieved. Thus, it can be concluded that it is
important to decrease the electrostatic repulsion
barrier in the emulsions systems stabilised by
Span 20 by using aluminium sulphate prior to
flotation as this has a greater effect on the quan-
tity of air supplied. While standard double layer
theory qualitatively explains improvements in
clarification produced by aluminium sulphate, it
does not appear to explain the lack of improve-
ment when the polyelectrolytes were used. It can
be concluded that reducing zeta potential of oil
droplets alone using polymers does not mean that
oil droplets will flocculate in all cases, because the
adsorption of polymer might change the oil wa-
ter interfacial property which might prevent oil
droplet coalescence as it has been observed in this
work.
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