Colloids and Surfaces

A: Physicochemical and Engineering Aspects 172 (2000) 153 161

www.elsevier.nl/locate/colsurfa

Treatment of oil-in-water emulsions by coagulation and

dissolved-air flotation
A.I. Zouboulis *, A. Avranas
Department of Chemistry, Aristotle Uni6ersity, 54006 Thessaloniki, Greece
Received 19 November 1999; accepted 16 March 2000

Abstract
The treatment of oil-in-water emulsions containing n-octane (used as simulated wastewater) was investigated by
means of dissolved-air flotation jar-tests. The effect of several parameters on flotation efficiency for separation of the
emulsified oil was examined, namely, (a) the presence the nonionic surfactant Tween 80, used for the stabilization of
the emulsions, (b) the initial pH value of the emulsions, (c) the concentration of chemical additives, such as
polyelectrolytes (organic flocculants of cationic or anionic type) or ferric chloride (inorganic coagulant), (d) the
concentration of sodium oleate (used as flotation collector) and (e) the recycle ratio. Zeta-potential measurements
were also performed in order to interpret the obtained results. The use of polyelectrolytes was not able to effectively
treat the studied emulsions, while the addition of ferric chloride and the subsequent application of dissolved-air
flotation was found very efficient. At the optimum defined experimental conditions (recycle ratio: 30%, pH: 6, [Fe3 + ]:
100 mg l 1 and [sodium oleate]: 50 mg l 1) more than 95% of the emulsified oil was effectively separated from an
initial concentration of 500 mg l 1. 2000 Elsevier Science B.V. All rights reserved.
Keywords: Octane-in-water emulsions; Wastewater treatment; Tween 80; Dissolved-air flotation; Zeta-potential

1. Introduction
The continuous expansion of hydrocarbon processing industry and the extensive utilization of
oil-related products in most industrial branches
(automobile industries, aircraft plants, chemical
industries, machine shops, etc.), have increased
the threat of oil pollution to the environment. The
concentration of oil in effluents from different

* Corresponding author. Tel.: +30-31-997794; fax: + 3031-206138.

E-mail address: zoubouli@chem.auth.gr (A.I. Zouboulis)

industrial sources is found to vary widely, from

several to as high as 40 000 mg l 1 [1]. Unlike
free or floating oil spilled in the sea, lakes or
rivers, most of industrial wastewaters contain oilin-water emulsions among their basic contaminants. Emulsified oil droplets of the order of few
micrometers in diameter due to electrostatic repulsion forces are protected from spontaneous coalescence into larger ones, making oil separation by
simple gravity separation a difficult and time-consuming process [2]. Several methods have been
applied for the removal of oil from wastewaters
[3], such as adsorption [4], flocculation [5], electrocoagulation [6] and flotation [710].

0927-7757/00/$ - see front matter 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 7 - 7 7 5 7 ( 0 0 ) 0 0 5 6 1 - 6

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Flotation techniques, in which finely suspended

particles are separated by adhering to the surface
of rising bubbles, have proved efficient, practical
and reliable separation methods for the removal
of oils, as well as other contaminants, such as
dissolved ions, fats, biomolecules and/or suspended solids from water [11]. Flotation is mainly
used, when the application of sedimentation is not
feasible, due to the presence of extremely fine
particles or globules, which do not possess a
significant settling rate, because the phases do not
appreciably differ in density from the parent liquid. This process is thus very similar to the separation occurring in an American Petroleum
Institute (API) gravity separator. The difference is
that flotation is more effective for the removal of
emulsified-oil droplets, because the buoyancy difference is enhanced by attachment to small air
bubbles.
The flotation process relies on the surface
chemistry of material to be separated. The naturally hydrophobic materials are ideal candidates.
This process involves a number of physical phenomena simultaneously occurring while several
variables have been found to influence the process. It has also been theoretically predicted that
the collection efficiency of emulsions will be increased, on increasing the droplet size and decreasing the bubble size [12].
Oil is usually removed from wastewater mainly
by using the dissolved-air flotation (DAF) technique for bubble generation. The other flotation
techniques, namely dispersed or induced air and
electrolytic flotation, are less frequently used [13].
There are three basic flow sheets for DAF process: (a) total pressurization of influent wastewater, (b) partial pressurization, and (c) recycle
pressurization, where a stream consisting of 20
50% of clarified effluent flow is being recycled,
pressurized and mixed with the raw influent. The
latter mode is the preferred process in most oily
wastewater treatment systems. Oil droplets with
size greater than 40 mm can be effectively removed
by applying DAF units. However, the flotation
rate occasionally would be smaller than that predicted. In order to overcome the smaller droplet
sizes and the hydrophilic nature of most wastewater contaminants, coagulants and flocculants are
useful additives [14].

Most of the published papers dealing with

emulsified oil treatment by flotation are case studies of specific wastewaters and therefore, they
could be considered as rather empirical approaches. Relatively few systematic investigations
have appeared in the literature while several aspects still remain to be investigated [1517].
Therefore, the main aim of this study was to
optimize DAF process for efficient treatment of
emulsified oil, through the careful selection of pH
conditions and type and dose of chemical additives (flocculants, coagulant), which could maximize the separation/removal of oil from
wastewaters, to determine the limits of DAF process and to provide certain theoretical explanations of the obtained results.

2. Experimental part

2.1. Materials
n-Octane, a typical hydrocarbon and a common constituent of most petroleum products was
used as the oil phase. It was selected for the
preparation of emulsions, since as it had been
referred, evaporation did not occur during flotation of aliphatic hydrocarbons with molecular
weights equal or higher than that of octane, and
also because of its very low solubility in water
(0.66 mg l 1) [18]. Octane (of puriss quality) was
obtained from Carlo Erba and its initial concentration in the prepared emulsions was 500 mg l 1.
The non-ionic surfactant Tween 80 (polyoxyethylene-(20)-sorbitane mono-oleate), a registered trademark of ICI America, of puriss quality
for bacteriology obtained from Fluka, was used
as emulsifier. The concentration of Tween 80 in
the emulsion systems studied was 0.05% w/w, i.e.
slightly above its critical micelle concentration
[19]; it was selected during preliminary experiments.
Two different flocculants (organic polyelectrolytes) were also examined: the anionic polyacrylamide and the cationic K-1384, both
supplied by Kemira Oy, Finland. Stock aqueous
solutions were prepared according to the instructions of the supplying company and they were

A.I. Zouboulis, A. A6ranas / Colloids and Surfaces A: Physicochem. Eng. Aspects 172 (2000) 153161

used at final concentrations up to 10 mg l 1.

Stock solutions of the common inorganic coagulant ferric chloride (technical grade, obtained
from Riedel-de-Haen) were always freshly prepared.
Sodium oleate (99% purity, denoted as SO) was
obtained from Sigma and was used as a common
anionic flotation collector in order to enhance the
floatability of coagulated solids and emulsion
droplets. The concentration of sodium oleate
added in the coagulated emulsions was 50100
mg l 1 (1.5 3.0 10 4 M), i.e. below its critical
micelle concentration [20], unless otherwise stated.
The pH of the emulsions was adjusted by the
addition of HNO3 or NaOH, if necessary. Millipore water was used in all the experiments.

2.2. Methods
The preparation of oil-in-water emulsions was
performed according to the following procedure:
0.5000 g of n-octane was added in a glass-stoppered bottle containing 100 ml water or aqueous
solution of Tween 80. After hand-shaking of the
mixture for approximately 15 min, the emulsion
was ultrasonically prepared using a Minisonic 4
Ultrasonic Laboratory homogeniser. The oil/water mixture was irradiated for 230 s with an 1
min pause to avoid overheating. This time period
was found sufficient for the preparation of emulsions, while longer time did not further increase
the stability of prepared emulsions. The proportion of fairly larger droplets was kept around
25% of the total number. The mean diameter of
the droplets immediately after emulsification,
ranged from 2 to 6 mm, in presence or absence of
Tween 80 respectively as it was found by direct
optical observations with a microscope. The produced emulsion was stable for at least 1 h (without Tween 80) or for at least 3 h (in the presence
of Tween 80).
In DAF systems, water or wastewater is pressurized in a separate tank with air addition at
approximately 4 5 atm; as a result, air dissolves
and super-saturates the liquid. When the pressurized solution flows into another (open) flotation
tank, under the release of pressure, air precipitates
out of solution on nucleation sites, formed by the

155

presence of colloidal particles or droplets and as a

result very fine gas bubbles (30120 mm) are
created. These bubbles carry the oil droplets, as
well as other suspended solids, to the surface of
the tank, whether they can be easily removed. The
DAF jar-test unit used in this study was supplied
by AZTEC, UK. A plastic cylindrical column
with 10 cm internal diameter and 60 cm height
was used as the flotation cell (column). One-liter
equilibrated emulsion sample, prepared as previously described, was transferred to the flotation
column by slowly pouring. The recycle ratio
(RR%) parameter was approached in laboratoryscale flotation tests by controlling the volume
difference in flotation cell during the experiment,
caused by the addition of pressurized solution.
Therefore, a recycle ratio of 30% corresponding to
an increase of the initial volume (1 l) by 30%, was
used for most experiments, unless otherwise
stated.
The measurement of emulsion turbidity was
performed using a HACH 2000 turbidimeter with
a highest sensitivity of 0.001 NTU. Turbidity was
used to determine oil concentrations using a standard reference line, obtained by measuring known
oil concentrations (with or without Tween 80).
The accuracy of this line was frequently checked
having a correlation coefficient (r 2) of 0.98. The
effectiveness of emulsified octane separation by
flotation was evaluated from the degree of treatment (Re%), calculated using the formula: Re%=
[(To T)/To] 100, where To and T are the initial
and final emulsion turbidities, corresponding to
the initial and final oil concentrations, respectively.
The electrophoretic mobility of oil droplets was
determined using a modified demountable apparatus containing a cell of flat design. A direct current was applied between the electrodes and the
electrophoretic velocity of oil droplets was measured under a microscope equipped with a
graticule and focused upon the stationary level.
The details of this system have already been published [21].
A concentrated solution of NaCl was added
immediately after emulsification at a final concentration of 0.02 M in order to keep the ionic
strength constant for zeta potential measure-

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ments. A background electrolyte concentration of

0.02 M had been found necessary to facilitate a
good response time, stabilise pH measurements
and improve the repeatability of mobility measurements. Higher electrolyte levels were avoided,
due to the adverse effects of double layer compression, which would reduce the stability of
emulsion and hence, the mobility values would be
lowered. The electrophoretic mobility was measured 1 h after the emulsification. The emulsions
were stored at 22C. No change in the electrophoretic mobility was observed upon short
ageing. The electrophoretic mobilities of droplets
in the same sample had almost identical values,
with a very small variation, due to the similar
diameters of droplets. The experimental uncertainty during electrophoretic determinations was
within 3%. The respecting zeta-potential values
were calculated by means of the Smoluchowski
equation [22].

Fig. 1. Influence of polyelectrolyte concentration on flotation

efficiency for different pH values; (a) anionic polyacrylamide,
(b) cationic K-1384.

The pH values of emulsions were controlled by

using a specific glass electrode, supplied by
Metrohm in order to avoid membrane fouling. All
flotation experiments were performed at ambient
temperature (2025C).

3. Results and discussion

Emulsion breaking is usually brought about by
changing its pH value (usually by sulfuric acid
addition) or by the addition of other chemicals,
such as ferric or aluminum salts, lime or polyelectrolytes [23]. Lime was the selected chemical some
years ago, while polyelectrolytes or inorganic coagulants are nowadays more popular, because
their use produces less sludge. Flocculants are
usually high molecular weight polymers of
cationic, anionic or nonionic character. They adsorb at solid/liquid or liquid/liquid interfaces and
promote the aggregation of colloids, by the formation of bridges between the dispersed oil
droplets, and the formation of particles of sufficient size which can be attached to the surface of
air bubbles. Coagulants are useful in overcoming
or reducing electrostatic barriers in order to allow
closer approach between individual particles and
particles and bubbles; they are usually ferric or
aluminum salts. There is an optimum chemical
additive concentration at an optimum wastewater
pH range. The concentration of the chemical additive is an important factor that significantly
affects the separation efficiency. Therefore, the
subsequent experiments were designated to find
the most efficient combination of parameters (pH
value, concentration of polyelectrolyte), which
would give a high level of oil removal.
During preliminary experiments, regarding only
the influence of pH, i.e. without any other chemical reagent, the separation of emulsified oil was
found to be very low. The influence of pH was
subsequently examined by adding simultaneously
the polyelectrolyte (anionic or cationic). The results are shown in Figs. 1 and 2 with or without
Tween 80; inorganic coagulant was not added
during these experiments.
The maximum removal of emulsified oil by
flotation was around 50% and it was achieved by

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157

efficiencies were also observed in the examined

pH range (1.512) (Fig. 2). Consequently, the
combined effect of pH and polyelectrolyte concentrations was not found to significantly alter the
separation of emulsified hydrocarbons.
Treatment performance with respect to the removal of the emulsified oil can be enhanced by
the addition to flotation cell influent of certain
coagulant chemicals, such as ferric salts [17]. Coagulation is widely used in water and wastewater
treatment [24] and seawater flocculation has also
been examined for emulsified oil treatment [25].
Coagulants can provoke a physicochemical effect, apparently serving to demulsify and increase
droplet size and to improve droplet-bubble adhesion, thereby improving overall removal. It has
been demonstrated that pH is also an important
control parameter, when coagulant chemicals are

Fig. 2. Influence of pH on flotation efficiency; (a) addition of

anionic polyacrylamide at different concentrations, (b) addition of cationic K-1384 (5 mg l 1).

Fig. 3. Influence of pH on flotation efficiency, applying different experimental conditions (shown in the legend).

the addition of 2.5 mg l 1 polyacrylamide at pH

around 4 (without Tween 80) or by the addition
of 78 mg l 1 K-1384 at pH around 10 (with
Tween 80) (Fig. 1). Small changes at the removal

Fig. 4. Influence of Fe3 + concentration on oil separation by

flotation at pH 6 for two different initial sodium oleate
concentrations (50 or 100 mg l 1); (a) without Tween 80, (b)
with Tween 80.

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A.I. Zouboulis, A. A6ranas / Colloids and Surfaces A: Physicochem. Eng. Aspects 172 (2000) 153161

Fig. 5. Influence of sodium oleate concentrations on flotation

efficiency at pH 6, after the addition of different Fe3 + concentrations; (a) without Tween 80, (b) with Tween 80.

employed [3]. In the following Figs. 3 and 4 the

influence of ferric chloride, sodium oleate and
emulsion pH value is presented, with or without
the emulsifier Tween 80.
It is thus observed that coagulation and flotation perform well within the pH range 6 9, which
is a common range for most oil-containing
wastewaters, producing oil removal efficiencies
over 90%, when [Fe3 + ] is 100 mg l 1 and [SO] is
50 mg l 1 (Fig. 3). In Fig. 4 it is shown that oil
removal increases on increasing coagulant concentration, till it reaches a maximum value (around
9095%). Lower oil removal is observed for Fe3 +
concentrations up to approximately 100 mg l 1 in
the presence of Tween 80, compared to the case
without it. For even higher Fe3 + concentrations,
oil removal is in both cases above 90%. The oil
separation is thus hindered, due to the presence of
Tween 80.

Flotation of hydrocarbons from their aqueous

emulsions considerably depends on the efficiency
of collision of air bubbles with the emulsified
droplets. The collision efficiency greatly depends
on the surface energy of airwater, hydrocarbon
water, and hydrocarbonair boundaries. Two of
these parameters, which influence the surface energy, are the type and concentration of the surface-active substance which is usually present in
the flotation system. For this reason, sodium
oleate, a common anionic surfactant, is used as
flotation collector in order to enhance the
floatability of coagulated solids. Fig. 5 presents
the results on flotation efficiency, in the presence
of sodium oleate.
The highest obtained percentage of oil removal
(over 95%) is a function of the concentration of
coagulant and collector, as well as of Tween 80.
The best results are again obtained at a coagulation dosage of 100 mg l 1 and sodium oleate
concentration between 3060 mg l 1. The aforementioned results show a synergistic enhancement, when using a combination of coagulation
and flotation to treat emulsified hydrocarbon
droplets under the applied experimental conditions. A possible explanation for this synergism is
that the floc caused by the hydrolytic reaction of
coagulant reagent can effectively capture the oil
particles and then quickly float.
Chemical coagulants can destabilize colloidal
particles or emulsions by four distinct mechanisms: double layer compression, charge neutralization, entrapment in a precipitate and
intraparticle bridging [24]. If the solution pH is
below the isoelectric point (iep) of the respecting
metal hydroxide, which in the present study is
around 6.2, then positively charged polymers will
prevail and the adsorption of these can destabilize
the negatively charged colloids or emulsion
droplets by the mechanism of charge neutralization. Above iep, anionic polymers will predominate and particle destabilization may take place
through adsorption and bridge formation. When
ferric salts are used as coagulants, monomeric and
polymeric ferric species are formed, which are
highly dependent on pH.
In Fig. 6 the influence of recycle ratio (RR%),
an important operational parameter of DAF pro-

A.I. Zouboulis, A. A6ranas / Colloids and Surfaces A: Physicochem. Eng. Aspects 172 (2000) 153161

cess, on flotation efficiency is presented, considering different experimental conditions. It can be

observed that best removal results (around 95%)
are obtained for [Fe3 + ] 100 mg l 1, [SO] 50 mg
l 1, without Tween 80, where the influence of
recycle ratio is rather negligible.
In the light of flotation theory of fine particles
it has been assumed that flotation of oils from
emulsions should proceed according to the model
of inertialess interception [12]. This is due to the
fact that the respecting Stoke values calculated for
droplets of 1 10 mm diameter and bubbles of
0.24 mm diameter, which are most often encountered in the studied flotation system, are
equal to 10 5 10 3, i.e. much smaller than the
critical Stoke value of 0.1.
The effect of hydrocarbons removal from their
emulsions by the flotation method depends on the
forces exerted between a hydrocarbon droplet and
a bubble. These forces may be divided into three
groups: (i) hydrodynamic forces, such as interception and drainage, (ii) repulsive forces, due to
electric double layer interaction, and (iii) Londonvan der Waals adhesive forces, resulting
from intermolecular attraction. Experimental results in the previous section showed that the
flotation efficiency is strongly dependent upon the
added chemical species and their concentrations.
The density and viscosity of solution, which affect
the hydrodynamic force, and the Hamaker constant, which affects the London attraction force,

Fig. 6. Influence of recycle ratio on flotation efficiency at pH

6, applying different experimental conditions, as shown in the
legend.

159

do not significantly change under these experimental conditions. Thus, the dependence of flotation efficiency upon the chemical reagents and
their concentrations is mainly ascribed to changes
of the double layer repulsion forces.
Zeta-potential is a controlling factor of double
layer repulsion for both particle and bubble. It is
known that the presence of surface-active substances, as well as of inorganic salts, may enhance
or depress flotation efficiency [25]. Zeta-potential
data, usually determined by micro-electrophoresis,
can easily be used to interpret the trend of flotation efficiency and the modification of flotation
parameters, caused by the presence of chemical
additives.
The manner in which zeta-potential affects the
flotation procedure is dictated by its influence on
magnitude and sign of charge on the emulsified
material droplets. Ideally for agglomeration, oil
droplets should have zero net surface charge;
therefore, there will be no repulsive electrostatic
forces between them. This can be achieved by the
adsorption of ions (e.g. H+ ions or surface-active
agents) on negatively charged surfaces. Strongly
adsorbing surface-active ions may increase the
negative charge of oil droplets, if they are of
anionic type, or depress it if they are cations.
Charge neutralization polymers or coagulants can
be also adsorbed at interfaces to change the respecting zeta-potential. Flotation is improved,
when the zeta-potential of droplets is reduced
towards zero values.
An oil droplet acquires a surface electric
charge, when brought into contact with aqueous
solutions. It has been stated that oil droplets in
water have a negative charge on their surface
[16,26]. This negative charge is probably due to
preferential adsorption of hydroxyl ions from the
dissociation of water molecules. Thus, in pure
water electrostatic repulsion between hydrocarbon
droplets and air bubbles occurs.
In Fig. 7(a) the zeta-potential values of n-octane emulsified droplets as a function of pH in
aqueous solutions of 0.02 M NaCl, i.e. in constant
ionic strength, are presented (without Tween 80).
In the pH region below 4, zeta-potentials have
positive values in all the cases studied. The charge
is due to the preferential adsorption of potential-

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Fig. 7. Influence of pH on zeta-potential measurements, applying different experimental conditions, as shown in the legend.

determining ions on droplet surfaces from the

bulk. High zeta-potential values are also obtained
in the presence of sodium oleate. The addition of
non-ionic surfactant Tween 80 (Fig. 7b), which
covers the oil/water interface, results to lower
positive values of zeta-potential (approximately
close to 10 mV).
The increase of pH over 4 in both cases results
to decrease of zeta-potential values. On further
increasing pH values, a charge reversal is observed, the emulsion droplets are negatively
charged and zeta-potential shifts to negative values, hence, the emulsion stability increases progressively in aqueous environment at pH close to
6. In this case, the electrostatic repulsion forces
clearly dominate the dispersion forces of attraction in the system. The more negative values of
zeta-potential are again mainly observed at the
bare octane/water interface. A maximum (negative) zeta-potential value is observed at pH close

to 6.5, while on further increasing pH values, a

decrease of the absolute value of zeta-potential
can be noticed.
Rather high zeta-potential values are also observed in the presence of anionic collector. The
driving force for the adsorption of sodium oleate
is the hydrophobic effect. There is a displacement
of ions already present in the Stern layer by the
surface-active molecules, which penetrate the
Stern layer and adsorb onto the oil/water interface, therefore causing a negative increase of zetapotential, until a maximum value is reached. The
presence of Tween 80 in all the cases studied
results in a decrease of absolute values of zetapotential.
The addition of iron chloride at pH values
above 4 results in the appearance of respecting
ferric hydroxide precipitate. In this case, the measurement of electrophoretic mobility is performed
after the removal of precipitate. Intermediate pH
values (close to 5) yield inadequately low mobilities with zeta potential values close to zero. Measurements at pH values higher than 10 are
avoided, because of pH instability problems associated with atmospheric CO2 absorption in solution and reduced affinity. The iep value is not
found to be the same for all the studied cases and
varies from 4 to approximately 6.5. The iep remains almost unchanged in the presence of Tween
80, although it is moved towards higher pH values by the addition of ferric chloride.
It should be noticed that the decrease of electrostatic potential barrier in the dispersion system,
leads to coalescence of hydrocarbon emulsion
droplets, hence to increase of droplets size. This
process proceeds very quickly at pH values close
to the iep, facilitating the separation velocity of
liquid hydrocarbon phase, towards the surface of
solution. The zeta-potential of bubble surfaces
was not measured. However, on the basis of
literature data it is expected that the sign and
values of zeta potentials of bubbles in water will
be similar to those of hydrocarbon droplets in the
studied emulsions, i.e. negative [27,28].
The results of flotation efficiency are in good
agreement with zeta-potential measurements. The
electrophoretic measurements show that zeta-potential of hydrocarbon particles is nearly zero at

A.I. Zouboulis, A. A6ranas / Colloids and Surfaces A: Physicochem. Eng. Aspects 172 (2000) 153161

pH around 5 and the electrostatic barrier is

greatly reduced, improving drop-bubble detachment.

4. Conclusions
This investigation has looked into the feasibility
of treating an emulsified system, stabilized by the
addition of a non-ionic surfactant. The destabilization of oil-in-water emulsion is successfully
performed by the application of a combination of
coagulation and dissolved-air flotation, which
shows a synergistic enhancement for the effective
separation of emulsified oil. The addition of
cationic coagulant ferric chloride is necessary to
allow effective agglomeration of individual
droplets. The increase of droplet size and the
hydrophobic nature of agglomerates, induced by
the addition of anionic collector sodium oleate, is
found to increase the effectiveness of flotation.
The application of chemical conditioning and
flotation can remove a high percentage of
emulsified oil from an oil-in-water emulsion. The
application of flotation treatment in jar-test laboratory apparatus resulted in higher than 95% reduction of oil content in the treated effluent. The
probable reasons for such behavior are discussed.
In order to reduce oil content from an influent
emulsified oil concentration of 500 mg l 1 to less
than 30 mg l 1, the following optimum parameters have been found: [Fe3 + ] 100 mg l 1, [SO] 50
mg l 1, pH around 6, recycle ratio 30%.

Acknowledgements
Thanks are due to Mr Bakalidis, chemist, for
collaboration during the experimental work.

References
[1] N.L. Nemerow, Industrial Water Pollution: Origins,
Characteristics and Treatment, Second Edition, AddisonWesley, Reading, MA, 1978.

161

[2] P. Becher (Ed.), Encyclopedia of Emulsion Technology,

Marcel Dekker, New York, 1983.
[3] P.L. Dold, Water Pollut. Res. J. Can. 24 (1989) 363.
[4] Q. Zunan, Z. Yi, F. Yuquiao, Water Qual. Res. J. Can.
30 (1) (1995) 89.
[5] M.P. Aronson, in: J. Sjoblom (Ed.), Emulsions A
Fundamental and Practical Approach, Kluwer Academic
Publishers, Netherlands, 1992, p. 75.
[6] N. Biswas, G. Lazarescu, Int. J. Environ. Stud. 38 (1991)
65.
[7] C. Angelidou, E. Keshavarg, M.J. Richardson, G.J.
Jameson, Ind. Eng. Chem. Process Des. Dev. 16 (1977)
436.
[8] N.J.M van Ham, L.A. Behie, W.Y. Svrcek, Can. J. Chem.
Eng. 61 (1983) 541.
[9] A. Mathews, P.R. Bishnoi, W.Y. Svrcek, Water Res. 13
(1979) 385.
[10] D.R. Woods, E. Diamadopoulos, in: T.D. Wasan, E.M.
Ginn, O.D. Shah (Eds.), Surfactants in Chemical Engineering, Marcel Dekker, New York, 1988, p. 369.
[11] K.E. Bremmell, G.J. Jameson, T.R. Farrugia, Chem. Eng.
Aust. 19 (1994) 23.
[12] K.B. Medrzycka, Sep. Sci. Technol. 28 (1993) 1379.
[13] K.A. Matis, A.I. Zouboulis, in: K.A. Matis (Ed.), Flotation: Science and Engineering, Marcel Dekker, New
York, 1995, p. 385.
[14] J.E. Barker, V.W. Foltz, R.J. Thompson, Chem. Eng.
Prog. Symp. Ser. 67 (1970) 423.
[15] S. Pondstabodee, J.F. Scamehorn, S. Chavedej, J.H. Harwell, Sep. Sci. Technol. 33 (1998) 591.
[16] Y. Sato, Y. Murakami, T. Hirose, H. Yamamoto, Y.
Uryo, J. Chem. Eng. Jpn. 12 (1979) 454.
[17] B. Volesky, S. Agathos, Water Pollut. Res. Can. 9 (1974)
328.
[18] J.A. Riddick, W.B. Bunger, Organic Solvents, vol. II, 3rd
Edition, Wiley-Interscience, New York, 1970.
[19] P. Becher, in: M.J. Shick (Ed.), Nonionic Surfactants,
Marcel Dekker, New York, 1967, p. 481.
[20] S. Sotiropoulos, A. Avranas, N. Papadopoulos, Langmuir
13 (1997) 7230.
[21] A. Avranas, G. Stalidis, G. Ritzoulis, Colloid Polym. Sci.
266 (1988) 937.
[22] K. Okada, Y. Akagi an, N. Yoshioka, Can. J. Chem.
Eng. 66 (1988) 276.
[23] F.N. Kemmer, Emulsion breaking, in: The NALCO Water Handbook, McGraw-Hill, New York, 1988, p. 11.
[24] C.R. OMellia, in: W.J. Weber (Ed.), Physico-chemical
Processes for Water Quality Control, Wiley Interscience,
New York, 1972, p. 61.
[25] M.H. Al-Malack, N.S. Abuzaid, A.H. El-Mubarak, Water Res. 33 (2) (1999) 521.
[26] D.E. Dunstan, Langmuir 8 (1992) 1507.
[27] S. Usui, H. Sasaki, J. Colloid Interface Sci. 65 (1978) 36.
[28] R.H. Yoon, J.L. Jordan, J. Colloid Interface Sci. 113
(1986) 430.