Minerals Engineering 18 (2005) 701707

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The FF (occulationotation) process

Jailton J. da Rosa, Jorge Rubio *

Laboratorio de Tecnologia Mineral e Ambiental, Departamento de Engenharia de Minas,

PPGEM-Universidade Federal do Rio Grande do Sul., Av. Osvaldo Aranha 99/512, 90035-190 Porto Alegre, RS, Brazil

Received 18 September 2004; accepted 19 October 2004

Abstract

A new on-line occulation system (FF) has been developed which is coupled with a rapid otation to remove the aerated ocs
(ocs with entrained and entrapped bubbles). These aerated ocs are formed only in the presence of high molecular weight polymers
and bubbles and under high shearing (and head loss) in special occulators. The air excess air abandons the otation tank (a
centrifuge or a column) by the top and the ocs oat after very short residence times (within seconds). The aerated ocs are large
units (some millimetres in diameter) having an extremely low-density. Process eciency was found, in all cases, to be a function of
the trilogy, head loss, type (and concentration) of occulants and air ow rate. Mechanisms involved appear to include small bubble
formation and their rapid occlusion (entrapment) within ocs, nucleation of bubbles at oc/water interfaces, polymer coiling as a
result of salting out eects at the aqueous/air interface and plug ow type of mixing (occulation) instead of perfect. Successful
examples of emulsied oil and solids removal from water are shown and because in all cases were obtained high eciencies (>90%
removal), at high hydraulic loadings (>130 m h 1) it is believed that this kind of occulationotation appears to have a great poten-
tial in solid/liquid or liquid/liquid separation.

2004 Elsevier Ltd. All rights reserved.

Keywords: Flocculation; Flotation; Wastewater treatment; Environmental

1. Introduction Industrial euents and even otation tailings com-

Flocculation and otation processes in the mineral
industry are primarily designed to separate one particle
type from another. In contrast, for wastewater treat-
ment, the otation is designed to remove all parti-
clesgenerally encountered as very ne emulsions,
suspended solids, microorganisms and colloidal disper-
sions. Thus, processes are optimized by the maximum
recovery of cleaned water with the lowest concentration
of pollutants and sludge containing low percentage of
solids (or oils) (Rubio, 2003).
*
Corresponding author. Tel.: +55 51 3316 3540; fax: +55 51 3316
3530.
E-mail address: jrubio@ufrgs.br (J. Rubio).
URL: http://www.lapes.ufrgs.br/ltm
monly bear wastewater that contains a mixture of sus-
pended particles and stable oil emulsions. It is well
known that it is dicult to remove ne colloidal parti-
cles and highly emulsied oil from process wastewater.
Oil can be present as a free, non-dispersed surface
layer, usually oating at the air/water interface. The oily
layers can be readily separated o by gravity but the sep-
aration, as in the case of ne particle dispersions, is al-
ways very poor in the case of oil-in-water emulsions,
especially if oil is present as a physically dispersed phase
in the form of ne droplets, say <10 lm. The separation
is even more dicult when emulsions are stabilized with
surfactants or other emulsifying agents (Toyoda et al.,
1999).
Flotation of organic uids such as oil spills, oily sew-
ages or oil-in-water emulsions has been known for dec-
ades in various elds but is not commonly used in the

0892-6875/$ - see front matter
2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2004.10.010
702 J.J. da Rosa, J. Rubio / Minerals Engineering 18 (2005) 701707
mining and/or metallurgy industries. Oil in water may be
dispersed, emulsied or soluble in concentrations usu-
ally up to 1000 mg L 1. Here, residual oily waste-waters
are common in the form of otation and solvent extrac-
tion reagents losses, free wasted oil and oil spills in pro-
cess waters (Gu and Chiang, 1999; Capps et al., 1993;
De Oliveira, 1995).
The otation separation of very ne oil droplets
(<10 lm) or dispersed ne solids is even more compli-
cated and usually requires ne bubbles, ecient occu-
lants, and quiescent hydrodynamic conditions in the cell
separation zone (Gopalratnam et al., 1988). This is due
to collection and adhesion factors, which makes the pro-
cess very slow, especially when treating high ow-rates.
Induced air otation, IAF and dissolved air otation,
DAF, have been used extensively in the removal of sta-
ble oily emulsions or ne particles suspensions (Strick-
land, 1980; Bennett, 1988; Van Ham et al., 1983). IAF
utilizes bubbles sizing between (6002000 lm), turbulent
hydrodynamic conditions and has low retention times,
normally <5 min. Conversely, DAF employs micro-bub-
bles (30100 lm), and quiescent regimes. However,
when retention times are higher (2060 min) this process
is inecient when treating euents having high volumes
and high ow-rate. A new basis for the separation of oil-
in-water emulsions, based on the concept of carrier o-
tation, has been reported (Rubio and Santander, 1997).
Here, the carrier solids (coal or coal beneciation resi-
dues) adsorbs or absorbs the oil extensively and ota-
tion is used to separate o the loaded oily adsorbent.
The addition of polymeric occulants may, some-
times, assist the particles settling but the eciency highly
decreases when dispersions are diluted or when particles
are in the range of ultranes or colloidal range (Rubio,
2003). The recovered water in most cases carries sus-
pended particles aecting the clarity and quality. On
the other hand, otation, in those cases, is a more reli-
able technique for the removal of diluted (<4% solids
content) suspensions and oily emulsions from waste-
water (Da Rosa et al., 2002).
Yet, the classical dissolved air otation (DAF) is still
the most common process removing ne colloidal dis-
persions and oily emulsions, mainly in renery waste-
waters (Kiuru, 2001; Rubio et al., 2002b). In DAF, a
stream of treated wastewater (recycle) is saturated with
air at elevated pressures up to 5 atm (4070 psig). Bub-
bles are formed by a reduction in pressure of the water
pre-saturated forced to ow trough needle valves or spe-
cial orices, and clouds of bubbles, 3070 lm in diame-
ter, are produced just down-stream of the constriction
(Rodrigues and Rubio, 2003). More, recently, DAF
has been employed to remove suspended solids from
neutralized AMD waters (acid mining drainage water)
(Menezes et al., 2004) and to remove ions from copper
concentrates ltered water (Rubio, 2003; Rubio et al.,
2002a).
However, future technologies will have to deal with
highly loaded (high solids by weight) process wastewa-
ters, exiting mining and metallurgical industries, and
DAF might not meet legislation standards and reuse
eciently the water, due to the low carrying power of
the tiny bubbles and the low hold-up. For this reason,
DAF may be considered a slow process with high resi-
dence time (minutes) and requiring high foot print
space.
Various publications (Rubio et al., 2002a; Voronin
and Dibrov, 1999; Matis, 1995; Mavros and Matis,
1992; Parekh and Miller, 1999), reviewed fundamentals
and general features of otation (usually accompanied
by occulation) for environmental applications. All
publications show the great potential of conventional
and upcoming novel separation concepts and devices.
This article constitutes an advance within this line of
research and development.
2. The FF (occulationotation) process: development
and main features
The occulationotation system (FF, Rubio et al.,
2003) is composed of a turbulent occulator to gener-
ate aerated polymeric ocs coupled with solid/liquid, so-
lid/liquid/liquid2 or liquid/liquid2 separation devices
(columns, tanks, centrifuges). Here, the basic concept
is that of a reactor (zigzag or static mixer types)
(Fig. 1) of occulator (Fig. 2) and a oc otation sepa-
rator (Fig. 3). The resulting ocs are rapidly formed in-
side the occulator, are very light because of the trapped
air (see below). Yet, these special ocs are generated
only in the presence of high molecular weight polymers,
bubbles (from the injected air), high shearing forces
(caused by the zigzag kind of ow) and a high head loss.
Process eciency was found, in all cases, to be a func-
tion of the trilogy, head loss, type (and concentration)
of occulants and air ow rate (Da Rosa et al., 2002;
Rubio, 2003; Rubio et al., 2003).
In the otation tank separator the oc oat, within
seconds, as large units (some millimeters in diameter)
having very low densities. The exceeding air abandons
the otation device by the top through a special water
seal (avoiding ow turbulence).
Conversely, in conventional occulation, the poly-
meric oc (non-aerated) are commonly formed after
polymer diusion and adsorption at the solid particle/
water interface under high stirring (agitation) stage, fol-
lowed by ocs build-up and growth at slow mixing stage.
An advanced ASH (air sparger hydrocyclone) type of
otation, which appears to work similarly to FF has
been reported in applications to remove oil, grease,
BOD, etc. BAF, or bubble accelerated otation system,
uses the contactor-separation concept with very low
detention times in the contactor (Owen et al., 1999).
 J.J. da Rosa, J. Rubio / Minerals Engineering 18 (2005) 701707 703

Flowmeter

Pressure gauge In

Out

Sampling Flocculant

Flocculator Pressure
MS-10 gauge
Compressed
Air

Fig. 1. The FF-occulationotation system. Lay out of the aerated oc generation system. MS10 is for the occulator with 10 zigzags units. The
outlet connects with the oc otation separation unit (cylinder type, see below).

Fig. 2. FF system: dierent occulators employed.

Overflow 3. Applications

Feed 3.1. Oil separation from oil-in-water emulsions

(synthetic euent)
Coaxial
Cylinder FF results for the separation of dicult-to-separate
oil from emulsied oil dispersions (Table 1), using the
Centrifuge cell
Table 1
Oil separation from oil-in-water emulsions by FF (2 m3 h 1). Exper-
imental conditions
Pedestal Parameters Values
1
Oil concentration, Co 695 mg L
Oil mean droplet diameter (volumetric), d(4, 3) 10 lm
Underflow Temperature, T 20 C
NaCl, concentration 60 g L 1
Nalco, Cationic polymer 2 mg L 1
Fig. 3. The aerated oc otation separator.
704 J.J. da Rosa, J. Rubio / Minerals Engineering 18 (2005) 701707

Fig. 4. The FF pilot system used in the removal of oils from oil-in-water emulsions (2 m3 h 1).

100 Results in Figs. 6 and 7 show that, despite the high

90 degree of emulsication, the oil separation of the aerated
Final oil concentration. mg/L

CONDITION FLOCCULATOR
80 oc (Fig. 7) was very rapid and almost complete. The
Qefluent : 50.0 L/min ME-1"
70 [Flocculant]: 2 mg/L ME-3/4"
kinetics was very rapid, within seconds, yielding hydrau-
60 MS-10 lic loadings of more than 130 m h 1 (m3/m2/h).
MS-20
50

40
ME-1/2"
3.3. Flocculationotation of suspended (dispersed) solids
30
All aqueous suspensions (2% by weight) were pre-
20
pared by dispersing the solids in water using a high
10
speed stirring. After occulationotation, FF% values
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5
were calculated from the dry weights of dispersions,
Head loss in the flocculator. kgf/cm 2
before and after the separation:
% FF = (1 0 0)(Do-Df/Do) where Do is the degree of
Fig. 5. Oil in water emulsion (synthetic) separation by the FF process: dispersion (dispersibility) calculated from the feed dis-
eect of head loss and type of occulator.
persed solids content (by weight) before FF (Do = initial
dispersion degree) and Df is the dispersion degree after
FF, using the same cationic polymer (Nalco) as in the
equipment described in Fig. 4 showed excellent results
oils.
only after reaching a minimum head loss in the satura-
Particles were ground to 100% less than 37 lm and
tor, i.e. independently on the occulator design (Fig. 5).
the solids studied were:
3.2. Oil separation from oil-in-water emulsions
(renery euent)

Studies were conducted with a typical petroleum

renery euent using the same FF equipment used
before (Table 2).

Table 2
Main parameters used in the euent separation by FF
Parameters Values
Oil 77115 mg/L
Turbidity 5567 NTU
TSS-total suspended solids 4351 mg/L
Fig. 6. Oil in water emulsion (petroleum renery euent) separation
OM-organic matter 480515 mg O2/L
by the FF process, using two dierent polymer concentrations (Nalco,
Oil mean droplet diameter (volumetric), d(4,3) 12 lm
Cationic polymer).
 J.J. da Rosa, J. Rubio / Minerals Engineering 18 (2005) 701707
Fig. 7. The aerated oil oc formed with a cationic polyacrylamide in
the FF process.
Bentonite (smectite) from Brasgel-Brazil;
Quartz, pure sample from South Brazil;
Coal beneciation tailings, corresponds to a ground
jigging tailings sample (South Brazil);
Hematite, pure sample from North Brazil (Minas
Gerais).
Fig. 8 shows comparative results obtained in each
case. With the exception of bentonite, a dicult to oc-
culate solids suspensions, the FF separations of all other
solid models was ecient, almost complete and pro-
ceeded at a very rapid rate.
3.4. Flocculationotation of colloidal dispersions
Fig. 9 shows FF results obtained with ferric hydroxide
[Fe (OH)3], containing 50 mg L 1 Fe hydrolyzed at pH 6.
The ferric colloidal suspensions were occulated with the
same cationic polyacrylamide studied with the solids sus-
100
80
60
FF %
40
20
0 rate.
0 2 4 6 8 10
-1
[Nalco 8589], mgL
Fig. 8. Flocculationotation values for various solids suspensions.
s = Hematite; d = Quartz; m = Bentonite; h = Coal beneciation
tailing.
705
100
90
Removal, %
80
70
60
50
0 20 40
-1
Surfactant, mgL
Fig. 9. Flocculationotation of colloidal Fe(OH)3 oc (using a
cationic polyacrylamide) as a function of lauryl sulphate concentra-
tion. Removal of the ferric ion content, before and after FF separation.
pensions but ocs were readily broken apart (not stable
at all!). However, in the presence of sodium lauryl sul-
phate, these ocs were resistant to shearing in the FF
equipment and they were able to separate o. It is be-
lieved that the role of the surfactant was to avoid the oc
rupture by reducing the air/liquid surface tension.
4. Mechanisms involved
It is believed that in the FF process occurs a pneu-
matic, on line occulation whereby the polymer diu-
sion and adsorption are rapidly ensured by the
shearing forces given by the bubbles (minutes ones)
and by the head loss in the occulator, minimum 0.5
to1.0 kgf/cm2 (Fig. 2). More, the turbulent mixing of
the ow is characterized as a plug ow regime where
all particles have the same residence time (slow disper-
sion), ideal for occulation, (Bratby and Marais, 1977).
Mechanisms involved are not well elucidated but at
least one of the following phenomena may be operating:
1. Small bubble formation and their rapid occlusion
(entrapment) within ocs; Nucleation of bubbles at
oc/water interfaces and bubbles entrainment.
Qualitative measurements of the bubble size gener-
ated in the FF system, using the technique developed
by Rodrigues and Rubio (2003), yielded values of the
order of 100 lm bubbles diameter (Sauter). These values
considered very nes (microbubbles) and of the order of
those generated in DAF units, are formed at head losses
(measured by the pressure dierences before and after
the occulator) of the order of 3 atmospheres and at
4 Lmin 1 for the feed rate and 7 Lmin 1 for the air ow
Because the uprising rates of the aerated ocs (more
than 130 m h 1) are faster than the rising bubbles sizes
alone (3040 m h 1), it is believed that air is entrapped
(occluded) inside the ocs, highly decreasing the aggre-
gate density as a function of the incorporated air volume.
706 J.J. da Rosa, J. Rubio / Minerals Engineering 18 (2005) 701707
More, because some air must be dissolved in water
following the ow pressure inside the occulator, these
microbubbles behave as in DAF. Thus, a very important
feature concerns with the mechanisms of bubble/particle
(aggregates) interactions other than the common adhe-
sion through hydrophobic forces (Rubio et al., 2002a).
Apart from particles-bubbles collisions and adhesion,
part of the dissolved air in water, which does not convert
into bubbles, remains in solution and nucleate at the
particle surface (Solari and Gochin, 1993).This mecha-
nism is independent on surface hydrophobicity and al-
lows otation of hydrophilic particles. In addition,
entrainment by the rising bubbles may be also operating.
2. Polymer uncoiling or salting out at the aqueous/
air interface.
The aerated ocs looked like lamentous, elongated
and sticky (plastic like) units. This characteristic
may be the result of an uncoiling phenomenon of the
polymer chains at the solid (liquid1)/liquid2 (water)/air
interface (high, because of the small bubbles). Thus, at
the ocs/water/air interface, a fraction of the adsorbed
polymer may become ordered (small entropy) with a
high local activity. As a result, the polymer appears
to suer a sort of salting out or insolubility. This pre-
cipitation may explain the shape (form) of the ocs and
their high resistance to turbulence and high shearing
forces in the occulation contactor.
5. Conclusions
A new in-line occulationotation unit, named
FF-FlocculationFlotation, was developed for the gen-
eration and separation of aerated polymeric ocs. The
studies showed a high process eciency for the separa-
tion of oil from oil emulsions, suspended solids and col-
loidal suspensions [Fe(OH)3] with the employment of a
cationic, high molecular weight, polymer. The polymer
ocs obtained were well structured, big and with elon-
gated (string like) format. The FF appears to have some
advantages, namely an adequate turbulence, low area
required, absence of mobile parts, simple design, and
low mechanical and electrical energy required. Process
eciency depended on a minimum head loss (0.5 e
1.0 kgf/cm2) and not on occulator design, on polymer
concentration and on the air feed ow rate. Finally,
the uprising rates of the aerated ocs reached to more
than 130 m h 1, values higher than those found in con-
ventional sedimentation tanks or DAF-dissolved air
otation units.
Acknowledgments
Jorge Rubio thanks to the students and colleagues
from LTMUniversidade Federal do Rio Grande do
Sul, for the friendship, and to all Institutions supporting
research in Brazil (FAPERGS, CAPES, CNPq,
UFRGS). Authors thank also to the graduate and
undergraduate students for their assistance in the hard
experimental work.
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