Journal of Membrane Science 228 (2004) 8388

A hybrid MF process based on flotation

N.K. Lazaridis a , C. Blcher b , J. Dorda b , K.A. Matis a,
a

Section of Chemical Technology & Industrial Chemistry, School of Chemistry, Aristotle University, Box 116, Thessaloniki, Hellas GR-54124, Greece
b Institute for Environmentally Compatible Process Technology (upt) Ltd., Im Stadtwald Geb. 47, D-66123 Saarbrcken, Germany
Received 13 February 2003; accepted 15 July 2003

Abstract
In the present work, a two-stage process was used for zinc ions removal from aqueous solutions. The first stage consists of the sorption of
metal ions onto zeolite and the second one the separation of the metal-loaded sorbent in a hybrid cell. The later combines dispersed-air flotation
and micro-filtration in one unit. The main parameters investigated were zeolite concentration, solution pH, collector type and concentration as
well as the submerged membranes backflush. The higher the zeolite dose the higher the transmembrane pressure and the lower the permeability
was observed. Backflush found to have a small effect on hybrid cell operation, under the studied conditions, while the collector type was
a crucial parameter. Zinc ion removal was almost complete. A 90% zeolite recovery by flotation, which was the foreseen aim, reached
successfully.
2003 Elsevier B.V. All rights reserved.
Keywords: Membranes; Dispersed air; Zeolites; Metal ions; Industrial wastewater

1. Introduction
Integrated membrane filtration processes have been recently developed, usually combined in a bioreactor with
immersed membranes [1,2]. Compared with traditional
wastewater treatment processes, this type of membrane
bioreactors offers several advantages. Fouling control in
these is usually done by air bubbling, creating an upward
air/liquid flown and thus turbulence inside the modules [3].
Air injection has been also used to improve filtration performance (flux, energy consumption) in crossflow filtration
[4,5], in which it was also applied to a ceramic flat sheet
membrane [6]. In the latter, the membrane orientation was
evaluated. For given conditions of aeration, periodic backwashing (15 s every 5 min) gave an additional efficiency
by decreasing internal fouling. Bubbles have been found to
be efficient for limiting particle deposition and polarization
phenomena.
Fouling problems, very low membrane permeability
and low water yield (up to 75%) are the main problems
encountered with conventional membrane processes (i.e.
electrodialysis, nanofiltration and reverse osmosis) applied
Corresponding author. Tel.: +30-2310-997743;
fax: +30-2310-997759.
E-mail address: kamatis@chem.auth.gr (K.A. Matis).

0376-7388/$ see front matter 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2003.07.024

for metal ions removal. High investment costs and periodical membrane cleaning are entailed, while high quantities
of wastewater are generated. On the other hand, selective
adsorbents with fast reaction kinetics for binding the toxic
metals (like zinc) have been practiced for long time [7].
Scope of this paper constitutes the introduction of flotation in the same unit of operation with MF/UF separation,
the impact of this hybrid cell being a new separation technology [8]. In this way, the air bubbles being the necessary
transport medium of particulate matter for flotation would
be also and together used to the vacuum-driven membranes
in their cleaning. Fig. 1 gives an idea of the integration of
the process investigated into the overall process for heavy
metals removal from wastewater.
For this reason, the dispersed-air flotation technique was
applied for fine pore diffusion [9]. Flotation is a well-known
separation method both in minerals processing as froth
flotation, where it was originated, and nowadays in water and wastewater treatment [10]. Further, a pilot study
suggested that dissolved-air flotation (DAF) pretreatment
helped reduce membrane fouling in hollow-fiber microfiltration [11]. Membrane fouling by the DAF-pretreated water was characterized by reduced pore blockage and lower
cake compressibility.
The use of a synthetic zeolite (of NaY type) for zinc ion
removal from dilute aqueous solution was published [12], in

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N.K. Lazaridis et al. / Journal of Membrane Science 228 (2004) 8388

bonding and recycling stage

bonding agents
higher contaminated
water with
toxic metal ions

selective
bondage
of metal ions

separation stage

vacuum-driven hybrid process:

flotation combined with
submerged membranes

membrane
filtration

purified water
for re-use or
discharge

recycled
bonding agent

regenerator/
separator

metal ions
concentrates or
solid metal for re-use

Fig. 1. The two-stage flow scheme for high concentrated (up to 500 mg l1 ) metal ion removal [8].

a combined process later termed as sorptive flotation. Certainly, what is worth noting, in this case it significant to pay
attention to chemical speciation [13]. For a number of years,
zeolite A (4A) has been used in extensive tonnages throughout the world as a builder in detergents to replace phosphates;
lately, the maximum aluminum p-type zeolite (MAP) was
introduced, which has a more flexible structure [14].

2. Experimental
Zinc, used as a mere example of pollutant to be removed,
was the metal ion under investigation. Its initial concentration in the feed solution was 50 mg l1 . The solution
was kept agitated in a feed tank, of around 20 l content,
in a continuous flow rig. Chemical analysis of the metal
in the collected effluent samples was conducted by atomic
absorption spectrometry (AAS), in the standard manner. In
the tank, with the help of mixing the zinc removal by ion
exchange and precipitation was accomplished.
The zinc-bonding agent (adsorbent) used in the present,
as a suitable model system for the separation, was a zeolite of type 4A with chemical structure Na2 O2SiO2
Al2 O3 nH2 Okindly supplied by Ineos Silicas. This zeolite (designated as CA 150), according to the company
information, has an ion exchange capacity of 6 meq. g1
and particle size (sedigraph) 3 m.
The suspension was fed by a peristaltic pump to the constructed cell, at a superficial velocity of 7.4 105 m s1
(liquid flowrate 0.58 106 m3 s1 ), as imposed by the
available membranes area. The duration of each experimental cycle was 550 min, noting that the residence time in the
cell was about 108 min; the respective flotation time was

only 1015 min [12]. The cell was a perspex column with
height 0.48 m and inside diameter 0.10 m. The feed water
was provided to the cell with or without the simultaneous
air supply from the base, through a blower at around one
atmosphere excess pressure. The air superficial velocity
was 8.5 105 m s1 (air flowrate 6.7 106 m3 s1 ).
The arrangement was similar to the type used for
dispersed-air flotation experiments, as normally [15]. The
diaphragm used for air bubbles generation, was from fritted glass (D4 type), with mean pore diameter 1016 m.
Ethanol was applied, if required (at pH 6) as frother, meanwhile reducing the bubbles size.
Hexadecyl or cetyl trimethyl-ammonium bromide (denoted as HDTMA) was the cationic collector applied in natural pH, usually at the concentration of 10 mg l1 and with
conditioning time of 10 min. At pH 6, the anionic collector sodium dodecyl-sulphate was used (60 mg l1 SDS, plus
0.15% v/v ethanol), as found appropriate. Recovery of zeolites, denoted as Rzeo (%), was calculated with turbidity
measurements often coupled by gravimetric measurements
to close the material balance.
The membranes were coming from Hermsdorfer Institut fr Technische Keramik (Thuringia, Germany) and the
module was prepared in upt Ltd., Saarbrcken. The latter,
with two vertical membranes was used here. These membranes were patented ceramic membranes with flat-sheet
multi-channel geometry and hydrophilic surface properties.
The mean pore size was 0.3 m, the pure water flux about
2 m3 m2 h1 bar1 . The membranes surface area was
0.021 m2 . The module was placed at around the one-sixth
of the column height from the bottom, over the air diffuser.
The permeate flux (provided by another peristaltic pump
at the exit) was 2.78 105 m3 m2 s1 . Pressure was

N.K. Lazaridis et al. / Journal of Membrane Science 228 (2004) 8388

It is known that zeolite 4A exchanges its sodium ions by

calcium and magnesium ions in hard waters. In order to elucidate the mechanism of zinc ions uptake by zeolite batch
wise sorption experiments were performed, for 20 min contact time. At the end of sorption the bulk, after filtration, was
analyzed for sodium and zinc content. The following results
were deduced: (i) employing 0.5 g l1 zeolite, at pH = 6,
ion exchange was responsible for 43% of zinc ions removal;
and (ii) employing 2 g l1 zeolite, at pH = 6, ion exchange
was responsible for 99% of zinc ions removal. However,
the latter became about 83% in the presence of 50 mg l1
of calcium ions; hence, a non-selective removal. Generally,
the removal of the metal(s) was a matter of the amount of
bonding agent (zeolites) added.
To shed more light on zinc ion removal mechanism blank
tests were performed versus pH. The following results were
obtained: (i) at pH = 6, zinc precipitation was almost nil;
(ii) at pH 7 it was 51.4%; (iii) at pH 8 it was 94%; and (iv) at
pH 9 it was 99.7% [13]. The natural pH of zeolite was found
around 10.5. From the pH value of about 4.5 and towards the
acidic region, it is noted that the zeolites were dissolving.
The two most common systems with dispersed air are subsurface and mechanical; in the former, air is introduced in
the form of very small bubbles by diffusers or other devices
submerged in the wastewater. Fine bubble aeration results in
more bubble surface area per unit volume, also greater number of bubbles for the same air volume, but lower rise rate
[15]. The size of bubbles that are released is a function of
the pore diameter of the opening, liquid density and surface
tension. The specific role of bubbles size in flotation has
been examined; bubble coalescence was discussed too [16].
Three methods of bubble generation in terms of average bubble diameter, bubble size distribution and power consumed,
during production, were elsewhere published [17].
Table 1 presents some selected results of batch flotation.
The necessity of applying different flotation collector (either
Table 1
Batch flotation results: [Zn] 50 mg l1
[Zeolite] (g l1 )

pH

[Collector] (mg l1 )

Rzeo (%)a

2
2
2
2

6
6
10.5
10.5

[SDS] = 20
[SDS] = 40
[HDTMA] = 10
[HDTMA] = 20

97
>99
71
>96

Batch flotation.

0
-100

Ptm (mbar)

3.1. Metal sorption and loaded zeolites flotation

-200
-300
without air
without flotation
with flotation

-400
-500
0

120

(a)

240

360

480

600

time (min)
1400

3. Results and discussion

SDS or HDTMA) depending on the solution pH was noticed.

It was also observed, from the chemical analysis of surfactants, that as flotation time was increased, the remaining in
the solution collector was decreasing, being transferred by
the air bubbles towards the liquid surface.
Another finding had to do with the influence of zeolite
aging in solution or wetting. At pH 6, a drop of flotation
recovery with time was observed. Zeolites contain large
amounts of water, at ambient conditions; upon dehydration, they undergo considerable structural changes, such as
pore shrinkage, cation migration, and even total collapse
[18]. In this pH case, as a possible counteract, the advantageous use of a polyelectrolyte (2 mg l1 Zetag 87) was
found.
In this observation, a further assistance was given by an
electrokinetic insight, in the laboratory. The measurements
showed an immediate iso-electric point (i.e.p.) of pH 8;
which, however, was moved to about 5.75 when the zeolites were well wet. At acidic pH values under the i.e.p.,
the solid had a positive surface charge, being changed to
a negative charge when overpassing that value, moving towards basicity. This study also helped in the decision of
the suitable flotation collector, according to the conditions.
The -potential was shifting towards the basic or acidic region, when respectively the cationic or anionic surfactant

permeability [L/m hbar]

measured by a transducer installed in the permeate line, for

the calculation of transmembrane pressure, Ptm . The applied backflushing was normally every 30 min for 0.5 min,
as found suitable.

85

without air
without flotation
with flotation

1200
1000
800
600
400
200
0
0

(b)

120

240

360

480

600

time (min)

Fig. 2. Influence of air and flotation on the time variation of (a)

transmembrane pressure and (b) permeability. Experimental conditions:
[Zn] = 50 mg l1 , [zeolite] = 5 g l1 , [HDTMA] = 10 mg l1 , pH = 10.5.

86

N.K. Lazaridis et al. / Journal of Membrane Science 228 (2004) 8388

was added. It is also known that flotation should be working

at optimum conditions [10,15].
So, in the continuous flow experiments (of around 9 h
operation), given in details in the next chapter, with 1 g l1
zeolites in the feed, the zinc removal was 95% at natural
pH and only 85% at pH 6. While, with 3 g l1 zeolites, zinc
removal was 97% at natural pH and 90% at pH 6.

Ptm (mbar)

-100

-200

-300

without air
without flotation
with flotation

3.2. The hybrid flotation-MF cell

-400
0

Ptm (mbar)

-100
-200
-300
without air
without flotation
with flotation

-400
-500
0

120

(a)

240

360

480

600

480

600

time (min)
1400

360

480

600

time (min)
1400

1200
1000
800
600
400
without air
without flotation
with flotation

200
0

120

240

360

480

600

time (min)

Fig. 4. Effect of air and flotation on the time variation of (a) transmembrane
pressure and (b) permeability. Experimental conditions: [Zn] = 50 mg l1 ,
[zeolite] = 1 g l1 , [HDTMA] = 10 mg l1 , pH = 10.5.

permeability [L/m hbar]

240

(b)

1200
1000
800
600
400
without air
without flotation
with flotation

200
0
0

(b)

120

(a)

permeability [L/m hbar]

It was earlier found that the more fine were the air bubbles applied, experienced by inserting in the solution a
frother (ethanol) or changing the mean pore diameter of
the air diffuser used (D2 instead of D4), the lower was the
pressure drop through the membranes. So, this led to the
use of the said sparger, and also the addition of a surfactant
that anyway is required to undergo flotation. The likely explanation to this finding is that the flow with finer bubbles
is more uniform, which means that the small bubbles are
more likely to be effective at the surface of the membrane.
With bigger bubbles, at the same flow rate, it is possible that the main bubble flow passes in a greater distance
from the membrane; thus, creating lower effective shear
rate.

120

240

360

time (min)

Fig. 3. Influence of air and flotation on the time variation of (a)

transmembrane pressure and (b) permeability. Experimental conditions:
[Zn] = 50 mg l1 , [zeolite] = 3 g l1 , [HDTMA] = 10 mg l1 , pH = 10.5.

The air presence, in other words, improved the membranes

operation. Figs. 24 present some of the obtained results
with the operation cell, giving good behavior. Lower transmembrane pressures and higher permeabilities were found
with air flow; at the greater solids concentration this effect
was more apparent and particularly, during flotation. In any
case, there were no zeolites passing through the membranes.
Similar results were found for the other solids concentration tested: for example, with 4 g l1 zeolites, the Ptm
was 120 mbar for the hybrid operation, 250 mbar for air
and 0.1% ethanol present (no flotation), 280 mbar for air
sparging alone, and 350 mbar for only microfiltration. The
respective permeability figures were 800, 400, 363.6 and
285.7 l m2 h1 bar1 .
From the figures, it can be concluded that membrane
performance is to a higher extent influenced by the concentration of zeolites in the bulk solution (related to flotation
efficiency) than by the presence of air. The relative increase
in membrane permeability by introducing air is about 20%,
whereas, if this air is used for flotation, permeability is
nearly doubled.
Then, the effect of the collector was investigated at natural pH (Fig. 5). With 10 mg l1 HDTMA, the Ptm was
140 mbar and the permeability 714.3 l m2 h1 bar1 .
The respective values at the adding of 20 mg l1 HDTMA
were 120 mbar and 800 l m2 h1 bar1 in other words,

N.K. Lazaridis et al. / Journal of Membrane Science 228 (2004) 8388

0

87

0
with
without

-100

800
-100

600
400

-150

-150
-200

-1

-200
0

120

240

(a)

360

480

100

200

300

400

500

0
600

time (min)

600

time (min)

Fig. 6. Effect of backflushing on the time variation of transmembrane

pressure and permeability. Experimental conditions: [Zn] = 50 mg l1 ,
[zeolite] = 4 g l1 , pH = 10.5, [HDTMA] = 10 mg l1 .

1400

200

with backflushing
without backflushing

-1

20 mg L HDTMA
5 mg L HDTMA

permeability [L/m hbar]

Ptm (mbar)

Ptm (mbar)

1000

-50

-50

permeability [L/m hbar]

1200

1200
1000

plain the results. For a batch experiment the zeolites that

are not floated to the surface within the 1015 min flotation
time are not recovered in the froth but remain in the bulk solution. In contrast, in membrane flotation these zeolites are
retained by the membranes and are thus likely to be trapped
by the bubbles or other particles later on and thus finally
also transferred to the froth.
The influence of backflushing was also examined. The cell
was working better than the simple system (without backflushing), as shown in Fig. 6. Again this can be explained by
the membrane operation, as with backflushing the zeolites
that form a cake layer on the membrane surface, are forced
back into the liquid and can be transferred to the froth, thus,
increasing recovery.
Nevertheless, the process at pH 6, even with varied collector, was seen quite problematic (Fig. 7), the possible reasons
were explained in the aforementioned. Table 2 presents further comparisons, being in favor at the natural pH (i.e. giving higher recoveries, greater feed solids concentration, less
of collector). The obtained recovery of 97% is noteworthy.
In wastewater treatment processes, generally, aeration introduces air into a liquid providing an aerobic medium for
microbial degradation of organic matter [9]. In the present,
it may be said that a different application of bubble aera-

800
600
400
200

-1

20 mg L HDTMA
-1

5 mg L HDTMA

0
0

120

(b)

240

360

480

600

time (min)

Fig. 5. Effect of collector concentration on the time variation of (a)

transmembrane pressure and (b) permeability. Experimental conditions:
[Zn] = 50 mg l1 , [zeolite] = 1 g l1 , pH = 10.5.

improved. However, in the latter case difficulties were experienced to control frothing; hence, the used collector concentration was excessive. With 5 mg l1 HDTMA, the Ptm
and the permeability were a little lowered in comparison to
20 mg l1 .
Table 2 shows the comparison with the batch flotation results alone, presenting may be a surprise; which is rather
usual, steady state flotation results to improvement. The
membranes forming a 100% barrier for the zeolites can exTable 2
Comparison between continuous flotation and hybrid system
[Zeolite] (g l1 )

1
2
3
4
5
1
1
1
3

pH

10.5
10.5
10.5
10.5
10.5
10.5
10.5
6
6
a

BF: backflushing.

[Collector] (mg l1 )

[HDTA] = 10
[HDTA] = 10
[HDTA] = 10
[HDTA] = 10
[HDTA] = 10
[HDTA] = 5
[HDTA] = 20
[SDS] = 40
[SDS] = 60

Rzeo (%)
Continuous flotation

Hybrid without BFa

Hybrid with BFa

85
85
78
82
80

89
93
90
93
94
82
89
66
74

97
97

77

88

N.K. Lazaridis et al. / Journal of Membrane Science 228 (2004) 8388

0

1000

-50

Ptm (mbar)

1200

permeability [L/m hbar]

with
without

800
-100

600
400

-150

200

with backflushing
without backflushing

-200
0

100

200

300

400

500

0
600

time (min)
Fig. 7. Effect of backflushing on the time variation of transmembrane
pressure and permeability. Experimental conditions: [Zn] = 50 mg l1 ,
[zeolite] = 3 g l1 , [SDS] = 40 mg l1 , pH = 6.

tion has been investigated. Certain limitations were further

imposed on the parameters examined, like the air flow,
bubbles size and apparatus design. It is necessary to use
the generated bubbles in flotation and membranes cleaning
simultaneously.

4. Conclusions
The hybrid cell is now a reality. The main conclusions of
this work are the following
(a) There was an influence of solids concentration, as expected.
(b) Frothing, with the appropriate dosage of surfactant
and/or frother, should be controlled. Backflushing (gentle) contribution had no important influence and rather
improved the operation.
(c) The results were better at natural pH, where flotation
should be operated. The cells efficiency, expressed as
flotation recovery, was found better than the respective
batch flotation results.
The hybrid cell was observed in the laboratory to work
well: the combination of flotationmembranes filtration
was proved satisfying (recovery of 90%). This means automatically that, in a hypothetical case, if has to separate
a feed with 4 g l1 solid particles (here, the metal bonding
agent), following flotation the actual system, treated by the
membranes will only have the concentration 0.4 g l1 ; with
all its fouling effects onto membranes. It is needless to add
the apparent advantage of having a compact volume of the
hybrid cell and that no energy was necessary for the fouling
control, in addition to that needed anyway for the flotation
separation.

Acknowledgements
This research comprises part from a program funded by
EU, with contract no. EVK1-CT-2000-00083. Many thanks

are due to the coordinator Dr. V. Mavrov (Saarland University) for his help; also, to Dr. M. Webb (ex-Crosfield) for
the zeolites sample and relative information, Ms. E. Peleka
(AUTh) for experimental collaboration and Prof. M. Dohnal
(TU Brno) for useful discussion.
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